Annual Report

2012

Annual Report
20122102 tropeR launnA

年
報
年 報

2010
2012

京都大学
福井謙一記念研究センター

fukui2012_01.indb 1

14.1.9 1:23:02 PM

fukui2012_01.indb 2

14.1.9 1:23:02 PM

はじめに2012 年度(平成 24 年度)の京都大学福井謙一記念研究センターの活動をまとめた年報をお届けします。本センターは、京都大学本部構内の北、約１キロの高野川沿いの静かな住宅街に独立して位置しております。専任教員は理論研究部門と総合研究部門に准教授各 1
名を持っているに過ぎませんが、センター長のほか副センター長とスーパーバイザーとして工学研究科、理学研究科、化学研究所所属の 11 名の教員にご協力頂いており、このメンバーが運営委員会を構成しています。そして優れた博士研究員に研究活動の機会を与える制度を持っており、若手研究者が国際的な雰囲気の中で日夜研究にいそしんでいます。
福井センターフェローと呼ばれる博士研究員はセンターの雇用で、自分自身のアイデアで一定期間、自由闊達に研究できる身分を保証しています。
2006 年(平成 18 年)9 月に福井謙一記念研究部第一のリサーチリーダーとして世界的な理論化学者の諸熊奎治先生(分子科学研究所名誉教授)を米国エモリー大学から招聘し、研究面でのリーダーシップを発揮して頂いております。諸熊先生は，科学技術振興機構の戦略的創造研究推進事業の予算で博士研究員を採用され、全員がセンターで研究に励んでおられます。さらに 2009 年度(平成 21 年度)には福井謙一記念研究部第二も設置し、名古屋大学名誉教授（前副学長）の大峯巖先生をリサーチリーダーとして招聘し、研究体制を拡大しました。なお、大峯先生は 2010 年(平成 22 年)4 月に分子科学研究所長に転出されました。その後任として、2011 年(平成 23 年)4 月に京都大学物質―細胞統合システム拠点(iCeMS)特任教授の榊茂好先生を研究部第二のリサーチリーダーとして招聘しました。
榊先生は、遷移金属化合物や類縁化合物に関する研究で顕著な業績を挙げておられ、現在は科学研究費補助金「d－電子複合系の理論化学：新しい高精度大規模計算法による微視的理解と予測」を推進しておられます。榊先生は、この予算で博士研究員を採用され、そのメンバーはセンターで研究に励んでいます。私達は、センターが若手研究者の登竜門となることを期待しています。実際に、センターの博士研究員であった多くの方々が、現在、国内外の大学、研究機関で活躍しておられます。
当センターの歴史を簡単にご紹介します。ご承知のように故福井謙一京都大学名誉教授
はフロンティア軌道理論を提案したご功績により、1981 年(昭和 56 年)にわが国で最初のノーベル化学賞を受賞されました。福井先生が京都大学ご退官後に研究を続けられるため、京都市と産業界などのご支援で 1985 年(昭和 60 年)に財団法人「基礎化学研究所」が設立されました。専任研究員数名の規模でしたが、研究のレベルは高く、当時の研究員は現在、東京大学、名古屋大学、分子科学研究所の教授になり、理論化学分野でトップクラスの研究者として活躍しています。この基礎化学研究所は 1998 年（平成 10 年）の福井先生のご逝去の後、2002 年(平成 14 年)に本学に寄贈され、福井謙一記念研究センターとなり、現在にいたっています。
本センターは、国際活動も活発で、2005 年(平成 17 年)よりチェコおよびスロバキアと－i－

fukui2012_01.indb 3

14.1.9 1:23:02 PM

理論化学・計算化学シンポジウムを定期的に開催しております。2011 年(平成 23 年)には国内外(主にドイツ、東欧、中国、韓国)から第一線の研究者を招き、第 1 回福井センター
理論化学・計算化学国際シンポジウムを開催しました。こうした国際連携活動をさらに活性化するという観点から、2011 年(平成 23 年)10 月に国際連携研究室を設置し、その運営上必要となるコーディネーター役として、特定准教授及び特定助教各 1 名を配置しました。
2012 年度(平成 24 年度)には国際連携強化プロジェクトの一環として、センター教員が海外の研究機関を訪問し、研究所の運営に関して意見交換を行いました。本センターは、今後も、理論化学・計算化学分野におけるわが国の窓口の役割を果たし、国際連携活動を展開して行きたいと考えております。
例年晩秋に福井センターシンポジウムを開催しており、学外のトップクラスの研究者による特別講演、運営委員の講演、並びに京都大学内外からのポスター発表を行っております。研究発表のレベルは高く、特別講演に来られた講師からも毎年高い評価を得ております。
さらに社会貢献活動の一環として、2011 年(平成 23 年)が福井先生のノーベル化学賞受賞 30 周年にあたるため、これを節目として本センター玄関ロビーに先生ゆかりの文物の展示コーナーを設置しました。コーナーでは先生が使用された机、椅子、ノーベル賞メダ
ル・賞状(複製)、研究ノート・メモ、写真などを展示し、常設展示として一般に公開しています。
また、本センターの諸熊奎治先生は、複雑分子系の理論研究の発展に多大な貢献をしたとして、2012 年(平成 24 年)11 月に文化功労者の顕彰を受けられました。これは、先生ご自身の栄誉はもとより、本センターの名を大いに高めて頂いたことでもあり、大変喜ばしいことでした。
本センターは、上述のように規模は大きくありませんが、研究活動は活発です。今後も、京都大学あるいは国内外との共同研究を積極的に進めて行きたいと考えております。とくに実験科学者との共同研究は重要であり、そのような連携研究をさらに活発化したいと考
えております。
この年報により、本センターの活動に興味をお持ち頂ければ幸甚です。そして、それが共同研究の契機となり、時間をかけて大きな成果に結実していくことを念願しています。
最後になりましたが、本センターの順調な活動はひとえに工学研究科、理学研究科、化学研究所のご協力、ご援助の賜物であり、ここに心から御礼申し上げる次第です。

平成 25 年 12 月
京都大学福井謙一記念研究センター長

田中一義－ ii －

fukui2012_01.indb 4

14.1.9 1:23:02 PM

目
はじめに

Ⅰ

Ⅱ

Ⅲ

次

京都大学福井謙一記念研究センター長

田中一義�������

i

１．教員組織 ����������������������������

1

２．教員プロフィール ������������������������

2(1) センター長 �������������������������

2(2) 副センター長 ������������������������

3(3) スーパーバイザー ����������������������

5(4) 専任教員 ��������������������������

16(5) シニアリサーチフェロー �������������������

19(6) リサーチリーダー ����������������������

21

専任教員・スーパーバイザー

博士研究員
１．博士研究員組織 �������������������������

22

２．博士研究員プロフィール ���������������������

23

研究広報活動１．福井謙一記念研究センターシンポジウム ��������������

56

２．福井謙一記念研究センターセミナー ����������������

57

３．国際交流 ����������������������������

57

４．社会へのアウトリーチ活動 ��������������������

57

５．栄誉
― 諸熊奎治シニアリサーチフェローに文化功労者の顕彰 ― �����

Ⅳ

58

研究業績
１．専任教員 ����������������������������

59

２．シニアリサーチフェロー ���������������������

78

３．リサーチリーダー ������������������������

89

４．博士研究員 ���������������������������

94－ iii －

fukui2012_01.indb 5

14.1.9 1:23:02 PM

Ⅴ資料
１．外国人共同研究者受入れ状況 ………………………………………………… 233
２．海外渡航一覧 …………………………………………………………………… 234
３．研究業績一覧 …………………………………………………………………… 235
４．福井謙一記念研究センター シンポジウム ポスター・プログラム ……… 247
５．福井謙一記念研究センター セミナー ポスター・プログラム …………… 256
６．国際交流― 海外の研究機関との研究所運営に関する意見交換のための出張報告書 ―……… 257
７．社会へのアウトリーチ活動紹介記事…………………………………………… 276
８．諸熊奎治シニアリサーチフェローに文化功労者の顕彰に関する記事 …… 278（本冊子は下記アドレス(URL)にて、ウェブ上でも閲覧いただけます。
http://www.fukui.kyoto-u.ac.jp/publication/AnnualReport2012.pdf）－ iv －

fukui2012_01.indb 6

14.1.9 1:23:02 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)Ⅰ

専任教員・スーパーバイザー

１．教員組織平成２４年度
職

名

氏

センター長

田 中

名

備

一 義

考

工学研究科分子工学専攻

総合研究部門副センター長長谷川 淳 也

専任（平成 24 年 9 月 30 日まで）

理論研究部門副センター長赤 木

和 夫

工学研究科高分子化学専攻

工学研究科長北 野

正 雄

工学研究科電子工学専攻

理学研究科長山 極

壽 一

理学研究科生物科学専攻

化学研究所長佐 藤

直 樹

化学研究所複合基盤化学研究系

協

議

員

物質－細胞統合システム拠点

教

授

北 川

進

教

授

田 中

勝 久

教

授

田 中 耕一郎

教

授

時 任

宣 博

教

授

八 尾

誠

理学研究科物理学・宇宙物理学専攻

教

授

田 中

功

工学研究科材料工学専攻

教

授

田 中

庸 裕

工学研究科分子工学専攻

教

授

谷 村

吉 隆

理学研究科化学専攻

教

授

山 本

量 一

工学研究科化学工学専攻

教

授

高 田

彰 二

理学研究科生物科学専攻

准 教 授

林

重 彦

理学研究科化学専攻

総合研究部門准 教 授

長谷川 淳 也

理論研究部門

准 教 授

中 尾

嘉 秀

国際連携研究室

特定准教授

石 田

俊 正

専任

国際連携研究室

特定助教

池 野

豪 一

専任

永瀬グループ

シニアリサーチ
フェロー

永 瀬

茂

研究員（学術研究奨励）諸熊グループ

シニアリサーチ
フェロー

諸 熊

奎 治

研究員（学術研究奨励）

榊グループ

リサーチ
リーダー

榊

茂 好

研究員（学術研究奨励）

総合研究部門スーパーバイザー

理論研究部門スーパーバイザー（工学研究科合成・生物化学専攻）

工学研究科材料化学専攻
物質－細胞統合システム拠点（理学研究科物理学・宇宙物理学専攻）

化学研究所物質創製化学研究系

専任（平成 24 年 9 月 30 日まで）
（工学研究科合成・生物化学専攻協力講座）

専任(工学研究科分子工学専攻協力講座)－1－

fukui2012_01.indb 1

14.1.9 1:23:03 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)

２. 教員プロフィール
⑴

センター長

【氏名（ふりがな）】 田中

一義 （たなかかずよし）【職名】 教授【所属】 工学研究科分子工学専攻【研究室】 桂 A4 棟 205【直通電話】 075-383-2549【FAX】 075-383-2555【電子メールアドレス】 ktanaka@moleng.kyoto-u.ac.jp【ホームページ】 http://www.moleng.kyoto-u.ac.jp/~moleng_03/index_J.html【研究分野】 物理化学・量子化学【現在の研究課題】 量子機能化学、物理化学【研究内容キーワード】 単一分子スピン、単一分子発光、元素化学の量子論【学歴】 1978 年 3 月【学位】 1978 年 3 月

京都大学工学研究科石油化学専攻博士課程修了
工学博士（京都大学）【略歴】 1979 年 6 月米国エナージー・コンバージョン・デバイシズ社リサーチケミスト、
1981 年 12 月京都大学工学部助手、1988 年 12 月 同 助教授、1996 年 11 月
京都大学大学院工学研究科教授【所属学会】 日本化学会・日本物理学会・高分子学会【学会活動】 フラーレン・ナノチューブ・グラフェン学会幹事【主な著書、学術論文】 1. 物理化学（化学マスター講座）（共著 , 丸善 , 2010）（過去 5 年以内） 2. 炭素学（共編著 , 化学同人 , 2011）（以上著書）
1. A Stable Germanone as the First Isolated Heavy Ketone with a Terminal Oxygen
Atom (L. Li, T. Fukawa, T. Matsuo, D. Hashizume, H. Fueno, K. Tanaka, and K.
Tamao) Nature Chem., 4, 361-365 (2012).
2. 1,3,5-Benzenetriamine Double- and Triple-Decker Molecules (D. Sakamaki, A. Ito,
K. Tanaka, K. Furukawa, T. Kato, and M. Shiro) Angew. Chem. Int. Ed., 51, 82818285 (2012).
3. Electronic Spectra of Cycl[3.3.2]azine and Related Compounds: Solvent Effecton Vibronic Couplings (Y. Shigemitsu, M. Uejima, T. Sato, K. Tanaka, and Y.
Tominaga) J. Phys. Chem. A, 116, 9100-9109 (2012).
4. A Triphenylamine Double-Decker: From a Delocalized Radical Cation to a
Diradical Dication with an Excited Triplet State (Y. Yokoyama, D. Sakamaki, A.
Ito, K. Tanaka, and M. Shiro) Angew. Chem. Int. Ed., 51, 9403-9406 (2012).
5. Mechanisms of Localization in Isotope-Substitutes Dynamical Jahn-Teller Systems(N. Iwahara, T. Sato, K. Tanaka, and L. F. Chibotaru) Eur. Phys. Lett., 100, 43001
1-6 (2012).
6. Chemical Reactivity in Nucleophilic Cycloaddition to C70: Vibronic Coupling
Density and Vibronic Coupling Constants as Reactivity Indices (N. Haruta, T. Sato,and K. Tanaka) J. Org. Chem., 77, 9702-9706 (2012).
7. A Polymacrocyclic Oligoarylamine with a Pseudobeltane Motif: Towards a
Cylindrical Multispin System (D. Sakamaki, A. Ito, K. Furukawa, T. Kato, M.
Shiro, and K. Tanaka) Angew. Chem. Int. Ed., 51, 12776-12781 (2012).
8. Meta-Para-Linked Octaaza[18]cyclophanes and Their Polycationic States (D.
Sakamaki, A. Ito, K. Furukawa, T. Kato, and K. Tanaka) J. Org. Chem., 78, 29472956 (2013).
9. Vibronic Couplings in Cycloadditions to Fullerenes (N. Haruta, T. Sato, N. Iwahara,
and K. Tanaka) J. Phys. C: Conf. Ser., 428, 012003 1-7 (2013).
10.Vibronic Coupling Density and Related Concepts (T. Sato, M. Uejima, N. Iwahara,
N. Haruta, K. Shizu, and K. Tanaka) J. Phys. C: Conf. Ser., 428, 012010 1-19 (2013).
（以上学術論文）－2－

fukui2012_01.indb 2

14.1.9 1:23:03 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)⑵

副センター長【氏名（ふりがな）】 長谷川

淳也 （はせがわ

じゅんや）【職名】 教授【所属】 北海道大学

触媒化学研究センター【研究室】 北海道大学

創成科学研究棟 05-217-C【直通電話】 011-706-9145【FAX】 011-706-9145【電子メールアドレス】 hasegawa@cat.hokudai.ac.jp【ホームページ】 http://www.cat.hokudai.ac.jp/hasegawa/【研究分野】 計算化学・理論化学・触媒化学【現在の研究課題】 光機能性分子の励起状態と分子間相互作用、触媒反応機構【研究内容キーワード】 励起状態理論、光機能性蛋白質、触媒反応機構【最終学歴】 1998 年 3 月【学位】 1998 年 3 月

京都大学工学研究科合成・生物化学専攻博士後期課程修了
工学博士（京都大学）【略歴】 1999 年 11 月京都大学工学研究科合成・生物化学専攻助手、2007 年 4 月京都
大学工学研究科合成・生物化学専攻助教、2008 年 12 月京都大学工学研究科
合成・生物化学専攻講師、2011 年 10 月京都大学福井謙一記念研究センター准教授、2012 年 10 月北海道大学触媒化学研究センター教授【在外研究歴】 1998 年 4 月 -1999 年 10 月 Lund 大学理論化学科（B. O. Roos 教授、スウェーデン）【所属学会】 日本化学会、米国化学会、分子科学会、理論化学研究会、日本生物物理学会【学会活動】 Chem. Lettters 編集委員、量子化学研究協会理事【主な著書、学術論文】 1. J. Hasegawa, K. J. Fujimoto, and T. Kawatsu, “A Configuration Interaction Picture
for a Molecular Environment Using Localized Molecular Orbitals: The Excited（過去 5 年以内）
States of Retinal Proteins”, J. Chem. Theo. Comp. 8(11), 4452-4461(2012).
2. T. Kawatsu and J. Hasegawa, “Sequentially Coupled Hole-Electron Transfer
Pathways for Bridge-Mediated Triplet Excitation Energy Transfer”, J. Phys. Chem.
C 116(44), 23252-23256 (2012).
3. J. Hasegawa, T. Kawatsu, K. Toyoya, and K. Matsuda, “Chemical-intuition based
LMO transformation simplifies excited-state wave functions of peptides”, Chem.
Phys. Letters, 508(1-3), 171-176 (2011).
4. J. Hasegawa, T. Ise, K. Fujimoto, A. Kikuchi, E. Fukumura, A. Miyawaki, and Y.
Shiro, “Excited States of Fluorescent Proteins, mKO and DsRed: Chromophoreprotein Electrostatic Interaction Behind the Color Variations”, J. Phys. Chem. B,
114(8), 2971-2979 (2010).
5. K. Fujimoto, J. Hasegawa, and H. Nakatsuji, “Color tuning mechanism in humanred, green, and blue cone visual pigments: SAC-CI theoretical study”, Bull. Chem.
Soc. Jpn. 82(9), 1140-1148 (2009).
【学術関係の受賞】 平成 9-11 年 日本学術振興会特別研究員、平成 21 年 9 月 分子科学会奨励賞、
平成 23 年 9 月 QSCP Promising Scientist Prize of CMOA
－3－

fukui2012_01.indb 3

14.1.9 1:23:03 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)【氏名（ふりがな）】 赤木

和夫 （あかぎかずお）【職名】 教授【所属】 工学研究科高分子化学専攻【研究室】 赤木研究室【直通電話】 075-383-2595【FAX】 075-383-2760【電子メールアドレス】 akagi@fps.polym.kyoto-u.ac.jp【ホームページ】 http://www.fps.polym.kyoto-u.ac.jp【研究分野】 高分子化学、液晶化学、物質化学【現在の研究課題】 導電性、液晶性、発光性、階層らせん性の共役系高分子の合成と性質【研究内容キーワード】 導電性高分子、液晶性共役高分子、不斉液晶反応場、階層構造制御【最終学歴】 京都大工学研究科博士後期課程【学位】 工学博士【略歴】 福井大工助手、筑波大物質工講師、助教授、教授、同大学院数理物質科学研
究科教授、学際物質科学研究センター長【在外研究歴】 カリフォルニア大学サンタバーバラ校交換研究員、コーネル大学客員研究員【所属学会】 日本化学会、高分子学会、日本液晶学会、アメリカ化学会【学会活動】 文部科学省科研費（特定領域研究、2005-2008）「次世代共役ポリマーの超階層制御と革新機能」領域代表、Chair of International Conference onScience andTechnology of Synthetic Metals (2010).
【主な著書、学術論文】 1. B. A. San Jose, S. Matsushita, K. Akagi, “Lyotropic Chiral Nematic Liquid
Crystalline Aliphatic Conjugated Polymers Based on Di-Substituted Polyacetylene（過去 5 年以内）
Derivatives that Exhibit High Dissymmetry Factors in Circularly Polarized
Luminescence”, J. Am. Chem. Soc., 134, 19895 (2012).
2. K. Watanabe, H. Iida, K. Akagi, “Circularly Polarized Blue Luminescent
Spherulites Consisting of Hierarchically Assembled Ionic Conjugated Polymers
with a Helically π-Stacked Structure”, Adv. Mater., 24, 6451 (2012).
3. H. Hayasaka, T. Miyashita, M. Nakayama, K. Kuwada, K. Akagi, “Dynamic
Photoswitching of Helical Inversion in Liquid Crystals Containing Photoresponsive
Axially Chiral Dopants”, J. Am. Chem. Soc., 134, 3758 (2012).
4. S. Matsushita, M. Kyotani, K. Akagi, “Hierarchically Controlled Helical
Graphite Films Prepared from Iodine-Doped Helical Polyacetylene Films Using
Morphology-Retaining Carbonization”, J. Am. Chem. Soc., 133, 17977 (2011).
5. K. Akagi, “Helical Polyacetylene - Asymmetric Polymerization in a Chiral Liquid
Crystal Field”, Chem. Rev., 109, 5354 (2009).
【学術関係の受賞】 日本化学会学術賞 (1999 年度 )、日産科学賞 (2000 年度 )、日本液晶学会賞論文賞 (2001 年度 )、つくば賞 (2001 年度 )、高分子学会賞 (2002 年度 )、文部科学大臣表彰科学技術賞 (2005 年度 )、筑波大学名誉教授称号授与（2009年度）、日本液晶学会賞業績賞（2010 年度）－4－fukui2012_01.indb 4

14.1.9 1:23:03 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)⑶

スーパーバイザー【氏名（ふりがな）】 北川

進 （きたがわすすむ）【職名】 副拠点長【所属】 物質－細胞統合システム拠点【研究室】 桂キャンパス A4 棟 319 号室【直通電話】 075-383-2733【FAX】 075-383-2732【電子メールアドレス】 kitagawa@icems.kyoto-u.ac.jp【ホームページ】 http://www.sbchem.kyoto-u.ac.jp/kitagawa-lab/index.html【研究分野】 錯体化学、無機化学【現在の研究課題】 多孔性配位高分子の化学とその応用【研究内容キーワード】 配位空間の化学、メゾスコピック化学、多孔性配位高分子、金属－有機骨格体【最終学歴】 1979 年 3 月京都大学大学院石油化学専攻博士課程修了【学位】 1979 年 7 月工学博士（京都大学）【略歴】 1979 年 4 月近畿大学理工学部助手、1983 年 4 月近畿大学理工学部講師、1988
年 4 月近畿大学理工学部助教授、1992 年 4 月東京都立大学理学部化学教室無機化学第一講座教授、1998 年 6 月京都大学大学院工学研究科合成・生物化学専攻教授、2007 年 10 月京都大学物質－細胞統合システム拠点・副拠点長および京都大学大学院工学研究科合成・生物化学専攻（兼任）教授【在外研究歴】 1986 年 -1987 年 Texas A&M 大学 Cotton 研究室博士研究員【所属学会】 日本化学会、錯体化学会、物理学会、高分子学会、米国学会【主な著書、学術論文】 1.“One-dimensional imidazole aggregate in aluminum porous coordination polymers（過去 5 年以内）
with high proton conductivity”, S. Bureekaew, S. Horike, M. Higuchi, M. Mizuno, T.
Kawamura, D. Tanaka, N. Yanai and S. Kitagawa, Nature Materials, 2009, 8, 831836.
2.“Photoactivation of a nanoporous crystal for on-demand guest trapping andconversion”, H. Sato, R. Matsuda, K. Sugimoto, M. Takata and S. Kitagawa,Nature Materials, 2010, 9, 661-666.
3.“Mesoscopic architectures of porous coordination polymers fabricated bypseudomorphic replication”, J. Reboul, S. Furukawa, N. Horike, M. Tsotsalas,
K. Hirai, H. Uehara, M. Kondo, N. Louvain, O. Sakata and S. Kitagawa, Nature
Materials, 2012, 11,717-723. (Cover Picture)【学術関係の受賞】 1. 2002 年第 19 回日本化学会学術賞
2. 2007 年 Earl L. Muetterties Memorial Lectureship (University of California,
Berkeley)、平成 19 年度錯体化学会賞
3. 2008 年 Humboldt Research Award, Germany
4. 2009 年第 61 回日本化学会賞
5. 2010 年トムソン・ロイター引用栄誉賞受賞
6. 2011 年 平 成 23 年 度 科 学 技 術 分 野 の 文 部 科 学 大 臣 表 彰 研 究 部 門、The
Honorary Fellowship of the Council of the Chemical Research Society of India(CRSI)、平成 23 年春の紫綬褒章、京都新聞大賞文化学術賞－5－fukui2012_01.indb 5

14.1.9 1:23:04 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)【氏名（ふりがな）】 田中

勝久 （たなかかつひさ）【職名】 教授【所属】 工学研究科 材料化学専攻【研究室】 桂キャンパス A3 クラスター 018【直通電話】 075-383-2801【FAX】 075-383-2420【電子メールアドレス】 tanaka@dipole7.kuic.kyoto-u.ac.jp【ホームページ】 http://dipole7.kuic.kyoto-u.ac.jp/【研究分野】 無機固体化学【現在の研究課題】 酸化物薄膜および非晶質酸化物の磁気的性質・表面プラズモンを利用した光機能材料の作製【研究内容キーワード】 酸化物、薄膜、非晶質、表面プラズモン、磁気的性質、光学的性質【学歴】 1984 年 3 月 京都大学工学部工業化学科卒業
1986 年 3 月 京都大学大学院工学研究科工業化学専攻修士課程修了【学位】 1991 年 3 月 京都大学工学博士【略歴】 1986 年 4 月 三重大学工学部助手
1989 年 4 月 京都大学工学部助手
1999 年 7 月 京都工芸繊維大学工芸学部助教授
2004 年 4 月 京都大学大学院工学研究科教授
2009 年 10 月 豊橋技術科学大学客員教授【所属学会】 日本セラミックス協会、日本化学会、応用物理学会、日本物理学会、粉体
粉 末 冶 金 協 会、 日 本 材 料 学 会、Materials Research Society、Optical Society ofAmerica【学会活動】 粉体粉末冶金協会 理事、日本化学会近畿支部 副支部長
【主な著書、学術論文】 1. X. Meng, K. Fujita, S. Murai, and K. Tanaka, “Coherent Random Lasers in Weakly
Scattering Polymer Films Containing Silver Nanoparticles”, Physical Review A 79
（過去 5 年以内）
(2009) 053817-1-7.
2. H. Akamatsu, S. Oku, K. Fujita, S. Murai, and K. Tanaka, “Magnetic Properties of
Mixed-Valence Iron Phosphate Glasses”, Physical Review B 80 (2009) 134408-1-9.
3. H. Akamatsu, K. Fujita, S. Murai, and K. Tanaka, “Ferromagnetic Eu2+-Based
Oxide Glasses with Reentrant Spin Glass Behavior”, Physical Review B 81 (2010)
014423-1-9.
4. X. Meng, K. Fujita, S. Murai, T. Matoba, and K. Tanaka, “Plasmonically Controlled
Lasing Resonance with Metallic-Dielectric Core-Shell Nanoparticles”, Nano Letters
11 (2011) 1374-1378.
5. H. Akamatsu, K. Fujita, H. Hayashi, T. Kawamoto, Y. Kumagai, Y. Zong, K. Iwata,
F. Oba, I. Tanaka, and K. Tanaka, “Crystal and electronic structure and magnetic
properties of divalent europium perovskite oxides EuMO3 (M=Ti, Zr, and Hf):Experimental and first-principles approaches”, Inorganic Chemistry 51 (2012)
4560-4567.
6. X. Meng, U. Guler, A. V. Kildishev, K. Fujita, K. Tanaka, and V. M. Shalaev,“Breaking symmetry of plasmonic nanostructures: an efficient route towards
unidirectional spaser”, Scientific Reports 3 (2013) 1241-1-5.
7. Y. Hasegawa, M. Maeda, T. Nakanishi, Y. Doi, Y. Hinatsu, K. Fujita, K. Tanaka, H.
Koizumi, and K. Fushimi, “Effective optical Faraday rotations of semiconductor
EuS nanocrystals with paramagnetic transition-metal ions”, Journal of the American
Chemical Society 135 (2013) 2659-2666.
8. T. Kawamoto, K. Fujita, H. Akamatsu, T. Nakamura, T. Kinoshita, M. Mizumaki, N.
Kawamura, M. Suzuki, Y. Kususe, S. Murai, and K. Tanaka, “Eu M4,5- and L2,3-edge
x-ray magnetic circular dichroism of ferromagnetic amorphous oxides in EuO-TiO2
system”, Physical Review B 88 (2013) 024405-1-9.
【学術関係の 受賞】 The Australasian Ceramic Society/Ceramic Society of Japan (ACS/CJS) Joint CeramicAward (1997 年 )、日本セラミックス協会学術賞 (2005 年 )－6－fukui2012_01.indb 6

14.1.9 1:23:04 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)【氏名（ふりがな）】 田中

耕一郎 （たなかこういちろう）【職名】 教授【所属】 物理学・宇宙物理学専攻【研究室】 理学研究科 5 号館 118 号室【直通電話】 075-753-3756【FAX】 075-753-3757【電子メールアドレス】 kochan ＠ scphys.kyoto-u.ac.jp【ホームページ】 http://www.hikari.scphys.kyoto-u.ac.jp/jp/index.php【研究分野】 光物性、テラヘルツ分光学【現在の研究課題】 超高速光学現象、テラヘルツ非線形分光、水のダイナミクス【研究内容キーワード】 テラヘルツ、非線形分光【学歴】 1990 年 3 月

京都大学大学院理学研究科博士後期課程修了【学位】 1990 年 3 月

理学博士（京都大学）【略歴】 1990 年 4 月 東京大学物性研究所極限物性部門極限レーザー助手、1995 年 1
月 新技術事業団（現在の科学技術振興事業団）平尾誘起構造プロジェクト
研究員（グループリーダー）、
1997 年 1 月 京都大学大学院理学研究科助教授、2004 年 4 月 京都大学大学院理学研究科教授、2008 年 4 月 京都大学物質－細胞統合システム拠点教授、2013 年 4 月 京都大学大学院理学研究科教授【所属学会】 Optical Society of America、日本物理学会、日本応用物理学会【学会活動】 物理学会京都支部長【主な著書、学術論文】 1. Tobias Kampfrath, Koichiro Tanaka and Keith A. Nelson, “Resonant and（過去 5 年以内）
nonresonant control over matter and light by intense terahertz transients”, Nature
Photonics 7,680–690 (2013)
2. K. Shinokita, H. Hirori, K. Tanaka, T. Mochizuki, C. Kim, H. Akiyama, L. N.
Pfeiffer and K. W. West, “Terahertz-Induced Optical Emission of Photoexcited
Undoped GaAs Quantum Wells”, Phys. Rev. Lett. 111, 067401 (2013)
3. F. Blanchard, A. Doi, T. Tanaka, and K. Tanaka, “Real-Time, SubwavelengthTerahertz Imaging”, Annu. Rev. Mater. Res. 43:11.1–11.23 (2013)
4. Shuntaro Tani, Francois Blanchard, and Koichiro Tanaka “Ultrafast Carrier
Dynamics Under High Electric Field in Graphene”, Phys. Rev. Lett. 109, 166603(2012)
5. E. Collet, H. Watanabe, N. Bréfuel, L. Palatinus, L. Roudaut, L. Toupet, K. Tanaka,
J.-P. Tuchagues, P. Fertey, S. Ravy, B. Toudic, H. Cailleau, “Aperiodic spin stateordering of bi-stable molecules and its photoinduced erasing”, Phys. Rev. Lett. 109,257206 (2012)
6. H. Hirori, K. Shinokita, M. Shirai, S. Tani, Y. Kadoya, K. Tanaka, “Extraordinary
carrier multiplication gated by a picosecond electric field pulse”, Nature
Communications 2, 594/1-594/6, (2011)－7－

fukui2012_01.indb 7

14.1.9 1:23:04 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)【氏名】 Norihiro Tokitoh【職名】 Professor【所属】 Institute for Chemical Research【研究室】 ICR Main Building C-456【直通電話】 0774-38-3200【FAX】 0774-38-3209【電子メールアドレス】 Tokitoh@boc.kuicr.kyoto-u.ac.jp【ホームページ】 http://boc.kuicr.kyoto-u.ac.jp/www/index.html【研究分野】 Organoelement Chemistry【現在の研究課題】 Synthesis and Characterization of Novel Low-coordinate Main Group Element
Compounds【研究内容キーワード】 Heavy Aromatics, Multiple-bond Compounds, d- π Conjugation【学歴】 1979 B.S.; 1982 M.S.; 1985 Ph.D.; The University of Tokyo【学位】 Doctor of Science from The University of Tokyo【略歴】 Research Associate (1986) and then Assistant Prof. (1987) of Tsukuba Univ.; AssistantProf. (1989) and Associate Prof. (1994) of The University of Tokyo; Professor of
IFOC, Kyushu Univ. (1998-2000); Professor of ICR, Kyoto Univ. (2000-present);
Visiting Prof. at Technische Universität Braunschweig, Germany (2004-2007); Vicedirector of ICR (2006-2008); Director of ICR (2008-2012).

【所属学会】 Chemical Society of Japan, American Chemical Society, The Society of PhysicalOrganic Chemistry, Japan, The Society of Silicon Chemistry, Japan, Kinki Kagaku
Kyokai, The Society of Synthetic Organic Chemistry, Japan.

【学会活動】 1996- The Society of Silicon Chemistry, Japan, Standing Board Member; 2006International Symposium on Inorganic Ring Systems, IAB Member; 2006International Conference on Heteroatom Chemistry, IAB Member; 2009-2011 The
Chemical Society of Japan, a Member of Board of Directors; 1998-2006 Journal of
Physical Organic Chemistry, Associate Editor for Asia; 2006-2009 Organometallics,
Advisory Board Member; 2011- The Society of Physical Organic Chemistry, Japan,
Standing Board Member; 2012 10th International Conference on Heteroatom
Chemistry, Chairman; 2012- International Symposium on Silicon Chemistry, IAB
Member; 2013- International Conference on Organometallic and Coordination
Chemistry of Germanium, Tin and Lead (ICCOC-GTL), IAB Member; 2013- Bulletinof the Chemical Society of Japan (CSJ), Editor-in-Chief【主な著書、学術論文】 1. Syntheses and Structures of an “Alumole” and Its Dianion, Agou, T.: Wasano, T.;
Jin, P; Nagase, S.; Tokitoh, N. Angew. Chem. Int. Ed. 2013, 125, 10215–10218.
（過去 5 年以内）
2. Synthesis and Properties of 4,5,6-Triphospha[3]radialene, Miyake, H.; Sasamori, T.;
Tokitoh, N. Angew. Chem. Int. Ed. 2012, 51, 3458-3461.
3. Synthesis of Kinetically Stabilized 1,2-Dihydrodisilenes, Agou, T.; Sugiyama,Y.; Sasamori, T.; Sakai, H.; Furukawa, Y.; Takagi, N.; Guo, J. D.; Nagase, S.;
Hashizume, D.; Tokitoh, N. J. Am. Chem. Soc. 2012, 134, 4120-4123.
4. Fluorination Reaction of a Ditelluride Bearing Bulky Aryl Substituents: Formationof Mixed-Valent Te(IV)-Te(II) Ditelluride Difluoride, Sasamori, T.; Sugamata, K.;
Tokitoh, N. Chem-Asian J. 2011, 6, 2301-2303.
5. Reactivity of an aryl-substituted silicon-silicon triple bond: 1,2-disilabenzenes
from the reactions of a 1,2-diaryldisilyne with alkynes, Han, J. S.; Sasamori, T.;
Mizuhata, Y.; Tokitoh, N. Dalton Trans. 2010, 39, 9238-9240.
【学術関係の受賞】 1992 Incentive Award of the Society of the Synthetic Organic Chemistry, Japan
1996 Incentive Award of the Society of Silicon Chemistry, Japan
1998 Japan IBM Science Award
2003 Chemical Society of Japan Award for Creative Work (CSJ)
2003 Alexander von Humboldt Research Award
2002, 2005, 2007, 2009, 2010 and 2013 BCSJ Awards (CSJ)
2007 Lectureship Award of National Science Council, Republic of China
2010 The 3rd Kim Yong Hae Lectureship Award (KAIST, Korea)
2010 Best Reviewer Commendation (Japan Society for the Promotion of Science)－8－

fukui2012_01.indb 8

14.1.9 1:23:05 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)【氏名（ふりがな）
】 八尾

誠 （やお

まこと）

【職名】 教授【所属】 大学院理学研究科【研究室】 理学研究科５号館

物理学第一教室
128 号室【直通電話】 075-753-3774【FAX】 075-753-3780【電子メールアドレス】 yao@scphys.kyoto-u.ac.jp【ホームページ】 http://www2.scphys.kyoto-u.ac.jp/Labos/fukisoku/【研究分野】 不規則系物理学【現在の研究課題】 X 線自由電子レーザー・放射光利用の不規則系実験研究【研究内容キーワ―ド】 液体、クラスター、分子、X 線自由電子レーザー、シンクロトロン放射光、金属・非金属転移、ナノプラズマ、プラズモン／エキシトン、超高速電荷・エネルギー
移動、クーロン爆発、電子分光／イオン分光、密度汎関数法【学歴】 1980 年 3 月 京都大学大学院理学研究科博士後期課程 研究指導認定
1982 年 3 月 京都大学理学博士 学位取得
【学位】 京都大学理学博士【略歴】 1985 年 8 月 京都大学理学部 助手 採用
1990 年 12 月 京都大学理学部 講師 昇任
1993 年 3 月 京都大学理学部 助教授 昇任
2003 年 6 月 京都大学大学院理学研究科 教授 昇任、現在に至る【所属学会】 日本物理学会、日本中性子科学会、日本放射光学会、国際教育学会【学会活動】 国際教育学会理事【主な著書、学術論文】 1. Contactless measurements of charge migration within single molecules, Kiyonobu
Nagaya, Hiroshi Iwayama, Akinori Sugishima, Yoshinori Ohmasa, Makoto Yao,
（過去 5 年以内）
Appl.Phys.Lett. 96 (2010) 233101.
2. Inhomogeneous charge redistribution in Xe clusters exposed to intense extreme
ultraviolet free electron laser, H. Iwayama, A. Sugishima, K. Nagaya, M. Yao,
H. Fukuzawa, K. Motomura, X.-J. Liu, A. Yamada,C. Wang, K. Ueda, N. Saito,
M. Nagasono, K. Tono, M. Yabashi, T. Ishikawa, H. Ohashi, H. Kimura, and T.
Togashi, J. Phys. B: At. Mol. Opt. Phys. Fast track 43 (2010) 161001.
3. Deep inner-shell multiphoton ionization by intense x-ray free-electron laser
pulses,H. Fukuzawa, S.-K. Son, K. Motomura, S. Mondal, K. Nagaya, S. Wada,
X.-J. Liu, R.Feifel, T. Tachibana, Y. Ito, M. Kimura, T. Sakai, K. Matsunami, H.
Hayashita, J. Kajikawa, P. Johnsson, M. Siano, E. Kukk, B. Rudek, B. Erk, L.
Foucar, E. Robert, C. Miron, K. Tono, Y. Inubushi, T. Hatsui, M. Yabashi, M. Yao, R.
Santra, and K. Ueda, Phys. Rev. Letts. 110, 173005 (2013).

－9－

fukui2012_01.indb 9

14.1.9 1:23:05 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)【氏名（ふりがな）】 田中

功 （たなかいさお）【職名】 教授【所属】 工学研究科

材料工学専攻【研究室】 吉田キャンパス

工学部物理系校舎

量子材料学研究室【直通電話】 075-753-5465【FAX】 075-753-5447【電子メールアドレス】 tanaka@cms.MTL.kyoto-u.ac.jp【ホームページ】 http://cms.mtl.kyoto-u.ac.jp/tanaka.html【研究分野】 材料科学

【現在の研究課題】 計算材料科学，構造材料科学，エネルギー材料学【研究内容キーワード】 量子材料設計，第一原理計算，材料ｲﾝﾌｫﾏﾃｨｸｽ，ｾﾗﾐｯｸｽ科学，電子分光【最終学歴】 1987 年 3 月大阪大学大学院基礎工学研究科物理系専攻博士後期課程修了【学位】 1987 年 3 月大阪大学工学博士【略歴】 1987 年 4 月 日本学術振興会特別研究員 (PD)、1987 年 6 月大阪大学産業科学研究所・助手、1993 年 4 月京都大学工学部・助手、1996 年 5 月京都大学大学
院エネルギー科学研究科・助教授、2001 年 7 月京都大学大学院工学研究科・助教授、2003 年 12 月京都大学大学院工学研究科・教授【在外研究歴】 1992 年 4 月 -1993 年 3 月 ドイツ マックスプランク金属研究所・客員研究員（アレキサンダー・フォン・フンボルト財団奨学研究員）【所属学会】 日 本 金 属 学 会、 日 本 セ ラ ミ ッ ク ス 協 会、 日 本 鉄 鋼 協 会， 応 用 物 理 学 会、American Ceramic Society、Materials Research Society【学会活動】 Journal of American Ceramics Society フ ェ ロ ー・ 編 集 委 員、World Academy of
Ceramics 会員、日本金属学会評議員【主な著書、学術論文】 1. A. Togo and I. Tanaka, "Evolution of crystal structures in metallic elements",
Physical Review B, 87 184104 1-6 (2013).
（過去 5 年以内）

2. H. Akamatsu, Y. Kumagai, F. Oba, K. Fujita, K. Tanaka, and I. Tanaka, "Strong
Spin-Lattice Coupling Through Oxygen Octahedral Rotation in Divalent Europium
Perovskites," Advanced Functional Materials, 23[15] 1864-72 (2013).
3. M. Choi, F. Oba, Y. Kumagai, and I. Tanaka, "Anti-ferrodistortive-Like OxygenOctahedron Rotation Induced by the Oxygen Vacancy in Cubic SrTiO3," Advanced
Materials, 25[1] 86-90 (2013).
4. R. Ishikawa, N. Shibata, F. Oba, T. Taniguchi, S. D. Findlay, I. Tanaka, and Y.
Ikuhara, "Functional Complex Point-Defect Structure in a Huge-Size-Mismatch
System," Physical Review Letters, 110[6] (2013).
5. D. Han, T. Uda, Y. Nose, T. Okajima, H. Murata, I. Tanaka, and K. Shinoda,"Tetravalent Dysprosium in a Perovskite-Type Oxide," Advanced Materials, 24[15]2051-53 (2012).

6. Y. Koyama, H. Arai, Z. Ogumi, I. Tanaka, and Y. Uchimoto, "Co K-edge XANESof LiCoO2 and CoO2 with a variety of structures by supercell density functional
calculations with a core hole," Physical Review B, 85[7] (2012).
7. Y. Kumagai, A. Seko, F. Oba, and I. Tanaka, "Ground-state search inmulticomponent magnetic systems," Physical Review B, 85[1] (2012).
8. B. Liu, A. Seko, and I. Tanaka, "Cluster expansion with controlled accuracy for the
MgO/ZnO pseudobinary system via first-principles calculations," Physical Review
B, 86[24] (2012).
【学術関係の受賞】 ドイツ政府
ﾌｨﾘｯﾌﾟ ･ ﾌﾗﾝﾂ ･ ﾌｫﾝ ･ ｼﾞｰﾎﾞﾙﾄ賞（2008 年）
ﾙｰﾏﾆｱ科学ｱｶﾃﾞﾐｰ ﾄﾞﾗｺﾞﾐｰﾙ・ﾌﾙﾑｾﾞｽｺ賞（2006 年）
米国ｾﾗﾐｯｸｽ学会 ﾘﾁｬｰﾄﾞ・ﾌﾙﾗｰｽ賞（2004 年）－ 10 －

fukui2012_01.indb 10

14.1.9 1:23:05 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)【氏名（ふりがな）】 田中

庸裕 （たなかつねひろ）【職名】 教授【所属】 工学研究科

分子工学専攻【研究室】 桂キャンパス A4 棟 126 号室【直通電話】 075-383-2558【FAX】 075-383-2561【電子メールアドレス】 tanakat@moleng.kyoto-u.ac.jp【ホームページ】 http://www.moleng.kyoto-u.ac.jp/~moleng_04/【研究分野】 触媒化学・固体物理化学【現在の研究課題】 固体と接触したナノ粒子・ものづくりの光触媒【研究内容キーワード】 元素戦略・ナノ粒子・X 線分光法
【学歴】 1987 年 3 月 京都大学工学研究科博士後期課程修了【学位】 1987 年 7 月 京都大学工学博士【略歴】 1987 年 10 月北海道大学理学部助手，1990 年 4 月京都大学工学部助手，1997
年 7 月京都大学工学研究科助教授，2004 年同教授
【所属学会】 触媒学会，日本化学会，石油学会，アメリカ化学会，日本 XAFS 研究会【学会活動】 前触媒学会会誌編集担当理事 ,【主な著書、学術論文】 1. Effects of Rreaction Temperature on the Photocatalytic Activity of Photo-SCR of（過去 5 年以内）
NO with NH3 over a TiO2 Photocatalyst, Akira Yamamoto, Yuto Mizuno, Kentaro
Teramura, Tetsuya Shishido and Tsunehiro Tanaka, Catal. Sci. Technol., 2013, 3,
1771-1775.
2. Characterization of Thermally Stable Brønsted Acid Sites on Alumina-Supported
Niobium Oxide Calcined at High Temperature Tomoyuki Kitano, Tetsuya Shishido,
Kentaro Teramura, and Tsunehiro Tanaka, Chem. Phys. Chem., 2013, 14(11), 25602564.
3. Development of Palladium Surface-Enriched Heteronuclear Au–Pd Nanoparticle
Dehalogenation Catalysts in an Ionic Liquid, Xiao Yuan, Geng Sun, Hiroyuki
Asakura, Tsunehiro Tanaka, Xi Chen, Dr. Yuan Yuan, Gabor Laurenczy, Yuan Kou,
Paul J. Dyson, Ning Yan, Chemistry –A European Journal., 2013, 19(4), 1227-1234.
4. Reaction Mechanism of Selective Photooxidation of Amines over Niobium Oxide:
Visible Light-Induced Electron Transfer Between Adsorbed Amine and Nb2O5,
Shinya Furukawa, Yasuhiro Ohno, Tetsuya Shishido, Kentaro Teramura, andTsunehiro Tanaka, J. Phys. Chem. C., 2013, 117(1), 442-450.
5. Insights into the Formation Mechanism of Rhodium Nanocubes, Siyu Yao, Yuan
Yuan, Chaoxiab Xiao, Weizhen Li, Yuan Kou, Paul Dyson, Ning Yan, Hiroyuki
Asakura, Kentaro Teramura, and Tsunehiro Tanaka, J. Phys. Chem. C., 2012,
116(28), 15076-15086.
6. Artificial Photosynthesis Using Typical Clays: Photocatalytic Conversion of CO2
in Water over Layered Double Hydroxides, Kentaro Teramura, Shoji Iguchi, Yuto
Mizuno, Tetsuya Shishido, and Tsunehiro Tanaka, Angew. Chem. Intern. Ed.., 2012,
51(32), 8008-8011.
7. Brønsted Acid Property of Alumina-Supported Niobium Oxide Calcined at High
Temperatures: Characterization by Acid-Catalyzed Reactions and Spectro- scopic
Methods, Tomoyuki Kitano, Tetsuya Shishido, Kentaro Teramura, and Tsunehiro
Tanaka, J. Phys. Chem. C., 2012, 116, 11615-11625－ 11 －

fukui2012_01.indb 11

14.1.9 1:23:05 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)【氏名】 Tanimura Yoshitaka【職名】 Professor【所属】 Department of Chemistry【研究室】 Rm. 256, Faculty of Science Building #6, North Wing
【直通電話】 075-753-4017【FAX】 075-753-4018【電子メールアドレス】 tanimura@kuchem.kyoto-u.ac.jp【ホームページ】 http://theochem.kuchem.kyoto-u.ac.jp【研究分野】 Chemical Physics【現在の研究課題】 Nonlinear Optical Response【研究内容キーワード】 Statistical Physics【学歴】 March, 1986, M.Sc., Keio University
March, 1989, Ph.D. , Keio University【学位】 Ph. D. in Physics, Keio University【所属学会】 The Physical Society of Japan, The Chemical Society of Japan, American Chemical
Society【主な著書、学術論文】 1. A. G. Dijkstra and Y. Tanimura, Role of the Environment Time Scale on Light（過去 5 年以内）
Harvesting Efficiency and Coherent Oscillations, New J. Phys. 14, 073027 [11pages](2012).
2. P. Hamm,J. Savolainen, J. Ono and Y. Tanimura, Note: Inverted Time-Orderingin 2D-Raman-THz Spectroscopy of Water, J. Chem. Phys. 136, 236101 [2pages](2012)
3. D. Packwood and Y. Tanimura, Dephasing by a continuous-time random walkprocess, Phys. Rev. E. 86, 011130 [9 pages] (2012).
4. Y. Tanimura, Reduced hierarchy equations of motion approach with Drude plus
Brownian spectral distribution: Probing electron transfer processes by means of
two-dimensional correlation spectroscopy, J. Chem, Phys 137, 22A550 [9 pages](2012).
5. A. Sakurai and Y. Tanimura, An approach to quantum transport based on reduced
hierarchy equations of motion: Application to a resonant tunneling diode, J. Phys.
Soc. Jpn 82, 033707 [4 pages] (2013).
【学術関係の受賞】 2002 Morino Foundation Award
2012 Humboldt Research Award from the Alexander von Humboldt Foundation inGermany－ 12 －

fukui2012_01.indb 12

14.1.9 1:23:06 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)【氏名（ふりがな）】 山本

量一 （やまもと

りょういち）【職名】 教授【所属】 工学研究科【研究室】 桂キャンパス

化学工学専攻A 棟 118 号室【直通電話】 075-383-2661【FAX】 075-383-2651【電子メールアドレス】 ryoichi@cheme.kyoto-u.ac.jp【ホームページ】 http://www-tph.cheme.kyoto-u.ac.jp/【研究分野】 ソフトマターの移動現象【現在の研究課題】 コロイド分散系の計算機シミュレーション【研究内容キーワード】 ソフトマター、コロイド、計算機シミュレーション、ガラス転移【最終学歴】 1992 年 3 月神戸大学大学院 工学研究科修士課程化学工学専攻修了【学位】 1996 年 3 月博士（工学）京都大学【略歴】 1994 年 9 月 神戸大学大学院自然科学研究科物質科学専攻助手、1996 年 3 月
京都大学大学院理学研究科物理学・宇宙物理学専攻助手、2000 年 1 月 同講師、2004 年 10 月 京都大学大学院工学研究科化学工学専攻助教授、2007 年 4 月 同准教授、2008 年 10 月 同教授【在外研究歴】 2000 年 9 月 -2001 年 8 月 英国ケンブリッジ大学化学教室（J-P. Hansen 教授）（文部省在外研究員（若手））【所属学会】 日本物理学会、化学工学会、分子シミュレーション研究会、コロイド部会（日本化学会）【主な著書、学術論文】 1. Rei Tatsumi and Ryoichi Yamamoto, Velocity relaxation of a particle in a confined（過去 5 年以内）
compressible fluid, J. Chem. Phys., 138, 184905 (2013).
2. John J. Molina, Yasuya Nakayama, and Ryoichi Yamamoto, Hydrodynamic
interactions of self-propelled swimmers, Soft Matter 9, 4923-4936 (2013).
3. Hideyuki Mizuno and Ryoichi Yamamoto, General constitutive model forsupercooled liquids: Anomalous transverse wave propagation, Phys. Rev. Lett. 110,095901 (2013).
4. Hideki Kobayashi and Ryoichi Yamamoto, Implementation of Lees-Edwards
periodic boundary conditions for direct numerical simulations of particle
dispersions under shear flow, J. Chem. Phys. 134, 064110 (2011).
5. S. Yasuda and R. Yamamoto, Rheological properties of polymer melt between
rapidly oscillating plates: an application of multiscale modeling, EPL 86, 18002(2009).
【学術関係の受賞】 2007 年 1 月 ホソカワ研究奨励賞、2002 年 12 月 分子シミュレーション研究会
学術賞－ 13 －

fukui2012_01.indb 13

14.1.9 1:23:06 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)【氏名（ふりがな）】 高田

彰二 （たかだ

しょうじ）【職名】 教授【所属】 理学研究科

生物科学専攻生物物理学教室【研究室】 理学部 1 号館 205 号室【直通電話】 075-753-4220【FAX】 075-753-4222【電子メールアドレス】 takada@biophys.kyoto-u.ac.jp【ホームページ】 http://theory.biophys.kyoto-u.ac.jp【研究分野】 理論生物物理学【現在の研究課題】 生体分子の構造機能についての理論およびコンピュータシミュレーション研
究【研究内容キーワード】 タンパク質フォールディング、分子モーター、遺伝子動態、生体分子モデリ
ング【最終学歴】 1991 年 9 月総合研究大学院大学数物科学研究科機能分子科学専攻博士後期課
程退学【学位】 1994 年 3 月理学博士（総合研究大学院大学）【略歴】 1991 年～ 1995 年岡崎国立共同研究機構技官（分子科学研究所）、1995 年～
1998 年日本学術振興会研究員（イリノイ大学化学科）、1998 年～ 2001 年神戸大学理学部化学科講師、2001 年～ 2007 年同助教授、2007 年～ 2013 年京都大学理学研究科生物科学専攻生物物理教室准教授、2013 同教授。
【在外研究歴】 1995 年 5 月 -1998 年 3 月

米国イリノイ大学化学科（日本学術振興会研究員）【所属学会】 日本生物物理学会【学会活動】 日本生物物理学会運営委員【主な著書、学術論文】 1. M.J.McGrath, I.F.Kuo, S.Hayashi, and S.Takada, ATP hydrolysis mechanism（過去 5 年以内）
in kinesin studied by combined quantum-mechanical molecular-mechanicalmetadynamics , JACS, 103: 8908-8919, 2013.
2. X.Yao, N.Kimura, S.Murakami, and S.Takada, Drug Uptake Pathways of Multidrug
Transporter AcrB Studied by Molecular Simulations and Site-Directed Mutagenesis
Experiments, JACS, 135: 7474-7485, 2013.
3. T.Terakawa, H.Kenzaki, & S.Takada, p53 searches on DNA by rotation-uncoupled
sliding at C-terminal tails and restricted hopping of core domains , JACS, 134:
14555-14562, 2012.
4. S.Takada, Coarse-grained molecular simulations of large biomolecules, Curr
Opinion in Struct Biol, 22: 130-137, 2012.
5. W.Li, P.G.Wolynes, & S.Takada, Frustration, specific sequence dependence, andnonlinearity in large-amplitude fluctuations of allosteric proteins, Proc Nat Acad
Sci USA, 108: 3504-3509, 2011.
6. X.Yao, H.Kenzaki, S.Murakami, & S.Takada, Drug export and allosteric coupling
in a multidrug transporter revealed by molecular simulations, Nature Comm,
1:117(8pages), 2010
7. *N.Koga, *T Kameda, K.Okazaki, & S.Takada, Paddling mechanism for thesubstrate translocation by AAA+ motor revealed by multiscale molecularsimulations, Proc Nat Acad Sci USA, 106: 18237-18242, 2009.
－ 14 －

fukui2012_01.indb 14

14.1.9 1:23:06 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)【氏名（ふりがな）】 林

重彦 （はやししげひこ）【職名】 教授【所属】 理学研究科

化学専攻【研究室】 理学研究科 6 号館 154 号室【直通電話】 075-753-4006【FAX】 075-753-4000【電子メールアドレス】 hayashig@kuchem.kyoto-u.ac.jp【ホームページ】 http://kuchem.kyoto-u.ac.jp/riron/hayashig【研究分野】 理論化学・生物物理学【現在の研究課題】 タンパク質分子機能の理論的研究【研究内容キーワード】 タンパク質機能・分子シミュレーション【学歴】 1997 年 11 月

京都大学大学院理学研究科化学専攻博士課程修了【学位】 1997 年 11 月

博士（理学）（京都大学）【略歴】 1998 年 4 月日本学術振興会特別研究員（名古屋大学）、2000 年 4 月米国イリノイ大学ベックマン研究所博士研究員、2003 年 6 月京都大学福井謙一記念研究センター博士研究員、2003 年 10 月科学技術振興機構さきがけ研究員、2005
年 5 月京都大学大学院理学研究科准教授、2013 年 7 月同教授
【所属学会】 分子科学会、生物物理学会【主な著書、学術論文】 1. Molecular mechanism of ATP hydrolysis in F1-ATPase revealed by molecular（過去 5 年以内）
simulations and single molecule observations. Shigehiko Hayashi*, Hiroshi Ueno,
Abdul Rajjak Shaikh, Myco Umemura, Motoshi Kamiya, Yuko Ito, Mitsunori
Ikeguchi, Yoshihito Komoriya, Ryota Iino, and Hiroyuki Noji. J. Am. Chem. Soc.
134, 8447-8454 (2012).
2. Crucial role of protein flexibility in formation of a stable reaction transition statein an a-amylase catalysis. Kosugi Takahiro and Shigehiko Hayashi*. J. Am. Chem.
Soc. 134, 7045-7055 (2012).
3. QM/MM reweighting free energy SCF for geometry optimization on extensive freeenergy surface of enzymatic reaction. Takahiro Kosugi and Shigehiko Hayashi*. J.
Chem. Theory Comput. 8, 322-334 (2012).
4. Protein collective motions coupled to ligand migration in myoglobin. Yasutaka
Nishihara, Shigeki Kato, and Shigehiko Hayashi*, Biophys. J. 98, 1649-1657(2010).
5. Electronic coulombic coupling of excitation-energy transfer in xanthorhodopsin.
Kazuhiro Fujimoto, and Shigehiko Hayashi*, J. Am. Chem. Soc. 131, 14152-14153(2009).
6. Photochemical reaction dynamics of the primary event of vision studied by a hybrid
molecular simulation. Shigehiko Hayashi*, Emad Tajkhoshid, and Klaus Schulten,
Biophys. J. 96, 403-416 (2009).

－ 15 －

fukui2012_01.indb 15

14.1.9 1:23:06 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)

⑷

専任教員

【氏名（ふりがな）】 中尾

嘉秀（なかおよしひで）【職名】 准教授【所属】 福井謙一記念研究センター

理論研究部門【研究室】 京都大学桂キャンパス A4-024【直通電話】 075-383-2546【FAX】 075-383-2799【電子メールアドレス】 nakao.yoshihide.5a@kyoto-u.ac.jp【ホームページ】 http://www.moleng.kyoto-u.ac.jp/~moleng_10/index_J.html【研究分野】 計算化学・理論化学【現在の研究課題】 機能性分子の物性の理論的解明【研究内容キーワード】 機能性金属錯体、スピン、発光【学歴】 2003 年 3 月 東京大学大学院工学系研究科応用化学専攻博士課程修了【学位】 2003 年 3 月 博士 ( 工学 ) ( 東京大学 )【略歴】 2003 年 4 月 京都大学大学院工学研究科助手、2007 年 4 月 京都大学大学院工学研究科助教、2011 年 1 月 京都大学福井謙一記念研究センター准教授【所属学会】 日本化学会、分子科学会【主な著書、学術論文】 1. Y. Nakao, K. Saito, S. Sakaki, “Theoretical investigation of μ-O-bridged dinuclear
Re complexes. Electronic structure, bonding nature, and absorption spectra”, Int. J.
（過去 5 年以内）
Quant. Chem. 109, 2319-2327 (2009).
2. K. Umakoshi, K. Saito, Y. Arikawa, M. Onishi, S. Ishizaka, N. Kitamura, Y. Nakao,
S. Sakaki, “Luminescent Heteropolynuclear Complexes of 3,5-Dimethylpyrazolate[Pt 2Au 2M 2(Me 2pz) 8] (M=Ag, Cu) Showing the Synergistic Effect of Three
Transition Elements in the Excited State”, Chem. Eur. J. 15, 4238-4242 (2009).
3. Y. I. Kurokawa, Y. Nakao, S. Sakaki, “Inverted Sandwich Type Dinuclear
Chromium(I) Complex and Its Analogues of Scandium(I), Titanium(I),
Vanadium(I), Manganese(I), and Iron(I): Theoretical Study of Electronic Structure
and Bonding Nature”, J. Phys. Chem. A, 114, 1191-1199 (2010).
4. H. Ando, Y. Nakao, H. Sato, S. Sakaki, “Comparison of Electronic Structures andLight-induced Excited Spin State Trapping between [Fe(2-picolylamine)3]2+ and Its
Iron(III) Analogue”, Dalton Trans. 39, 1836-1845 (2010).
5. Y. Nakajima, Y. Nakao, S. Sakaki, Y. Tamada, T. Ono, F. Ozawa, “Electronic
structure of four-coordinate iron(I) complex supported by a bis(phosphaethenyl)
pyridine ligand”, J. Am. Chem. Soc. 132, 9934-9936 (2010).

－ 16 －

fukui2012_01.indb 16

14.1.9 1:23:07 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)【氏名（ふりがな）】 石田

俊正 （いしだとしまさ）【職名】 特定准教授【所属】 福井謙一記念研究センター

国際連携研究室【研究室】 福井記念研究センター 205【直通電話】 075-711-7838【FAX】 075-711-7838【電子メールアドレス】 ishida@fukui.kyoto-u.ac.jp【ホームページ】 http://www.fukui.kyoto-u.ac.jp/~ishida【研究分野】 計算化学・理論化学【現在の研究課題】 光機能分子・生体分子の反応・ポテンシャル面生成法【研究内容キーワード】 光機能分子・生体分子・ポテンシャル面・非断熱遷移【最終学歴】 1989 年 3 月東京大学理学系大学院相関理化学専攻博士課程修了【学位】 1989 年 3 月理学博士（東京大学）【略歴】 1989 年 4 月 静岡大学教養部助手、1995 年 4 月静岡大学教養部助教授、1995
年 10 月静岡大学工学部助教授、2002 年 4 月岡崎国立共同研究機構分子科学研究所助教授（流動部門）、2004 年 4 月静岡大学工学部助教授、2004 年 10 月
京都大学福井謙一記念研究センター助教授、2007 年 4 月同准教授【在外研究歴】 1996 年 4 月 -1997 年 3 月 米国 Northwestern 大学化学（George C. Schatz 教授）（文部省在外研究員（若手））【所属学会】 日本化学会、日本分子化学会、日本コンピュータ化学会、American PhysicalSociety【主な著書、学術論文】 1. Toshimasa Ishida, Shinkoh Nanbu, and Hiroki Nakamura, Non-adiabatic ab initio
dynamics of two models of Schiff base retinal, J. Phys. Chem. A, 113(16), 4356–（過去 5 年以内）
4366 (2009).
2. Wilfredo C. Chung, Shinkoh Nanbu, and Toshimasa Ishida, “Nonadiabatic ab Initio
Dynamics of a Model Protonated Schiff Base of 9-cis Retinal”, J. Phys. Chem. A,
114 (32), 8190–8201 (2010).
3. Shinkoh Nanbu, Toshimasa Ishida and Hiroki Nakamura, “Future Perspectives ofNonadiabatic Chemical Dynamics” Chemical Science, 1, 663-674 (2010)
4. Wilfredo Credo Chung,* Shinkoh Nanbu, and Toshimasa Ishida, “A Nonadiabatic
Ab Initio Dynamics Study on Rhodopsin and its Analog Isorhodopsin: Chemical
Dynamics Reasons Behind Selection of Rhodopsin by Life”, Chem. Lett. 40, 13951397(2011).
5. Wilfredo Credo Chung, Shinkoh Nanbu, and Toshimasa Ishida, “A QM/MM
Trajectory Surface Hopping Approach to Photoisomerization of Rhodopsin
and Isorhodopsin. The Origin of Faster and More Efficient Isomerization for
Rhodopsin”, J. Phys. Chem. B 116, 8009−8023 (2012).

－ 17 －

fukui2012_01.indb 17

14.1.9 1:23:07 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)【氏名（ふりがな）】 池野

豪一 （いけのひでかず）【職名】 特別講師【所属】 大阪府立大学 21 世紀科学研究機構 ナノ科学・材料研究センター【研究室】 大阪府堺市中区学園町 1-2【直通電話】 072-254-9894【FAX】 072-254-9894【電子メールアドレス】 h-ikeno@21c.osakafu-u.ac.jp【ホームページ】 http://www.nanosq.21c.osakafu-u.ac.jp/ttsl/h_ikeno.html【研究分野】 計算材料科学，内殼電子分光【現在の研究課題】 第一原理計算と電子分光法によるナノ科学【研究内容キーワード】 電子論，量子化学，第一原理計算，内殼電子分光，固体物理，無機化学【学歴】 京都大学大学院工学研究科材料工学専攻博士後期課程修了【学位】 2007 年 3 月 京都大学 博士（工学）【略歴】 2007 年 4 月 – 2009 年 3 月 京都大学大学院工学研究科 博士研究員
2009 年 4 月 – 2010 年 3 月 ユトレヒト大学（オランダ）博士研究員
2010 年 4 月 – 2011 年 10 月 福井謙一記念研究センター フェロー2010 年 11 月 – 2013 年 3 月 福井謙一記念研究センター 特定助教
2013 年 4 月 – 現在 大阪府立大学 21 世紀科学研究機構
ナノ科学・材料研究センター 特別講師（テニュアトラック講師）【所属学会】 日本金属学会，日本物理学会【学会活動】 第 19 回 WIEN2k ワークショップ実行委員 (2012)【主な著書、学術論文】 1. Hidekazu Ikeno, Michael Krause, Thomas Hoöhe, Christian Patzig, Yongfeng Hu,
Antje Gawronski, Isao Tanaka and Christian Rüssel, Variation of Zr-L2,3 XANES in（過去 5 年以内）
tetravalent zirconium oxides, J. Phys.: Condens. Matter 25 (2013) 165505.
2. Hidekazu Ikeno, Teruyasu Mizoguchi, Yukinori Koyama, Zenpachi Ogumi,
YasuharuUchimoto, and Isao Tanaka, “Theoretical Fingerprints of Transition Metal
L2,3 XANES/ELNES for Lithium Transition Metal Oxides by ab initio Multiplet
Calculations”, J. Phys. Chem. C 115, 11871 (2011).
3. Hidekazu Ikeno, Teruyasu Mizoguchi and Isao Tanaka, “Ab initio charge transfer
multiplet calculations on the L 2,3 XANES and ELNES of 3d transition metaloxides”, Phys. Rev. B 83, 155107 (2011).
4. Teruyasu Mizoguchi, Weine Olovsson, Hidekazu Ikeno and Isao Tanaka,“Theoretical ELNES using one-particle an multi-particle calculations”, Micron 41,
695-709, (2010).
5. Hidekazu Ikeno, Frank M.F. de Groot, Eli Stavitski and Isao Tanaka, “Multiplet
calculations of L2,3 x-ray absorption near-edge structures for 3d transition-metalcompounds”, J. Phys.: Condens. Matter 21, 104208 (2009).
【学術関係の受賞など】 日本学術振興会特別研究員 (DC2) 2005-2006－ 18 －

fukui2012_01.indb 18

14.1.9 1:23:07 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)⑸

シニアリサーチフェロー【氏名（ふりがな）
】 永瀬

茂（ながせ

しげる）

【職名】 シニアリサーチフェロー【所属】 福井謙一記念研究センター【研究室】 104 室【直通電話】 075-711-7792【FAX】 075-711-4757【電子メールアドレス】 nagase@fukui.kyoto-u.ac.jp【ホームページ】 http://www.fukui.kyoto-u.ac.jp/【研究分野】 理論化学・計算化学【現在の研究課題】 元素の特性とナノ構造を利用した分子設計の理論と計算【研究内容キーワード】 高周期典型元素、遷移金属、ナノカーボン、機能性分子【最終学歴】 1975 年 3 月大阪大学大学院基礎工学研究科博士課修了【学位】 1975 年 3 月工学博士（大阪大学）【略歴】 ロチェスター大学博士研究員、オハイオ州立大学博士研究員、分子科学研究所技官を経て、1980 年 4 月横浜国立大学助教授、1991 年 4 月横浜国立大大学
教授、1995 年 4 月東京都立大学教授、2001 年 4 月分子科学研究所教授、2012
年 4 月京都大学福井謙一記念研究センターシニアリサーチフェロー【所属学会】 日本化学会、分子科学会、ケイ素化学協会、アメリカ化学会【主な著書、学術論文】 1. T. Akasaka, F. Wudl, and S. Nagase, Eds., Chemistry of Nanocarbons, John Wiley（過去 5 年以内）
& Sons Ltd., Chichester (2010)
2. M. Yamada, T. Akasaka, and S. Nagase, Endohedral Metal Atoms in Pristine andFunctionalized Fullerene Cages, Acc. Chem. Res., 43, 92-102 (2010).
3. X. Lu, L. Feng, T. Akasaka, and S. Nagase, Current Statues and Future
Developments of Endohedral Metallofullerenes, Chem. Soc. Rev., 41, 7723-7760(2012).
4. S. Nagase, Multiple Bonds between Lead Atoms and Short Bonds between
Transition Metals, Pure Appl. Chem., 85, 649-659 (2013).
5. X. Lu, T. Akasaka, and S. Nagase, Carbide Cluster Metallofullerenes: Structure,
Properties, and Possible Origin, Acc. Chem. Res., in press.
6. M. Yamada, T. Akasaka, and S. Nagase, Carbene Additions to Fullerenes, Chem.
Rev., in press.
【学術関係の受賞】 2012 年 科学技術分野の文部科学大臣表彰科学技術賞（研究部門）、2012 年
福 井 メ ダ ル (Asia-Pacific Association of Theoretical & Computational Chemists) 、2013 年 日本化学会賞－ 19 －

fukui2012_01.indb 19

14.1.9 1:23:07 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)【氏名（ふりがな）】 諸熊

奎治 （もろくまけいじ）【職名】 シニアリサーチフェロー【所属】 福井謙一記念研究センター

福井謙一記念研究部門第一【研究室】 福井謙一記念研究センター 202【直通電話】 075-711-7843【FAX】 075-781-4757【電子メールアドレス】 morokuma@fukui.kyoto-u.ac.jp【ホームページ】 http://www.fukui.kyoto-u.ac.jp/~morokuma; http://kmweb.fukui.kyoto-u.ac.jp/【研究分野】 理論化学・計算化学【現在の研究課題】 複雑分子系の分子理論によるシミュレーション【研究内容キーワード】 分子理論。複雑分子系、シミュレーション、ナノ構造、酵素反応【最終学歴】 1962 年 3 月京都大学大学院工学研究科博士課程単位修得退学【学位】 1963 年 3 月工学博士（京都大学）【略歴】 1962 年 4 月 京 都 大 学 工 学 部 助 手、1964 年 9 月 Columbia 大 学 客 員 助 教 授、1966 年 9 月 Harvard 大 学 博 士 研 究 員、1967 年 9 月 Rochester 大 学 助 教 授、1971 年 9 月同教授、1976 年 12 月分子科学研究所教授、1993 年 1 月 Emory 大
学 William H. Emerson 教授、2006 年 9 月 Emory 大学名誉教授、2006 年 9 月京都大学福井謙一記念研究センターリサーチリーダー、2012 年４月同シニアリ
サーチフェロー
【所属学会】 日本化学会、American Chemical Society、分子科学会【主な著書、学術論文】 過去５年間に約１４０報（過去 5 年以内） 1. S. Maeda, E. Abe, M. Hatanaka, T. Taketsugu, and K. Morokuma, Exploring
Potential Energy Surfaces of Large Systems with Artificial Force Induced Reactionin Combination with ONIOM and Microiteration, J. Chem. Theo. Comp. 5, 5058–
5063 (2012).
2. A. J. Page, T. Isomoto, J. Knaup, S. Irle, and K. Morokuma, Effects of Molecular
Dynamics Thermostats on Descriptions of Chemical Non-Equilibrium, J. Chem.
Theo. Comp. 8, 4019–4028 (2012).
3. H.-B. Li, A. J. Page, S. Irle, and K. Morokuma, SWCNT Growth from Chiral
Carbon Nanorings: Prediction of Chirality and Diameter Influence on Growth
Rates, J. Am. Chem. Soc. 134, 15887–15896 (2012).
4. e Z. Ke, S. Abe, T. Ueno, and K. Morokuma, Catalytic Mechanism in Artificial
Metalloenzyme: QM/MM Study of Phenylacetylene Polymerization by Rhodium
Complex Encapsulated in apo-Ferritin J. Am. Chem. Soc. 134, 15418–15429 (2012).
5. H. Xiao, S. Maeda and K. Morokuma, Global Ab Initio Potential Energy Surfaces
for Low-lying Doublet States of NO3, J. Chem. Theo. Comp. 8, 2600–2605 (2012).
6. S. Sekharan, K. Katayama, H. Kandori and K. Morokuma. The“OH-Site”Rule for
Seeing Red and Green. J. Am. Chem. Soc. 134, 10706–10712 (2012).
7. S. Maeda, T. Taketsugu and K. Morokuma, Automated Exploration of Photolytic
Channels of HCOOH: Conformational Memory via Excited State Roaming, J.
Phys. Chem. Lett. 3, 1900-1907 (2012).
8. H.-B. Li, A. J. Page, Y. Wang, S. Irle, and K. Morokuma, Sub-Surface Nucleationof Graphene Precursers near a Ni(111) Step Edge. Chem. Comm. 48, 7937-7939(2012).
9. J. Kim, A. J. Page, S. Irle, and K. Morokuma, The Dynamics of Local Chirality
during SWCNT Growth: Armchair versus Zigzag Nanotubes, J. Am. Chem. Soc.
134, 9311–9319 (2012).
【学術関係の受賞など】 International Academy of Quantum Molecular Science (IAQMS) Medal, 1978; 日
本 化 学 会 賞 , 1992; The Schrödinger Medal, The World Association of Theoretical
Organic Chemists (WATOC), 1993; The Fukui Medal, Asian Pacific Association ofTheoretical & Computational Chemists, 2005; 恩賜賞、日本学士院賞 , 2008; 瑞宝
中綬章 , 2010; 文化功労者 , 2012－ 20 －

fukui2012_01.indb 20

14.1.9 1:23:08 PM

Ⅰ 専任教員 ･ スーパーバイザー (2012)⑹

リサーチリーダー【氏名（ふりがな）】 榊

茂好 （さかきしげよし）【職名】 リサーチリーダー【所属】 福井謙一記念研究センター：福井謙一記念研究部第２【研究室】 303

【直通電話】 075-711-7907【FAX】 075-711-4757【電子メールアドレス】 Sakaki.shigeyoshi.47e@st.kyoto-u.ac.jp【ホームページ】 http://www.users.iimc.kyoto-u.ac.jp/~z59354/【研究分野】 理論化学・計算化学【現在の研究課題】 遷移金属元素を含む複合電子系の構造、電子状態、反応過程の理論化学【研究内容キーワード】 電子状態理論・遷移金属錯体・反応解析・触媒作用・励起状態【学歴】 1974 年 3 月【学位】 1974 年 11 月

京都大学工学研究科燃料化学専攻博士課程単位取得退学
工学博士（京都大学）【略歴】 1975 年 4 月 熊本大学工学部助手、1982 年 1 月 同助教授、1990 年 4 月 同教授を経て、2002 年 4 月より京都大学工学研究科教授、2010 年 3 月定年、現在に至る。
【所属学会】 日本化学会、触媒学会、近畿化学協会、ケイ素化学協会、American Chemical Society【主な著書、学術論文】 1. Inverted Sandwich Type Dinuclear Chromium(I) Complex and Its Analogues of（過去 5 年以内）
Scandium(I), Titanium(I), Vanadium(I), Manganese(I), and Iron(I): Theoretical
Study of Electronic Structure and Bonding Nature, Y.-I. Kurokawa, Y. Nakao, S.
Sakaki, J. Phys. Chem. A, 114, 1191–1199 (2010).
2. Theoretical Study of Excited States of Pyrazolate- and Pyridinethiolate- Bridged
Dinuclear Platinum(II) Complexes: Relationship between Geometries of Excited
States and Phosphorescence Spectra, K. Saito, Y. Nakao, K. Umakoshi, S.Sakaki,
Inorg. Chem., 49, 8977–8985 (2010).
3. Multi-State CASPT2 Study of Native Iron(III)-dependent Catechol Dioxygenase
and Its Functional Models: Electronic Structure and Ligand-to-Metal ChargeTransfer Excitation, N. Nakatani, Y. Hitomi, S. Sakaki, J. Phys. Chem. B, 115,
4781–4789 (2011).
4. Theoretical Study of Pt(PR 3 ) 2 (AlCl 3 ) (R=H, Me, Ph, or Cy) Including an
Unsupported Bond between Transition Metal and Non-Transition Metal Elements;
Geometry, Bond Strength, and Prediction, S. Tsukamoto, S. Sakaki, J. Phys. Chem.
A, 115, 8520-8527 (2011).
5. Theoretical Study on High-Spin to Low-Spin Transition of Fe(pyrazine) [Pt(CN)4]}:
Guest-Induced Entropy Decrease, A. Hideo, Y. Nakao, H. Sato, M. Ohba,
S.Kitagawa, S. Sakaki, Chem. Phys. Lett. 511(4-6), 399-404 (2011).
6. Two-step evaluation of binding energy and potential energy surface of van der
Waals complexes, Milind Deshmukh, Shigeyoshi Sakaki, J. Compt. Chem.., 33,
617-628 (2012).
7. A Theoretical Study of an Unusual Y-Shaped Three-Coordinate Pt Complex: Pt(0)sigma-Disilane Complex or Pt(II) Disilyl Complex? N. Takagi, S. Sakaki, J. Am.
Chem. Soc., 134, 11749-11759 (2012).
14. Proposal of new QM/MM approach for geometry optimization of periodic
molecular crystal: Self-consistent point charge representation for crystalline effecton targetQM molecule, S. Aono and S. Sakaki, Chem. Phys. Lett. 544, 77-82 (2012).
15. Evaluation Procedure of Electrostatic Potential in 3D-RISM-SCF Method and Its
Application to Hydrolyses of Cis- and Transplatin Complexes, S. Aono and S.
Sakaki, J. Phys. Chem. B, 116, 13045-13062 (2012).
16. Complicated Electronic Process of C-C sigma-Bond Activation of Cyclopropene
by Ruthenium and Iridium Complexes: Theoretical Study
A. Ishikawa, Y. Tamura, Y. Nakao, H. Sato, and S. Sakaki, Organometallics, 31,
8189-8199 (2012).
【学術関係の受賞など】 第１回分子科学会賞 (2009 年 9 月 )－ 21 －

fukui2012_01.indb 21

14.1.9 1:23:08 PM

Ⅱ 博士研究員 (2012)

Ⅱ

博士研究員

１．博士研究員組織
平成２４年度職

名福井センターフェロー

氏

名

岩城

貴史

嶺澤

範行

岡本

隆一

齋藤

拓也

Fu-Quan Bai

長谷川グループ

Jingdong Guo

永瀬グループPeng Jin
Zhuofeng Ke

福井センターフェロー

Joonghan Kim
Alister Page
畑中

美穂

Fengyi Liu
Hong-yan Xiao

諸熊グループLina Ding
研究フェロー

Haibei Li
Lung Wa Chung
Galina Petrova
Travis Harris伊勢川

美穂

研究員（科学研究）山邊

信一

福井センターフェロー

土方

優

青野

信治

塚本

晋也

Milind Deshmukh
Guixiang Zeng
榊グループ

特推研究フェロー

髙木

望

中垣

雅之

吉澤

輝高

Wei Guan
Yue Chen

JSPS 特別研究員（受入れ研究者）分子科学研究所

専門研究職員

Sayyed Fareed Bhasha
松井

亨

河津

励

－ 22 －

fukui2012_01.indb 22

14.1.9 1:23:09 PM

Ⅱ 博士研究員 (2012)

２. 博士研究員プロフィール【氏名（ふりがな）】 岩城

貴史 （いわきたかふみ）【職名】 FIFC Fellow【所属】 京都大学福井謙一記念研究センター【研究室】 Room 209【直通電話】 075-711-7902【電子メールアドレス】 iwaki@fukui.kyoto-u.ac.jp【ホームページ】 http://www.fukui.kyoto-u.ac.jp/users/iwaki/topj.htm【研究分野】 Soft Matter, Biological Physics【現在の研究課題】 Interfacial Phenomena, PEMS of coarse-grained model polymer folding【研究内容キーワード】 Polyelectrolyte, DNA folding transition, Thermofluid, Photophoresis【学歴】 March 2001, Master of Sci., Graduate School of Science, Kyoto University
March 2004, Doctor of Sci., Graduate School of Science, Kyoto University【学位】 Doctor of Science from Kyoto University【略歴】 Apr. 2004, Postdoctoral Fellow at The City University of New York, USA
Apr. 2005, Okayama Institute for Quantum Physics【所属学会】 The Physical Society of Japan【主な著書、学術論文】 1. T. Saito, T. Iwaki, and K. Yoshikawa, “DNA compaction induced by neutralpolymer is retarded more effectively by divalent anion than monovalent anion”,（過去 5 年以内）
Chemical Physics Letters 465(1-3), 40-44(2008)
2. T. Iwaki, “Effect of internal flow on the photophoresis of a micron-sized liquid
droplet”, Physical Review E 81, 066315 (13 pages) (2010)
3. 吉川研一、岩城貴史、“細胞の自己組織化”に物理の視点から迫る”, パリ
ティ 2011年5月号 pp. 13-21
4. Y. Higuchi, K. Yoshikawa, T. Iwaki, “Stiffness causes opposite trend on the folding
transition of a single polymer chain in a confined space”, Physical Review E 84,
021924 (5 pages)

5. “Probability of double-strand breaks in genome-sized DNA by γ-ray decreases
markedly as the DNA concentration increases”, S. F. Shimobayashi, T. Iwaki, T.
Mori, and K. Yoshikawa, The Journal of Chemical Physics, Accepted.

－ 23 －

fukui2012_01.indb 23

14.1.9 1:23:09 PM

Ⅱ 博士研究員 (2012)【氏名（ふりがな）】 嶺澤

範行 （みねざわのりゆき）【職名】 福井センターフェロー【所属】 京都大学福井謙一記念研究センター【研究室】 京都大学福井謙一記念研究センター 209 号室【直通電話】 075-711-7902【FAX】 075-781-4757【電子メールアドレス】 minezawa@fukui.kyoto-u.ac.jp【研究分野】 計算化学・理論化学【現在の研究課題】 理論化学・計算化学【研究内容キーワード】 時間依存密度汎関数法を用いた溶液内分子の自由エネルギー計算【学歴】 時間依存密度汎関数法・積分方程式【学位】 2008 年 3 月京都大学大学院理学研究科化学専攻博士課程修了【略歴】 2008 年 5 月米国アイオワ州立大学 (Mark S. Gordon 教授 )2011 年 10 月京都大学福井謙一記念研究センター・センターフェロー【所属学会】 アメリカ化学会【主な著書、学術論文】 1. K. R. Brorsen, N. Minezawa, F. Xu, T. L. Windus, and M. S. Gordon, “Fragment
molecular orbital molecular dynamics with the fully analytic energy gradient”, J.
（過去 5 年以内）
Chem. Theory Comput. 8, 5008-5012 (2012).
2. N. Minezawa and M. S. Gordon, “Optimizing conical intersections of solvatedmolecules: The combined spin-flip density functional theory/effective fragment
potential method”, J. Chem. Phys. 137, article No. 034116 [12 pages] (2012).
3. A. Defusco, N. Minezawa, L. V. Slipchenko, F. Zahariev, and M. S. Gordon,“Modeling solvent effects on electronic excited states”, J. Phys. Chem. Lett. 2,
2184-2192 (2011).
4. N. Minezawa and M. S. Gordon, “Photoisomerization of stilbene: A spin-flip
density functional theory approach”, J. Phys. Chem. A 115, 7901-7911 (2011).
5. N. Minezawa, N. De Silva, F. Zahariev, and M. S. Gordon, “Implementation of
the analytic energy gradient for the combined time-dependent density functional
theory/effective fragment potential method: Application to excited-state molecular
dynamics simulations”, J. Chem. Phys. 134, article No. 054111 [12 pages] (2011).

－ 24 －

fukui2012_01.indb 24

14.1.9 1:23:09 PM

Ⅱ 博士研究員 (2012)【氏名（ふりがな）】 岡本

隆一 （おかもとりゅういち）【職名】 FIFC フェロー【所属】 福井謙一記念研究センター【研究室】 204 号室【直通電話】 075-711-7863【FAX】 075-781-4757【電子メールアドレス】 okamoto_r@fukui.kyoto-u.ac.jp【ホームページ】 http://www.fukui.kyoto-u.ac.jp/users/okamoto/index.html【研究分野】 ソフトマター、相転移【現在の研究課題】 ソフトマターにおける溶媒和効果、臨界溶液中の物体間相互作用【研究内容キーワード】 Soft matter, Phase transition, Wetting, Critical phenomena, Colloid【学歴】 2007 年３月

慶應義塾大学基礎理工学専攻後期博士課程修了【学位】 博士 ( 理学 )【略歴】 2007 年 4 月 -2012 年 3 月 京都大学理学研究科博士研究員
2012 年 4 月 - 京都大学福井謙一研究センター FIFC フェロー
現在に至る
【所属学会】 日本物理学会【主な著書、学術論文】 1. R. Okamoto and A. Onuki: “Ion distribution around a charged rod in one andtwo component solvents: Preferential solvation and first order ionization phase（過去 5 年以内）
transition”, J. Chem. Phys. 131, 094905 (2009). (Also in Virtual Journal of
Nanoscale Science and Technology, September 14, 2009)
2. R. Okamoto and A. Onuki: “Precipitation in aqueous mixtures with addition ofstrongly hydrophilic or hydrophobic solute”, Phys. Rev. E 82, 051501 (2010). (Alsoin Virtual Journal of Nanoscale Science and Technology, November 22, 2010)
3. R. Okamoto and A. Onuki: “Charged Colloids in an aqueous mixture with asalt”, Phys. Rev. E 84, 051401 (2011)
4. R. Okamoto and A. Onuki: “Casimir amplitudes and capillary condensation of nearcritical fluids between parallel plates: Renormalized local functional theory”, J.
Chem. Phys. 136, 114704 (2012)－ 25 －

fukui2012_01.indb 25

14.1.9 1:23:09 PM

Ⅱ 博士研究員 (2012)【氏名】 Takuya Saito【職名】 FIFC Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 204【直通電話】 075-711-7863【電子メールアドレス】 saito@fukui.kyoto-u.ac.jp【研究分野】 Polymer Physics and Biophysics【現在の研究課題】 Dynamics of Polymer Transportation【研究内容キーワード】 Stretching dynamics, DNA compaction, Chromatin【学歴】 March 2004, Master of Sci., Graduate School of Science, Kyoto University
March 2007, Doctor of Sci., Graduate School of Science, Kyoto University【学位】 Doctor of Science from Kyoto University【略歴】 May 2007, The University of Tokyo
Apr. 2010, Kyushu University【所属学会】 The Physical Society of Japan【主な著書、学術論文】 1. Takuya Saito, Takahiro Sakaue, “Process time distribution of driven polymertranslocation”, Phys. Rev. E, 85, 061803 (7 pages total) (2012).
（過去 5 年以内）

2. Takahiro Sakaue, Takuya Saito, Hirofumi Wada, “Dragging a polymer in a viscous
fluid: steady state and transient”, Phys. Rev. E, 86, 011804 (8 pages total) (2012).

3. 坂上貴洋、齋藤拓也, 日本物理學會誌 67(10), 705-709, 2012-10-05.「紐状分子の非平衡ダイナミクス：細孔通過現象を中心に」
4. Takuya Saito, Takahiro Sakaue, Daiji Kaneko, Masao Washizu and Hidehiro Oana,“Folding dynamics of tethered giant DNA under strong flow”, The Journal ofChemical Physics, 135, 154901 (5 pages total) (2011).
5. Takuya Saito and Takahiro Sakaue, “Driven Translocation of Semi-flexible Polymer
under Strong Force”, Progress of Theoretical Physics Supplement, 191, 210-214(2011).
6. Takuya Saito and Kenichi Yoshikawa, “Finite-width bundle is most stable in asolution with salt”, The Journal of Chemical Physics, 133, 045102 (6 pages total)(2010).
7. Takuya Saito, Takafumi Iwaki and Kenichi Yoshikawa, “Small Anion with Higher
Valency Retards the Compaction of DNA in the Presence of Multivalent Cation”,
Biophysical Journal, 96, 1068-1075 (2009).
8. Takuya Saito, Takafumi Iwaki and Kenichi Yoshikawa, “DNA compaction inducedby neutral polymer is retarded more effectively by divalent anion than monovalentanion”, Chemical Physics Letters, 465, 40-44 (2008).
【学術関係の受賞など】 JSPS Research Fellowships for Young Scientists(DC2) 2005.4-2007.3－ 26 －

fukui2012_01.indb 26

14.1.9 1:23:09 PM

Ⅱ 博士研究員 (2012)【氏名】 Fu-Quan Bai【職名】 Associate Professor【所属】 Jilin University【研究室】 State Key Laboratory Of Theoretical And Computational Chemistry【直通電話】 +86-431-88498966【FAX】 +86-431-88498966【電子メールアドレス】 baifq@jlu.edu.cn【ホームページ】 http://tcclab.jlu.edu.cn/gr/baifq.html【研究分野】 Theoretical Chemistry and Computational Chemistry【現在の研究課題】 Reaction in excited state and molecular spectroscopy【研究内容キーワード】 Exicted state, spectrum, reaction, bond break, DFT, TDDFT, MD【学歴】 Jun. 2004, B.S. Major in Chemistry, College of Chemistry, Jilin University
Jun. 2009, Ph.D. Major in Theoretical and Computational Chemistry, Institute ofTheoretical Chemistry, State Key Laboratory of Theoretical and Computational
Chemistry, Jilin University【学位】 Ph.D. of Science from Jilin University
Thesis: Quantum theoretical studies on the excited state and spectroscopic propertiesof transition metal complexes: Pt complexes【略歴】 Jul. 2009, Research assistant, Jilin University
Apr. 2012, FIFC Fellow, Kyoto University【所属学会】 Chinese Chemical Society【主な著書、学術論文】 1. Qi Cao, Jing Wang, Zhao-Shuo Tian*, Zai-Feng Xie*, Fu-Quan Bai*, “Theoreticalinvestigation on the photophysical properties of N-heterocyclic carbene Ir (III)（過去 5 年以内）
complexes (fpmb)xIr(bptz)3-x (x=1-2)”. Journal of Computational Chemistry, (2012),
33(10), 1038-1046.
2. Fu-Quan Bai, Jian Wang, Bao-Hui Xia, Qing-Jiang Pan, Hong-Xing Zhang*, “DFTand TD-DFT study on the electronic structures and phosphorescent propertiesof 6-phenyl-2,2 '-bipyridine tridentate iridium(III) complexes and their isomer”.
Dalton Transactions, (2012), 41(27), 8441-8446.
3. Juan Jin, Fu-Quan Bai, Ming-Jun Jia, Jie-Hui Yu*, Ji-Qing Yu*, “Newmonoacylhydrazidate-coordinated Mn2+ and Pb2+ compounds”. Dalton
Transactions, (2012), 41(20), 6137-6147.
4. Jian Wang, Fu-Quan Bai, Bao-Hui Xia, Hong-Xing Zhang*, “Efficient blueemitting ir(iii) complexes with phosphine carbanion-based ancillary ligand: a DFT
study”. Journal of Physical Chemistry A, (2011), 115(42), 11689-11695.
5. Lei Sun, Fu-Quan Bai, Zeng-Xia Zhao, Hong-Xing Zhang*, “Design of new
benzothiadiazole-based linear and star molecules with different functional groups
as solar cells materials: A theoretical approach”. Solar Energy Materials and Solar
Cells, (2011), 95(7), 1800-1810.
6. Fu-Quan Bai, Xin Zhou, Bao-Hui Xia，Tao Liu, Jian-Po Zhang, Hong-Xing
Zhang*. “Electronic structures and optical properties of neutral substituted fluorenebased cyclometalated platinum(II) - acetylide complexes: A DFT exploration”.
Journal of Organometallic Chemistry, (2009), 694(12), 1848–1860.
7. Guangjin Zhao, Guanglong Wu, Chang He, Fu-Quan Bai, Hongxia Xi, HongXing Zhang, Yongfang Li*, “Solution-Processable Multiarmed Organic Molecules
Containing Triphenylamine and DCM Moieties: Synthesis and Photovoltaic
Properties”. Journal of Physical Chemistry C, (2009), 113(6), 2636-2642.
【学術関係の受賞など】 Teaching scheme design award, 2009
NSFC Young Scholar, 2010
－ 27 －

fukui2012_01.indb 27

14.1.9 1:23:09 PM

Ⅱ 博士研究員 (2012)【氏名】 Jingdong Guo【職名】 SPR Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 104【直通電話】 075-711-7792【FAX】 075-711-7838【電子メールアドレス】 jdguo@ fukui.kyoto-u.ac.jp【研究分野】 Theoretical Chemistry【現在の研究課題】 Theoretical studies of C-H Activation of Cycloalkenes by Dimetallynes (M=Ge, Sn)【研究内容キーワード】 Reaction mechanism, heavier group 14 elements【学歴】 2004, Doctor of Philosophy in Theoretical Chemistry, Royal Institute of Technology,
Sweden【学位】 Doctor of Philosophy, Royal Institute of Technology, Sweden【略歴】 2007-2012,Postdoctoral Fellow, Institute for Molecular Science, Japan【主な著書、学術論文】 1. Katsuhiko Takeuchi, Masaaki Ichinohe, Akira Sekiguchi, Jing-Dong Guo, and（過去 5 年以内）
Shigeru Nagase, Reactivity of Disilyne RSiSiR (R=SiiPr[CH(SiMe3)2]2) toward
Nitriles: Unexpected Formation of Triaza-1,4-disilabicyclo-[2.2.2]octa-2,5,7-triene
Derivatives, Organometallics, 28, 2658-2660 (2009)
2. Katsuhiko Takeuchi, Masaaki Ichinohe, Akira Sekiguchi, Jing-Dong Guo, andShigeru Nagase, Reactivity of the Disilyne RSiSiR (R=SiiPr[CH(SiMe3)2]2) towardbis(silylcyanide) forming a 1,4-diaza-2,3-disilabenzene analog, J. Phys. Org.
Chem., 23, 390-394 (2009)

3. Yang Peng, Jing-Dong Guo, Bobby D. Ellis, Zhongliang Zhu, James C. Fettinger,
Shigeru Nagase, and Philip P. Power, Reaction of Hydrogen or Ammonia with
Unsaturated Germanium or Tin Molecules under Ambient Conditions: Oxidative
Addition versus Arene Ellmination, J. Am. Chem. Soc., 131, 16272-16282 (2009)
4. Xinping Wang, Yang Peng, Zhongliang Zhu, James C. Fettinger, Philip P. Power,
Jingdong Guo, and Shigeru Nagase, Synthesis and Characterization of Two of theThree Isomers of a Germanium-Substituted Bicyclo[2.2.0]hexane Diradicaloid:
Stretching the Ge-Ge Bond, Angew. Chem. Int. Ed., 49, 4593-4597 (2010)

5. Zachary D. Brown, Jing-Dong Guo, Shigeru Nagase, and Philip P. Power,
Experimental and Computational Study of Auxiliary Molecular Effects on the
Mechanism of the Addition of Hydrazines to a Low-Valent Germanium Complex,
Organometallics, 31, 3768-3772 (2012)
6. Satoru Sato, Yutaka Maeda, Jing-Dong Guo, Michio Yamada, Naomi Mizorogi,
Shigeru Nagase, and Takeshi Akasaka, Mechanistic Study of the Diels-Alder
Reaction of Paramagnetic Endohedral Metallofullerene: Reaction of La@C82 with
1,2,3,4,5-Pentamethylcyclopentadiene, J. Am. Chem. Soc., 135, 5582-5587 (2013)－ 28 －

fukui2012_01.indb 28

14.1.9 1:23:10 PM

Ⅱ 博士研究員 (2012)【氏名】 Peng Jin【職名】 Assistant Professor【所属】 Hebei University of Technology, China【電子メールアドレス】 China.peng.jin@gmail.com【研究分野】 Computational Chemistry【現在の研究課題】 Fullerenes and related cluster chemistry【研究内容キーワード】 Endohedral metallofullerenes, chemical functionalization of fullerenes【学歴】 October 2010, Doctor of Eng., School of Chemical Engineering, Dalian University ofTechnology, China【学位】 Doctor of Engineering from Dalian University of Technology【主な著書、学術論文】 1. Peng Jin, Ce Hao, Zhanxian Gao, Shengbai B. Zhang, and Zhongfang Chen,“Endohedral Metalloborofullerenes La2@B80 and Sc3N@B80: A Density Functional（過去 5 年以内）
Theory Prediction”, J. Phys. Chem. A 113, 11613-11618(2009).
2. Peng Jin, Zhen Zhou, Ce Hao, Zhanxian Gao, Kai Tan, Xin Lu, and Zhongfang
Chen, “NC Unit Trapped by Fullerenes: A Density Functional Theory Studyon Sc 3NC@C 2n (2n = 68, 78 and 80)”, Phys. Chem. Chem. Phys. 12, 1244212449(2010).
3. Peng Jin, Fengyu Li, Kevin Riley, Dieter Lenoir, Paul v. R. Schleyer, andZhongfang Chen, “What is the Preferred Structure of the Meisenheimer-Wheland
Complex between sym-Triaminobenzene and 4, 6-Dinitrobenzofuroxan?”, J. Org.
Chem. 75, 3761-3765(2010).
4. Peng Jin, Fengyu Li, and Zhongfang Chen, “Theoretical Design of Novel Trinuclear
Sandwich Complexes with Central M3 Triangles (M = Ni, Pd, Pt)”, J. Phys. Chem.
A 115, 2402–2408(2011).
5. Peng Jin, Yongsheng Chen, Shengbai B. Zhang, and Zhongfang Chen, “Interactions
between Al12X (X = Al, C, N and P) Nanoparticles and DNA Nucleobases/basePairs: Implication to Nanotoxicity”, J. Mol. Model. 18, 559-568(2012).

－ 29 －

fukui2012_01.indb 29

14.1.9 1:23:10 PM

Ⅱ 博士研究員 (2012)【氏名】 Zhuofeng Ke【職名】 Associate Professor【所属】 Sun Yat-sen University, China【研究室】 Physical Chemistry【直通電話】 +86-20-84113071【電子メールアドレス】 Kezhf3@mail.sysu.edu.cn【研究分野】 Computational Chemistry【現在の研究課題】 Computational and experimental study on novel molecular transformation.
【研究内容キーワード】 Computational study of catalysis processes in organometallic systems and bio-systems【学歴】 2002 B.Sc. in Chemistry, Sun Yat-sen University,
2005 M.Sc. in Polymer Chemistry and Physics, Sun Yat-sen University
2007 Jointly Educating Ph.D. in computational organometallic chemistry, Universityof North Texas,
2009 Ph.D. in Physical Chemistry (Theoretical and Computational Chemistry), Sun
Yat-sen University【学位】 Ph.D. in Physical Chemistry (Theoretical and Computational Chemistry), Sun Yat-sen
University【所属学会】 American Chemical Society【学会活動】 241st ACS National Meeting in Anaheim, CA.
【主な著書、学術論文】 1. Ke, Zhuofeng, Abe, S., Ueno, T., & Morokuma, Keiji, Catalytic Mechanism in（過去 5 年以内）
Artificial Metalloenzyme: QM/MM Study of Phenylacetylene Polymerization
by Rhodium Complex Encapsulated in apo-Ferritin. J. Am. Chem. Soc. 134 (37),15418–15429 (2012).
2. Ke, Zhuofeng, Abe, S., Ueno, T., & Morokuma, Keiji, J. Am. Chem. Soc. 133(20), 7926-7941 (2011) (JACS beta Select issue 13: Current Applications ofComputational Chemistry in JACS - Molecules, Mechanisms and Materials)

3. Liu, Y., Ke, Zhuofeng, Liu, Shuwen, Chen, Wen-Hua, Jiang, Shibo; Jiang, ZhiHong. ChemMedChem 6 (9), 1654- 1664 (2011)..
4. Gao, H., Ke, Zhuofeng, DeYonker N. J., Wang J., Xu H., Mao Z.-W., Phillips, D.L.,& Zhao C. J. Am. Chem. Soc., 2011, 133 (9), 2904–2915

5. Ke, Zhuofeng & Cundari, T.R. Organometallics 29 (4), 821-834 (2010). (Top10
Most Accessed Articles of Organometallics in 2010)【学術関係の受賞など】 Sun Yat-sen University Fellow 2009
State Scholarship Funds, China Scholarship Council (CSC) 2007

－ 30 －

fukui2012_01.indb 30

14.1.9 1:23:10 PM

Ⅱ 博士研究員 (2012)【氏名】 Joonghan Kim【職名】 FIFC Fellow【所属】 Fukui Kenichi Memorial Research Group 1, Fukui Institute for Fundamental
Chemistry【研究室】 Room 203【直通電話】 075-711-7708【FAX】 075-781-4757【電子メールアドレス】 joonghan@fukui.kyoto-u.ac.jp; quatum99@gmail.com【研究分野】 Computational Chemistry【現在の研究課題】 DFTB-MD simulation of chirality-controlled carbon nanotube growth anddetermination of local chirality of carbon nanotube【研究内容キーワード】 Carbon nanotube, density-functional tight-binding, chirality【学歴】 2004 B. Sc., Hanyang University, Seoul, Korea
2010 Ph. D., KAIST, Daejeon, Korea【学位】 Doctor of Philosophy, KAIST, Daejeon, Korea【略歴】 2010, Postdoctoral fellow, KAIST, Daejeon, Korea【所属学会】 Korean Chemical Society【主な著書、学術論文】 1. Joonghan Kim, Sunhong Jun, Jeongho Kim, and Hyotcherl Ihee, “Density
Functional and Ab Initio Investigation of CF2ICF2I and CF2CF2I Radicals in Gas（過去 5 年以内）
and Solution Phases”, J. Phys. Chem. A 113, 11059-11066 (2009).
2. Joonghan Kim, Tae Kyu Kim, and Hyotcherl Ihee, “Theoretical Study on theReaction of Ti+ with Acetone and the Role of Intersystem Crossing”, J. Phys. Chem.
A 113, 11382-11389 (2009).
3. Jeewon Kang, Joonghan Kim, Hyotcherl Ihee, and Yoon Sup Lee, “Molecular
Structures, Energetics and Electronic Properties of Neutral and Charged Hgn
Clusters (n= 2–8)", J. Phys. Chem. A 114, 5630-5639 (2010).
4. Joonghan Kim, Hyotcherl Ihee, and Yoon Sup Lee, “Spin-Orbit Density Functionaland Ab Initio Study of HgXn (X=F, Cl, Br, and I; n=1, 2, and 4)”, J. Chem. Phys.
133, 144309 (2010).
5. Joonghan Kim, Tae Kyu Kim, and Hyotcherl Ihee, “Density Functional and SpinOrbit Ab Initio Study of CF 3Br: Molecular Properties and Electronic CurveCrossing”, J. Phys. Chem. A 115, 1264-1271 (2011).
6. Joonghan Kim, Hyotcherl Ihee, and Yoon Sup Lee, “Spin-orbit ab initio study of
two low-lying states of chloroiodomethane cation”, Theor. Chem. Acc. 129, 343347 (2011).
7. Joonghan Kim, Stephan Irle, and Keiji Morokuma, “Determination of Local
Chirality in Irregular Single-Walled Carbon Nanotubes Based on Individual
Hexagons”, Phys. Rev. Lett. 107, 175505 (2011)
8. Joonghan Kim and Hyotcherl Ihee, “Theoretical Study on the Reaction of
Butadiynyl Radical (C 4H) with Ethylene (C 2H4) to Form C6H4 and H”, Int. J.
Quantum Chem. 112, 1913-1925 (2012).
9. Joonghan Kim, Alister J. Page, Stephan Irle, and Keiji Morokuma, “Determinationof Local Chirality in Irregular Single-Walled Carbon Nanotubes Based on
Individual Hexagons”, J. Am. Chem. Soc. 134, 9311-9319 (2012)－ 31 －

fukui2012_01.indb 31

14.1.9 1:23:10 PM

Ⅱ 博士研究員 (2012)【氏名】 Alister Page
【職名】 Fukui Fellow【所属】 Fukui Kenichi Memorial Research Group 1, Fukui Institute for Fundamental
Chemistry【研究室】 Room 203【直通電話】 075-711-7831【FAX】 095-781-4757【電子メールアドレス】 alisterpage@fukui.kyoto-u.ac.jp【研究分野】 Computational Chemistry【現在の研究課題】 Molecular Dynamics simulations and electronic structure calculations of nanoscale
self-assembly processes (in particular, carbon nanotube & graphene nucleation andgrowth).
【研究内容キーワード】 Single-walled carbon nanotube, garphene self-assembly, nucleation, growth, healing,(n,m)chirality, functionalization density-functional tight-binding【学歴】 2004, Bachelor of Mathematics (Honours Class I), The University of Newcastle,
Australia
2004, Bachelor of Science (Honours Class I), The University of Newcastle, Australia
2008, Doctor of Philosophy, The University of Newcastle, Australia【学位】 Doctor of Philosophy, The University of Newcastle, Australia【略歴】 2008, Postdoctoral Research Associate, Priority Research Centre for Energy,
Department of Chemical Engineering, The University of Newcastle, Australia
2009-2010, CREST Postdoctoral Research Fellow, Fukui Institute for Fundamental
Chemistry, Kyoto University, Japan
2010-2012, Fukui Postdoctoral Research Fellow, Fukui Institute for Fundamental
Chemistry, Kyoto University, Japan【所属学会】 American Chemical Society, Royal Australian Chemistry Institute【主な著書、学術論文】 1. Y. Wang, A. J. Page, H.-J. Qian, Y. Nishomoto, S. Irle, K. Morokuma, “Template
Effect in the Competition Between Haeckelite and Graphene Growth on Ni(111):（過去 5 年以内）
Quantum Chemical Molecular Dynamics Simulations.”, J. Am. Chem. Soc., 133,
18837, (2011)
2. A. J. Page, K.R.S. Chandrakumar, S. Irle, K. Morokuma, “SWNT Nucleation from
Carbon-Coated SiO2 Nanoparticles via a Vapor-Solid-Solid Mechanism”. J. Am.
Chem. Soc., 132, 15699, (2011)
3. A. J. Page, Y. Ohta, S. Irle, K. Morokuma, “Mechanisms of Single-Walled Carbon
Nanotube Nucleation, Growth and Healing Determined using QM/MD Methods”,
Acc. Chem. Res., 43, 1375, (2010)
4. A. J. Page, Y. Ohta, Y. Okamoto, S. Irle, K. Morokuma, “Defect Healing During
Single-Walled Carbon Nanotube Growth: A Density-Functional Tight-Binding
Molecular Dynamics Investigation”, J. Phys. Chem. C, 113, 20198, (2009)
5. A. J. Page, E. I. von Nagy-Felsobuki, “Rovibrational Spectra of LiH2+, LiHD+ and
LiD2+ Determined using FCI Property Surfaces”, J. Phys. Chem. A, 111, 4478, (2007)【学術関係の受賞など】 Australian Post-Graduate Award (2005-2008)
RACI Chemistry Honours Prize (2004)
Deans Medal, Faculty of Science and IT, The University of Newcastle (2004)－ 32 －

fukui2012_01.indb 32

14.1.9 1:23:11 PM

Ⅱ 博士研究員 (2012)【氏名（ふりがな）】 畑中

美穂 （はたなかみほ）【職名】 福井センターフェロー【所属】 福井記念研究センター
212 号室【研究室】 福井記念研究センター【直通電話】 075-711-7647【電子メールアドレス】 miho@fukui.kyoto-u.ac.jp【研究分野】 量子化学

理論化学

【現在の研究課題】 ・ ランタノイド触媒を用いる向山アルドール反応の配位構造と立体選択性
・ Gd(III)-MRI コントラスト剤の安定構造とその構造ゆらぎ
・ 人工力誘起反応 (AFIR) 法による IPNS 酵素の全反応経路探索
・ 一酸化窒素還元酵素（cNOR、qNOR）の反応機構
・ 密度行列繰り込み群 (DMRG) の方法を用いるアクチノイド二量体の電子状
態と結合性【研究内容キーワード】 ランタノイド触媒

酵素反応

反応自動経路探索法【学歴】 2011 年 3 月

慶應義塾大学大学院理工学研究科
基礎理工学専攻後期博士課程修了【学位】 2011 年 3 月

博士（理学） 慶應義塾大学【略歴】 2009 年 4 月 慶應義塾大学大学院理工学研究科助教 ( 有期・研究奨励 )2011 年 4 月 京都大学福井謙一記念研究センターフェロー【所属学会】 日本化学会、分子科学会【主な著書、学術論文】 1. M. Hatanaka, S. Maeda, K. Morokuma, “Sampling of Transition States for
Predicting Diastereoselectivity Using Automated Search Method―Aqueous（過去 5 年以内）
Lanthanide-Catalyzed Mukaiyama Aldol Reaction” J. Chem. Theory Comput. In
press.
2. S. Maeda, E. Abe, M. Hatanaka, T. Taketsugu, K. Morokuma, “Exploring Potential
Energy Surfaces of Large Systems with Artificial Force Induced Reaction Method
in Combination with ONIOM and Microiteration” J. Chem. Theory Comput. 8,
pp5058-5063 (2012).
3. M. Hatanaka, S. Yabushita, “An ab initio study on the f−f hypersensitive transition
intensities of lanthanide tribromide molecules”, Chemical Physics Letters 504, pp
193-198 (2011).
4. M. Hatanaka, S. Yabushita, “Theoretical Study on the f−f Transition Intensities ofLanthanide Trihalide Systems”, Journal of Physical Chemistry A 113, pp 1261512625 (2009).
5. T. Ikeno, I. Iwakura, A. Shibahara, M. Hatanaka, A. Kokura, S. Tanaka, T. Nagata,
T. Yamada, “Newly Designed Catalysts for the Enantioselective Borohydride
Reduction: Prediction from the Theoretical Analysis”, Chemistry Letters 36, pp
738-739 (2007).
6. I. Iwakura, M. Hatanaka, A. Kokura, H. Teraoka, T. Ikeno, T. Nagata, T. Yamada,“The Reactive Intermediate of Catalytic Borohydride Reduction by Schiff BaseCobalt Comples”, Chemistry – An Asian Journal 1, pp 656-663 (2006).
【学術関係の受賞など】 2009 年 3 月 日本化学会第 89 春季年会 学生講演賞
2010 年 4 月 公益信託 林女性自然科学者研究助成基金 林フェロー
2011 年 4 月 京都大学福井謙一記念研究センターフェロー－ 33 －

fukui2012_01.indb 33

14.1.9 1:23:11 PM

Ⅱ 博士研究員 (2012)【氏名】 Fengyi Liu【職名】 Postdoctoral Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 203【直通電話】 075-711-7831【電子メールアドレス】 fengyiliu@fukui.kyoto-u.ac.jp【研究分野】 Computational Chemistry【現在の研究課題】 Theoretical calculation of molecular motor and switch【研究内容キーワード】 Artificial/biological molecular motor, molecular switch【学歴】 Jun. 1998, B. Sc. in Chemistry, Hebei Normal University, China
Jun. 2001, M. Sc. in Chemistry, Hebei Normal University, China
Dec. 2005, Ph.D. in Chemistry, Beijing University of Chemical Technology, China【学位】 Ph. D. in Applied Chemistry, Beijing University of Chemical Technology【略歴】 Sep. 2007-Jun. 2009, Postdoctoral researcher, Lund University, Sweden【主な著書、学術論文】 1. Fengyi Liu and Keiji Morokuma, Computational Study on the Working Mechanism（過去 5 年以内）
of a Stilbene Light-Driven Molecular Rotary Motor: Sloped Minimal Energy Pathand Unidirectional Nonadiabatic Photoisomerization, J. Am. Chem. Soc., 2012, 134,
4864–4876.
2. Shu-Feng Chen, Ya-Jun. Liu, Fengyi Liu, Luca De Vico, Roland Lindh,Multireference calculations on the chemical origin and mechanism of fireflybioluminescence, Luminescence, 2010, 25, 89-90.
3. Fengyi Liu, Yajun liu, Luca De Vico, Roland Lindh, A CASSCF/CASPT2 Approachto the Decomposition of Thiazole-Substituted Dioxetanone: Substitution Effects
and Charge-Transfer Induced Electron Excitation, Chem. Phys. Lett. 2009, 484, 6975.
4. Fengyi Liu, Yajun Liu, Luca De Vico, Roland Lindh, Theoretical Study of the
Chemiluminescent Decomposition of Dioxetanone, J. Am. Chem. Soc., 2009, 131,6181-6188.
5. Shu-Feng Chen, Feng-Yi Liu, Ya-Jun Liu, An ab initio investigation of themechanisms of photodissociation in bromobenzene and iodobenzene, J. Chem.
Phys., 2009, 131, 124304.

－ 34 －

fukui2012_01.indb 34

14.1.9 1:23:11 PM

Ⅱ 博士研究員 (2012)【氏名】 Hong-Yan Xiao
【職名】 Associate professor【所属】 Technical Institute of Physics and Chemistry, Chinese Academy of Sciences【研究室】 Room 101【直通電話】 +86-010-8254-3530【FAX】 +86-010-8254-3529【電子メールアドレス】 hyxiao@mail.ipc.ac.cn【研究分野】 Computational Chemistry【現在の研究課題】 Photodissociation mechanism of small molecules【研究内容キーワード】 Photodissociation, excited state, conical intersection, nonadiabatic transition【学歴】 Jun. 2002, B. Sc. in Chemistry, Liaoning Normal University, China
Jun. 2005, M. Sc. in Physical Chemistry, Liaoning Normal University, China
Jun. 2008, Ph. D. in Physical Chemistry, Beijing Normal University, China【学位】 Ph. D. in Physical Chemistry, Beijing Normal University【略歴】 July 2008-till now, assistant professor, associate professor, Technical Institute ofPhysics and Chemistry, Chinese Academy of Science
July 2010-September 2012, Postdoctoral Fellow, Fukui Institute for Fundamental
Chemistry【主な著書、学術論文】 1. Hong-Yan Xiao, Satoshi Maeda and Keiji Morokuma. Excited-state roaming
dynamics in photolysis of a nitrate radical. J. Phys. Chem. Lett. 2, 934-938 (2011)（過去 5 年以内）

2. Michael P. Grubb, Michelle L. Warter, Hong-Yan Xiao, Satoshi Maeda, Keiji
Morokuma and Simon W. North. No straight path: roaming in both ground- andexcited-state photolytic channels of NO3 → NO +O2. Science 335, 1075-1078 (2012)

3. Hong-Yan Xiao, Satoshi Maeda and Keiji Morokuma. Global ab initio potential
energy surfaces for low-lying doublet states of NO3. J. Chem. Theory Comput. 8,
2600-2605 (2012)

4. Jie-Yun Wu, Shu-Hui Bo, Jia-Lei Liu, Ting-Ting Zhou, Hong-Yan Xiao, Ling Qiu,
Zhen Zhen and Xin-Lou Liu. Synthesis of novel nonlinear optical chromophore toachieve ultrahigh electro-optic activity. Chem. Commun. 48, 9637-9639 (2012)
5. Bi-Na Fu, Joel M. Bowman, Hong-Yan Xiao, Satoshi Maeda and Keiji Morokuma.
Quasiclassical trajectory studies of the photodissociation dynamics of NO3 from theD0 and D1 potential energy surfaces. J. Chem. Theory Comput. 9, 893-900 (2013)

6. Hong-Yan Xiao, Satoshi Maeda and Keiji Morokuma. CASPT2 study ofphotodissociation pathways of ketene. J. Phys. Chem. A in press (DOI: 10.1021/
jp312719a)【学術関係の受賞など】 Qiu Shi Graduate Student Scholarship in Beijing Normal University (2007)
National Natural Science Foundation of China (2010)－ 35 －

fukui2012_01.indb 35

14.1.9 1:23:11 PM

Ⅱ 博士研究員 (2012)【氏名】 Lina Ding （丁麗娜）【職名】 JST Fellow【所属】 Fukui Institute For Fundamental Chemistry【研究室】 Room 212【直通電話】 075-711-7631【電子メールアドレス】 ding@fukui.kyoto-u.ac.jp【現在の研究課題】 photobiology【研究内容キーワード】 Photo reaction mechanism of biochemical and metal-complexes systems【学歴】 Jun. 2004, B. Sc. in Chemistry, Zhengzhou University, China
Jun. 2007, M. Sc. in Organic Chemistry, Zhengzhou University, China
Jun. 2010, Ph.D. in Physical Chemistry, Beijing Normal University, China【学位】 Ph.D. in Physical Chemistry, Beijing Normal University, China【主な著書、学術論文】 1. Lina Ding, Lung Wa, Chung, Keiji Morokuma*, Excited-State Proton Transfer
Controls Irreversibility of Photoisomerization in Mononuclear Ruthenium(II)（過去 5 年以内）
Monoaquo Complexes: A DFT Study, submitted
2. Lina Ding, Naoki Ishida, Masahiro Murakami, and Keiji Morokuma*, sp3–sp2 vs
sp3–sp3 C–C Activation in Rh-Catalyzed Ring Opening of Benzocyclobutenol: A
DFT Study To be submitted
3. Lina Ding, Lung Wa Chung, Keiji Morokuma “Reaction Mechanism of
Photoinduced Decarboxylation of the Photoactivatable Green Fluorescent Protein:
An ONIOM(QM:MM) Study”, J. Phys. Chem. B, 2013, 117 (4), 1075–1084.
4. Ganglong Cui, Lina Ding, Feng Feng, Yajun Liu, and Weihai Fang, “Insights into
Mechanistic Photochemistry of Urea”, J. Chem. Phys. 2010, 132, 194308;
5. Lina Ding, Wei-Hai Fang, “Exploring Light-Induced Decarboxylation Mechanismof o-Acetylphenyl-Acetic Acid from the Combined CASSCF and DFT Studies”, J.
Org. Chem. 2010, 75, 1630-1636.
6. Lina Ding, Lin Shen, Xue-Bo Chen, Wei-Hai Fang, “Solvent Effects on
photoreactivity of Valerophenone: A Combined QM and MM Study”, J. Org. Chem.
Featured Article 2009, 74, 8956-8962.
7. Lina Ding, Xue-Bo Chen, Wei-Hai Fang, “Ultrafast Asynchronous Concerted
Excited-State Intramolecular Proton Transfer and Photodecarboxylation ofo-Acetylphenylacetic Acid Explored by Combined CASPT2 and CASSCF Studies”,
Org. Lett. 2009, 11(7), 1495-1498.
【学術関係の受賞など】 Beijing Normal University, Academic Excellence Award, 2009.
Beijing Normal University, Scientific Achievement Award, 2010.

－ 36 －

fukui2012_01.indb 36

14.1.9 1:23:12 PM

Ⅱ 博士研究員 (2012)【氏名】 Hai-Bei Li【職名】 Crest Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 203【直通電話】 075-711-7834【電子メールアドレス】 hpli@fukui.kyoto-u.ac.jp【研究分野】 Computational Chemistry【現在の研究課題】 MD simulations of the formation and growth of carbon nanostructures: fullerenes,
nanotubes, and graphene【研究内容キーワード】 Fullerene, Hydrocarbon combustions, Self-assembly, Single-walled carbon nanotube,
Chirality, Graphene growth, Density-functional tight-bingding【学歴】 2004, Bachelor of Chemistry, Qufu Normal University, China
2007, Master of Chemical Physics, University of Science and Technology of China,
China
2010, Doctor of Chemical Physics, University of Science and Technology of China,
China【学位】 Doctor of Philosophy, University of Science and Technology of China【主な著書、学術論文】 1. Hai-Bei Li, Alister. J. Page, Stephan Irle and Keiji Morokuma, Single-walled（過去 5 年以内）
Carbon Nanotube Growth from Chiral Carbon Nanorings: Prediction of Chirality
and Diameter Influence on Growth Rates. J. Am. Chem. Soc. 134, 15887, 2012
2. Hai-Bei Li, Alister. J. Page, Stephan Irle and Keiji Morokuma, Theoretical Insights
into Chirality-Controlled SWCNT Growth from a Cycloparaphenylene Template.
ChemPhysChem, 13, 1479, 2012
3. Hai-Bei Li, Alister. J. Page, Ying Wang, Stephan Irle and Keiji Morokuma, Subsurface nucleation of graphene precursors near a Ni(111) step-edge, ChemComm,48, 7937, 2012
4. Hai-Bei Li, Shanxi Tian, and Jinlong Yang. Propene oxidation on V 4O11− cluster:reaction dynamics to acrolein, J. Phys. Chem. A, 114, 6542, 2010
5. Hai-Bei Li, Shanxi Tian, and Jinlong Yang. Propene oxidation with anionic cluster
V4O11−: selective epoxidation, Chem. Eur. J (communications) 15, 10747, 2009
【学術関係の受賞など】 Qiu Shi Graduate Student Scholarship (2009)
Supported by the Scientific Research Foundation of Graduate School of USTC (2008)－ 37 －

fukui2012_01.indb 37

14.1.9 1:23:12 PM

Ⅱ 博士研究員 (2012)【氏名】 Lung Wa Chung【職名】 JST Fellow【所属】 Fukui Kennichi Memorial Research Group 1, Fukui Institute For Fundamental
Chemistry【研究室】 Room 212【直通電話】 075-711-7631【電子メールアドレス】 chung@fukui.kyoto-u.ac.jp【ホームページ】 https://sites.google.com/site/oscarlwchung/home【研究分野】 Computational Chemistry, Biochemistry and Biophysics【現在の研究課題】 Metalloenzymes, photobiology, multi-scale simulations【研究内容キーワード】 Reaction mechanism of metalloenzymes, photobiology, bio-inspired systems andcatalysis; multi-scale simulations development; strongly-correlated systems【学歴】 Aug. 2000, B.Sc. in Chemistry (1st Hon.), The Hong Kong University of Science &Technology;
Aug. 2003, M. Phil. in Chemistry, The Hong Kong University of Science & Technology;
Aug. 2006, Ph. D. in Chemistry, The Hong Kong University of Science & Technology【学位】 Ph. D. in chemistry, The Hong Kong University of Science & Technology【主な著書、学術論文】 1. Chung, L. W.; Li, X.; Sugimoto, H.; Shiro, Y.; Morokuma, K. “A DFT Study on a
Missing Piece in Understanding of Heme Chemistry: The Reaction Mechanism for（過去 5 年以内）
Indoleamine 2,3-Dioxygenase (IDO) and Tryptophan 2,3-Dioxygenase (TDO)” J.
Am. Chem. Soc. 2008, 130, 12298.
2. Chung, L. W.; Hayashi, S.; Lundberg, M.; Nakatsu, T.; Kato, H.; Morokuma, K.
“Mechanism of Efficient Firefly Bioluminescence via Adiabatic Transition Stateand Seam of Sloped Conical Intersection” J. Am. Chem. Soc. 2008, 130, 12880.
3. Li. X.; Chung, L. W.; Paneth, P.; Morokuma, K. “DFT and ONIOM(DFT:MM)
Studies on Co-C Bond Cleavage and Hydrogen Transfer in B12-Dependent
Methylmalonyl-CoA Mutase. Stepwise or Concerted Mechanism?” J. Am. Chem.
Soc. 2009, 131, 5115.
4. Li. X.; Chung, L. W.; Mizuno, H.; Miyawaki, A.; Morokuma, K. “A Theoretical
Study on the Natures of On- and Off-States of Reversibly Photoswitching
Fluorescent Protein Dronpa: Absorption, Emission, Protonation and Raman” J.
Phys. Chem. B 2010, 114, 1114
5. Chung, L. W.; Li, X.; Sugimoto, H.; Shiro, Y.; Morokuma, K. “ONIOM Study ona Missing Piece in Our Understanding of Heme Chemistry: Bacterial Tryptophan
2,3-Dioxygenase with Dual Oxidants”, J. Am. Chem. Soc. 2010, 115, 11993.
6. Nakamura, A.; Munakata, K.; Ito, S.; Kochi, T.; Chung, L. W.; Morokuma, K.;
Nozaki, K. “Pd-Catalyzed Copolymerization of Methyl Acrylate with Carbon
Monoxide: Structures, Properties and Mechanistic Aspects toward Ligand Design” J.
Am. Chem. Soc. 2011, 133, 6761.
7. Li, X.; Chung, L. W.; Morokuma, K. “Primary Events of Photodynamics of Alltrans Protonated Retinal Schiff Base in Bacteriorhodopsin, Methanol Solution and
Gas Phase” J. Chem. Theory Comput. (Lett.) 2011, 7, 2694.
8. Chung, L. W.; Li, X.; Hirao, H.; Morokuma, K. “Comparative Reactivity of FerricSuperoxo and Ferryl-Oxo Species in Heme and non-Heme Complexes” J. Am.
Chem. Soc. (Commun.) 2011, 133, 20076.
9. Tanaka, R.; Yamashita, M.; Chung, L. W.; Morokuma, K.; Nozaki, K.
“Hydrogenation of Carbon Dioxide Catalyzed by Ir-PNP Complex: Reversibility
and Reaction Mechanism” Organometallics 2011, 30, 6742.
10. Chung, L. W.; Hirao, H.; Li, X.; Morokuma, K. “The ONIOM Method: Its
Foundation and Applications to Metalloenzymes and Photobiology”, WIREs
Comput. Mol. Sci. 2012, 2, 327.
11. Ding, L.; Chung, L. W.; Morokuma, K. “Reaction Mechanism of Photoinduced
Decarboxylation of the Photoactivatable Green Fluorescent Protein: An
ONIOM(QM:MM) Study” J. Phys. Chem. B 2013, 117, 1075.
－ 38 －

fukui2012_01.indb 38

14.1.9 1:23:12 PM

Ⅱ 博士研究員 (2012)【氏名】 Galina Petrova【職名】 JSPS fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 208【直通電話】 075-711-7894【FAX】 075-711-7838【電子メールアドレス】 petrova@fukui.kyoto-u.ac.jp【研究分野】 Computational Chemistry【現在の研究課題】 Hetero- and homogeneous catalysis, Asymmetric organic catalysis【研究内容キーワード】 metalloenzymes, DNA based asymmetric catalysis, reaction mechanisms【学歴】 2009, Ph.D. degree in Organic chemistry, University of Sofia, Bulgaria
2003, B.Sc. in Chemistry (Theoretical and physical chemistry), University of Sofia,
Bulgaria【学位】 Ph.D. in Organic chemistry, University of Sofia, Bulgaria【略歴】 05/2012-05/2013, JSPS Fellow at FIFC, Kyoto University, Kyoto, Japan
12/2010-04/2012, Postdoctoral Scholar at FIFC, Kyoto University, Kyoto, Japan
02-11/2010, Postdoctoral Scholar at the Faculty of Chemistry, University of Sofia
06/2009–01/2010, Postdoctoral Scholar at the Faculty of Chemistry, University of
Sofia & Excellence Centre for Advanced Materials UNION
7/2008–5/2009, Research chemist at the Faculty of Chemistry, University of Sofia【所属学会】 Bulgarian Catalytic Club, Bulgarian Zeolite Association【主な著書、学術論文】 1. G. N. Vayssilov, G. P. Petrova, E. A. I. Shor, V. A. Nasluzov, A. M. Shor, P. S.
Petkov, N. Rösch, “Reverse hydrogen spillover on and hydrogenation of supported（過去 5 年以内）
metal clusters: Insights from computational model studies” Phys. Chem. Chem.
Phys. 14, 5879-5890 (2012).
2. G. N. Vayssilov, Y. Lykhach, A. Migani, T. Staudt, G. P. Petrova, N. Tsud, Tomáš
Skála, A. Bruix, F. Illas, K. C. Prince, V. Matolín, K. M. Neyman, J. Libuda,“Support nanostructure boosts oxygen transfer to catalytically active platinum
nanoparticles”, Nature Materials, 10, 310–315 (2011).
3. G. P. Petrova, G. N. Vayssilov, N. Rösch, “Interaction of ethene and ethyne withbare and hydrogenated Ir4 clusters. A density functional study”, Catalysis Science& Technology, 1, 958-970 (2011).
4. N. Rösch, G. P. Petrova, P. St. Petkov, A. Genest, S. Krüger, H. A. Aleksandrov, G.
N. Vayssilov, “Impurity Atoms on Small Transition Metal Clusters. Insights from
Density Functional Model Studies”, Topics in Catalysis, 54, 363-377 (2011).
5. M. A. Rangelov, G. P. Petrova, V. M. Yomtova, G. N. Vayssilov, “Catalytic Roleof Vicinal OH in Ester Aminolysis - Proton Shuttle versus Hydrogen-Bonds
Stabilization”, J. Org. Chem., 75, 6782–6792 (2010).
【学術関係の受賞など】 Student award for high academic achievements of the Foundation for support of the
Bulgarian Higher Education named after Prof. Michael Klett (2003)－ 39 －

fukui2012_01.indb 39

14.1.9 1:23:12 PM

Ⅱ 博士研究員 (2012)【氏名】 Travis Harris【職名】 Postdoctoral Fellow【所属】 Fukui Kenichi Memorial Research Group 1, Fukui Institute for Fundamental
Chemistry【研究室】 212
【直通電話】 075-711-7631【FAX】 075-781-4757【電子メールアドレス】 tvharris@fukui.kyoto-u.ac.jp【研究分野】 Computational Chemistry【現在の研究課題】 Computational studies of metalloenzymes and molecular magnets【研究内容キーワード】 ferritin, ferroxidase, di-iron, DMRG, magnetic exchange coupling【学歴】 2006, B.A. (summa cum laude), Willamette University, Salem, OR, USA
2011, Ph.D., Montana State University, Bozeman, MT, USA【学位】 Doctor of Philosophy, Montana State University, Bozeman, MT, USA【略歴】 2011, General Chemistry Lab TA, Montana State University
2007, Research Assistant, Montana State University
2006, Biochemistry Lab TA, Willamette University【主な著書、学術論文】 1. Harris, T. V.; Morokuma, K. QM/MM Structural and Spectroscopic Analysis of the
Di-iron(II) and Di-iron(III) Ferroxidase Site in M Ferritin Inorg. Chem., submitted（過去 5 年以内）
2013.
2. Harris, T. V.; Szilagyi, R. K. Comparative Assessment of the Composition andCharge State of Nitrogenase FeMo-Cofactor. Inorg. Chem., 2011, 50 (11), 4811.
3. Harris, T. V.; Szilagyi, R. K. Nitrogenase Structure and Function Relationships by
Density Functional Theory. In Nitrogen Fixation: Methods and Protocols; Ribbe, M.
W. Ed.; Humana Press: New York, 2011; pp 267-292.
4. Harris, T. V.; Szilagyi, R. K.; McFarlane Holman, K. L. Electronic Structural
Investigations of Ruthenium Compounds and Anticancer Prodrugs. J. Biol. Inorg.
Chem. 2009, 14 (6), 891.
5. Pool, V. L.; Klem, M. T.; Holroyd, J.; Harris, T.; Arenholz, E.; Young, M.; Douglas,T.; Idzerda, Y. U. Site Determination of Zn Doping in Protein Encapsulated ZnxFe3O Nanoparticles. J. Appl. Phys. 2009, 105 (7), 07B515.
x 4【学術関係の受賞など】 JSPS Fellowship, 2012
NSF Materials Computation Center Travel Grant, 2011
Kopriva Graduate Student Fellowship, 2009
Molecular Biosciences Fellowship, 2007–2011
Mildred Livingston Grant, 2007–2008－ 40 －

fukui2012_01.indb 40

14.1.9 1:23:13 PM

Ⅱ 博士研究員 (2012)【氏名（ふりがな）】 伊勢川

美穂 （いせがわみほ）【職名】 研究員【所属】 福井謙一記念研究センター【研究室】 福井謙一記念研究センター 203【電子メールアドレス】 isegawa@fukui.kyoto-u.ac.jp【研究分野】 計算化学、理論化学【現在の研究課題】 ニトロメタンの光解離、H2NO の光解離、Carbocation の rearrangement に関する研究【研究内容キーワード】 励起状態、光解離、遷移状態、有機化学反応【学歴】 2009年10月

京都大学大学院理学研究科博士課程修了【学位】 2009年10月 理学博士（京都大学）【略歴】 2010年1月-2013年2月 Research scholar, University of Minnesota
2013年3 月- 研究員、福井謙一記念研究センター【主な著書、学術論文】 1. Polarizable Force Field for protein with Charge Response kernel, M. Isegawa and S.
（過去 5 年以内）
Kato, J. Chem. Theory Comput. 5, 2809 (2009).
2. Incorporation of charge transfer into the explicit polarization fragment method by
grand canonical density functional theory, M. Isegawa, J. Gao, and D. G. Truhlar, J.
Chem. Phys. 135, 084107 (2011).
3. Polarized Molecular Orbital Model Chemistry 3. The PMO Method Extended
to Organic Chemistry, M. Isegawa, L. Fieldler, H. R. Leverentz, Y. Wang, S.
Nachimuthu, J. Gao, and D. G. Truhlar, J. Chem. Theory Comput. 9, 33 (2013).
4. Performance of Recent Approximation Density functional for Time-Dependent
Density Functional Theory Calculations of Valence and Rydberg Electronic
Transition Energies, M. Isegawa, R. Peverati, and D. G. Truhlar, J. Chem. Phys.
137, 244104 (2013).
5. Electrostatically Embedded Molecular Tailoring Approach and Validation for
Peptide, M. Isegawa, B. Wang, and D. G. Truhlar, J. Chem. Theory Comput.
9,1381(2013).

－ 41 －

fukui2012_01.indb 41

14.1.9 1:23:13 PM

Ⅱ 博士研究員 (2012)【氏名（ふりがな）】 山邊

信一 （やまべしんいち）【職名】 研究員【所属】 京都大学

福井謙一記念研究センター

榊グループ【直通電話】 075-711-7907【電子メールアドレス】 yamabes@fukui.kyoto-u.ac.jp【研究分野】 有機量子化学【現在の研究課題】 有機化学反応における水素結合の役割【研究内容キーワード】 反応経路、 軌道相互作用、 水素結合、プロトン移動【学歴】 1969年3月京都大学 工学部燃料化学科 卒業、工学研究科 燃料化学専攻 博士課程 終了。

1974年3月末

京都大学【学位】 工学博士【略歴】 1974年4月-1975年9月末 米国 Rochester大学 博士研究員、1975年10月-2012年3月末 奈良教育大学 教員。
【所属学会】 日本化学会【主な著書、学術論文】 1. "How is the anionic tetrahedral intermediate involved in the isomerization of
aspartyl peptides to iso-aspartyl ones? A DFT study on the tetra-peptide", Shinichi（過去 5 年以内）
Yamabe, Wei Guan and Shigeyoshi Sakaki, Org. Biomol. Chem., 2012,10, 80078015 DOI: 10.1039/C2OB26106E
2. "A new intermediate in the Prins reaction", Shinichi Yamabe, Takeshi Fukuda andShoko Yamazaki, Beilstein J. Org. Chem. 2013, 9, 476-485.
3. "Presence or absence of a novel charge-transfer complex in the base-catalyzedhydrolysis of N-ethylbenzamide or ethyl benzoate", Shinichi Yamabe, Wei Guan
and Shigeyoshi Sakaki, Beilstein J. Org. Chem. 2013, 9, 185-196.
4. "Three Competitive Transition States at the Glycosidic Bond of Sucrose in Its AcidCatalyzed Hydrolysis", Shinichi Yamabe, Wei Guan and Shigeyoshi Sakaki, J. Org.
Chem., 2013, 78 (6), pp 2527-2533. DOI: 10.1021/jo3027565
5. "An aniline dication-like transition state in the Bamberger rearrangement", Shinichi
Yamabe, Guixiang Zeng, Wei Guan and Shigeyoshi Sakaki, Beilstein J. Org. Chem.
2013, 9, 1073-1082.doi:10.3762/bjoc.9.119－ 42 －

fukui2012_01.indb 42

14.1.9 1:23:13 PM

Ⅱ 博士研究員 (2012)【氏名】 Yuh Hijikata【職名】 FIFC Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 303【直通電話】 075-711-7907【電子メールアドレス】 milind@fukui.kyoto-u.ac.jp【ホームページ】 hijikata@fukui.kyoto-u.ac.jp【研究分野】 http://www.users.iimc.kyoto-u.ac.jp/~z59354/member_e/hijikata.html【現在の研究課題】 Quantum Chemistry, Coordination Chemistry【研究内容キーワード】 Gas Adsorption, Proton Conductivity【学歴】 Mar 2008, Master of Eng., Graduate School of Engineering, Kyoto University
May 2011, Ph.D. of Eng., Graduate School of Engineering, Kyoto University【学位】 Ph.D. of Eng. from Kyoto University【略歴】 Oct. 2011FIFC Fellow (Kyoto University)
Apr. 2011-Sep. 2011 Specially Promoted Research Fellow (Kyoto University)
Apr. 2008-Mar. 2011 JSPS Research Fellow (DC1) (Kyoto University)【所属学会】 Chemical Society of Japan, Japan Society of Coordination Chemistry,
Japan Society for Molecular Science【主な著書、学術論文】 1. Yuh HIJIKATA, Satoshi HORIKE, Masayuki SUGIMOTO, Munehiro INUKAI,
Tomohiro FUKUSHIMA, and Susumu KITAGAWA, “Pore design of two（過去 5 年以内）
dimensional coordination polymers toward selective adsorption” Inorg. Chem. 52,
3634-3642 (2013)
2. Nobuhiro YANAI, Koji KITAYAMA, Yuh HIJIKATA, Hiroshi SATO, Ryotaro
MATSUDA, Yoshiki KUBOTA, Masaki TAKATA, Motohiro MIZUNO, Takashi
UEMURA, and Susumu KITAGAWA, “Reporting structural transformation of soft
porous crystals for detection of CO2”, Nat. Mater., 10, 787-793 (2011)

3. Yuh HIJIKATA, Satoshi HORIKE, Daisuke TANAKA, Juergen GROLL, Motohiro
MIZUNO, Jungeun KIM, Masaki TAKATA, and Susumu KITAGAWA, Differencesof crystal structure and dynamics between soft porous nanocrystal and bulk
crystal”, Chem. Commun., 47, 7632-7634 (2011)

4. Yuh HIJIKATA, Satoshi HORIKE, Masayuki SUGIMOTO, Hiroshi SATO,
Ryotaro MATSUDA, and Susumu KITAGAWA, “Relationship between Channel
and Sorption Properties in Coordination Polymers with Interdigitated Structures”,
Chem. Eur. J., 17, 5138-5144 (2011)
5. Yuh HIJIKATA, Hiroyuki NAKASHIMA, and Hiroshi NAKATSUJI, “Solving
non-Born-Oppenheimer Schrödinger equation for hydrogen molecular ion and its
isotopomers using the free complement method”, J. Chem. Phys., 130, 024102-1-11(2009)【学術関係の受賞など】 JSPS Research Fellowships for Young Scientists (DC1) 2008-2011－ 43 －

fukui2012_01.indb 43

14.1.9 1:23:13 PM

Ⅱ 博士研究員 (2012)【氏名（ふりがな）】 青野

信治 （あおのしんじ）【職名】 特定研究員【所属】 京都大学 福井謙一記念研究センター【研究室】 福井記念研究センター 303 号室【直通電話】 075-711-7907【電子メールアドレス】 saono@fukui.kyoto-u.ac.jp【研究分野】 Theoretical and Computational Chemistry【現在の研究課題】 溶液化学・計算化学・理論化学【研究内容キーワード】 溶液中の遷移金属錯体の化学反応の理論的解析【学歴】 3D-RISM-SCF法、平均場QM/MM法、自由エネルギー解析、溶媒和構造解
析、周期的結晶解析【学位】 2010年3月 京都大学大学院理学研究科化学専攻博士後期課程研究指導認定退学【略歴】 2010年4月 京都大学大学院理学研究科化学専攻 研修員
2010年5月 京都大学 物質-細胞統合システム拠点 教務補佐員
2010年10月 京都大学 物質-細胞統合システム拠点 特定研究員
2011年4月 京都大学 福井謙一記念研究センター 特定研究員【主な著書、学術論文】 1. Aono S., Hosoya T., and Sakaki S., “A 3D-RISM-SCF method with dual solvent
boxes for a highly polarized system: application to 1,6-anhydrosugar formation（過去 5 年以内）
reaction of phenyl alpha- and beta-D-glucosides under basic conditions” Phys.
Chem. Chem. Phys. 17 6368 (2013)
2. Aono S. and Sakaki S., “Evaluation Procedure of Electrostatic Potential in
3D-RISM-SCF Method and Its Application to Hydrolyses of Cis- and Transplatin
Complexes” J. Phys. Chem. B 116 13045 (2012)
3. Aono S. and Sakaki S., “Proposal of new QM/MM approach for geometry
optimization of periodic molecular crystal: Self-consistent point charge
representation for crystalline effect on target QM molecule” Chem. Phys. Lett. 544
77 (2012).
4. Aono S., Yamamoto T. and Kato S. “Solution reaction space Hamiltonian based onan electrostatic potential representation of solvent dynamics” J. Chem. Phys. 134
144108 (2011).
5. Aono S. and Kato S. “Proton Transfer in Phenol-Amine Complexes: Phenol
Electronic Effect on Free Energy Profile in Solution” J. Comput. Chem. 31 29242931 (2010).
6. Aono S., Minezawa N. and Kato S. “Electronic spectra of coumarin-151 in polar
solvents: Linear response free energy approach” Chem. Phys. Lett. 492 193-197(2010).

－ 44 －

fukui2012_01.indb 44

14.1.9 1:23:13 PM

Ⅱ 博士研究員 (2012)【氏名（ふりがな）】 塚本

晋也 （つかもと

しんや）【職名】 特推研究フェロー【所属】 福井謙一記念研究センター【研究室】 福井謙一記念研究センター

福井謙一研究部第二

榊グループ

301

【直通電話】 075-711-7907【FAX】 075-711-4757【電子メールアドレス】 stsukamoto@fukui.kyoto-u.ac.jp【ホームページ】 http://www.users.iimc.kyoto-u.ac.jp/~z59354/【研究分野】 計算化学・理論化学【現在の研究課題】 遷移金属錯体の理論研究【研究内容キーワード】 遷移金属
【学歴】 2010年九州大学大学院総合理工学府量子プロセス理工学専攻博士後期課程修了【学位】 2010年3月博士 (理学) (九州大学)【所属学会】 分子科学会、理論化学会、American Chemical Society【主な著書、学術論文】 1. “CASSCF and CASPT2 calculations for lanthanide trihalides LnX3 using model
core potentials” S. Tsukamoto, H. Mori, H. Tatewaki, and E. Miyoshi, Chem. Phys.
（過去 5 年以内）
Lett. 2009, 474, 28.
2. “Theoretical Study of Pt(PR3)2(AlCl3)(R-H, Me, Ph, or Cy) Including an
Unsupported Bond between Transition Metal and Non-Transition Metal Elements;
Geometry, Bond Strength, and Prediction” S. Tsukamoto and S. Sakaki, J. Phys.
Chem. A, 2011, 115, 8520.
3. “A theoretical study of luminescent vapochromic compounds including an
AuCu2(NHC)2 core” S. Tsukamoto and S. Sakaki, Dalton Trans. 2013, 42, 4809.

－ 45 －

fukui2012_01.indb 45

14.1.9 1:23:13 PM

Ⅱ 博士研究員 (2012)【氏名】 Milind Madhusudan Deshmukh【職名】 Special Promoted Research Post-doctoral Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 304【直通電話】 075-711-7907【電子メールアドレス】 milind@fukui.kyoto-u.ac.jp【ホームページ】 http://www.sakakigroup.fukui.kyoto-u.ac.jp/member_e/milind.html【研究分野】 Theoretical and Computational Chemistry【現在の研究課題】 Gas Absorption in Metal Organic Framework, Non covalent Interactions andActivation of small molecule by transition metal complexes.
【研究内容キーワード】 Metal-Organic Framework, Potential Energy Surface, Catalysis【学歴】 March 2001, Master of Sci., University of Pune, India
October 2008, Doctor of Philosophy, University of Pune, India【学位】 Doctor of Philosophy from Department of Chemistry, University of Pune, India【略歴】 August 2008 to April 2010: Postdoctoral Research Fellow, Tata Institute ofFundamental Research, Mumbai, India
June 2010 to present: Postdoctoral Research Fellow, Kyoto University, Japan【主な著書、学術論文】 1. Milind M. Deshmukh, Masaaki Ohba, Susumu Kitagawa, and Shigeyoshi Sakaki“Absorption of CO2 and CS2 into the Hofmann-Type Porous Coordination Polymer:（過去 5 年以内）
Electrostatic versus Dispersion Interactions” J. Am. Chem. Soc. 135, 4840 (2013).
2. Milind M. Deshmukh, and Shigeyoshi Sakaki, “Two-step Evaluation of Potential
Energy Surface and Binding Energy of van der Waals Complexes” J. Comput.
Chem. 33, 617 (2012).
3. Jayasree K. Kedkar, Milind M. Deshmukh, Shridhar R. Gadre. Shridhar P. Gejji,“Intramolecular Hydrogen Bonding and cooperative interactions in Calix[n]arenes(n = 4, 5)” J. Phys. Chem. A. 116, 3739 (2012).
4. Milind M. Deshmukh and Shigeyoshi Sakaki, “Binding Energy of Gas Moleculewith Two Pyrazine Molecules as Organic Linker in Metal-Organic Framework: Its
Theoretical Evaluation and Understanding of Determining Factors” Theo. Chem.
Acc. 130, 475 (2011).
5. Milind M. Deshmukh, Bartolotti Libero Jr., and Shridhar R. Gadre, “Intramolecular
Hydrogen Bond Energy and Cooperative Interactions in α-, β-, and γ-Cyclodextrin
Conformers”, J. Comput. Chem. 32, 2996 (2011).
6. Milind M. Deshmukh and Shridhar R. Gadre, “Estimation of N-H···O=C
Intramolecular Hydrogen Bond Energy in Polypeptides”, J. Phys. Chem. A. 113,
7927 (2009).
【学術関係の受賞など】 Senior Research Fellowship of CSIR, India, (2005-2008).
Senior Research Fellowship of C-DAC, Pune, India (2004-2005).

－ 46 －

fukui2012_01.indb 46

14.1.9 1:23:14 PM

Ⅱ 博士研究員 (2012)【氏名】 Guixiang Zeng
【職名】 SPR Fellow【所属】 Sakaki Group, Fukui Institute for Fundamental Chemistry【研究室】 Room 303【直通電話】 075-711-7907【電子メールアドレス】 guixiang.zeng@fukui.kyoto-u.ac.jp【研究分野】 Computational Chemistry【現在の研究課題】 1. Cooperative catalysis through new metal-Ligand cooperation modes
2. H-H and C-H bond activations
3. Dehydrogeanation and hydrogenation reactions【研究内容キーワード】 Cooperation catalysis, C-H bond, H-H bond, main group catalyst【学歴】 2005~2010, Ph. D. education, School of Chemistry & Chemical Engineering, Nanjing
University【学位】 Ph. D. in Physical Chemistry, Nanjing University【略歴】 Sep. 2010~, Postdoctoral Fellow, Kyoto University【主な著書、学術論文】 1. Guixiang Zeng, Yong Guo, Shuhua Li, “H2 activation by a (PNP)Ir(C6H5) complex
via the dearomatization/aromatization process of the PNP ligand: A computational（過去 5 年以内）
study” Inorg. Chem. 48, 10257 (2009).
2. Guixiang Zeng, Shuhua Li, “Mechanistic insight on the hydrogenation of
conjugated alkenes with H2 catalyzed by early main-group metal catalysts” Inorg.
Chem. 49, 3361 (2010).
3. Guixiang Zeng, Shuhua Li, “Insights on Dehydrogenative Coupling of Alcohols andAmines catalyzed by a (PNN)−Ru(II) Hydride Complex: Unusual Metal−Ligand
Cooperation” Inorg. Chem. 50, 10572 (2011).
4. Guixiang Zeng, Shigeyoshi Sakaki, “Noble Reaction Features of Bromoborane in
Oxidative Addition of B−Br σ−Bond to [M(PMe3)2] (M= Pt or Pd): Theoretical
Study” Inorg. Chem. 50, 5290 (2011).
5. Guixiang Zeng, Shigeyoshi Sakaki, “Theoretical Study on the Transition-Metal
Oxoboryl Complex: M−BO Bonding Nature, Mechanism of the Formation
Reaction, and Prediction of a New Oxoboryl Complex” Inorg. Chem. 51, 4597
(2012)
6. Guixiang Zeng, Shigeyoshi Sakaki, “Unexpected Electronic Process of H2
Activation by a New Nickel Borane Complex: Comparison with the Usual
Homolytic and Heterolytic Activations” Inorg. Chem. 52, 2844 (2013)－ 47 －

fukui2012_01.indb 47

14.1.9 1:23:14 PM

Ⅱ 博士研究員 (2012)【氏名（ふりがな）】 高木

望 （たかぎのぞみ）【職名】 特定研究員【所属】 福井謙一記念研究センター【研究室】 福井謙一記念研究センター

榊研究室【直通電話】 075-711-7907【電子メールアドレス】 takagi@fukui.kyoto-u.ac.jp【研究分野】 計算化学・理論化学【現在の研究課題】 d- 電子複合系および高周期典型元素化合物の理論化学【研究内容キーワード】 遷移金属元素、高周期典型元素、分子軌道計算【学歴】 1997年3月
1999年3月
2002年3月【学位】 2002年 3月

立教大学理学部化学科 卒業
東京都立大学大学院理学研究科化学専攻修士士課程 修了
東京都立大学大学院理学研究科化学専攻博士課程 修了
理学博士（東京都立大学）【略歴】 2002年4月 日本学術振興会 特別研究員(PD)2005年4月 自然科学研究機構・分子科学研究所 専門研究職員
2007年5月 ドイツ・フィリップス=マールブルク大学 博士研究員
2011年4月 京都大学・福井謙一記念研究センター 特定研究員【在外研究歴】 2007年5月-2010年12月 ドイツ・フィリップス=マールブルク大学員（Gernot Frenking教授）

博士研究【所属学会】 日本化学会、理論化学研究会【主な著書、学術論文】 1. "Theoretical Study of Reactivity of Ge(II)-hydride Compound: Comparison withRh(I)-hydride Complex and Prediction of Full Catalytic Cycle by Ge(II)-hydride"（過去 5 年以内）
N. Takagi, S. Sakaki, J. Am. Chem. Soc., in press.
2. "A Theoretical Study of Unusual Y-Shaped Three-coordinate Pt Complex: Pt(0)σ-Disilane Complex or Pt(II) Disilyl Complex?" N. Takagi, S. Sakaki, J. Am.
Chem. Soc., 134, 11749-11759 (2012).
3. "Carbodiphosphorane-Analogues E(PPh3)2 with E = C - Pb. A Theoretical Studywith implications for ligand design" N. Takagi, R. Tonner, G. Frenking, Chem. Eur.
J., 18, 1772-1780 (2012).
4. "Bonding Situation in "Early-Late" Transition Metal Complexes Cl3M-M'(PCl3)4(M = Ti, Zr, Hf; M' = Co, Rh, Ir) - Theoretical Study for a Ligand Fine Tuning of
M-M’ Bonds -" N. Takagi, A. Krapp, G. Frenking, Z. Anorg. Alleg. Chem. 637,
1728-1735 (2011).
5. "Divalent Pb(0) Compounds" N. Takagi, G. Frenking, Theor. Chem. Acc., 129, 615623 (2011).
6. "Bonding Analysis for Metal-Metal Multiple bonds in R3M-M’R3 (M, M’ = Cr, Mo,
W; R = Cl, NMe2)" N. Takagi, A. Krapp, G. Frenking, Inorg. Chem., 50, 819-826(2010).
7. "On the nature of homo- and heterodinuclear metal-metal quadruple bonds –Analysis of the bonding situation and benchmarking DFT against wavefunction
methods" N. Takagi, A. Krapp, G. Frenking, Can. J. Chem., 88, 1079-1093 (2010).
8. "Divalent E(0) Compounds (E = Si - Sn)" N Takagi, T. Shimizu, G. Frenking,Chem. Eur. J., 15, 8593-8604 (2009).
9. "Divalent Si(0) Compounds" N Takagi, T. Shimizu, G. Frenking, Chem. Eur. J., 15,3448-3456 (2009).
10. "Do Lead Analogues of Alkynes Take a Multiply Bonded Structure? " N. Takagi, S.
Nagase, Organometallics, 26, 3627-3629 (2007).
11. "Tin Analogues of Alkynes. Multiply Bonded Structures vs Singly Bonded
Structures" N. Takagi, S. Nagase, Organometallics, 26, 469-471 (2007).
12. "Effects of Bulky Substituent Groups on the Si-Si Triple Bonding in RSi≡SiR andthe Short Ga-Ga Distance in Na2[RGaGaR]. A Theoretical Study" N. Takagi, and S.
Nagase, J. Organomet. Chem. 692, 217-224 (2007).
【学術関係の受賞など】 2002年-2005年

日本学術振興会

特別研究員(PD)－ 48 －

fukui2012_01.indb 48

14.1.9 1:23:14 PM

Ⅱ 博士研究員 (2012)【氏名】 Masayuki Nakagaki【職名】 FIFC Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 303【直通電話】 075-711-7907【電子メールアドレス】 nakagaki@fukui.kyoto-u.ac.jp【ホームページ】 http://www.fukui.kyoto-u.ac.jp/【研究分野】 Computational Chemistry【現在の研究課題】 Electronic Structure of Inverted Sandwich Type Complexes【研究内容キーワード】 Electronic Structure of Metal Complex, Multireference Theory【学歴】 March 2005, Master of Sci., Graduate School of Science, Kyushu University
March 2009, Doctor of Sci., Graduate School of Science, Kyushu University【学位】 Doctor of Science from Kyushu University【略歴】 Apr. 2009, Postdoctoral Fellow, Kyushu University【所属学会】 Japan Society for Molecular Science【主な著書、学術論文】 1. K. Sakota, Y. Komoto, M. Nakagaki, W. Ishikawa, H. Sekiya “Observ- ation of acatalytic proton/hydrogen atom relay in microsolvated 7-azaindole-methanol cluster（過去 5 年以内）
enhanced by a cooperative motion of the hydrogen-bonded network” Chem. Phys.
Lett. 435, 1-4 (2007)
2. X. Zhang, Y. Komoto, K. Sakota, M. Nakagaki, H. Nakano, T. Shinmyozu, H.
Sekiya “Heavy mass effect on excited-state double-proton transfer in 7-azaindole
dimer by Cl substitution” Chem. Phys. Lett. 441, 176-180 (2007)
3. X. Zhang, Y. Komoto, K. Sakota, N. Masayuki, T. Shinmyozu, S. Nanbu, H.
Nakano, H. Sekiya “Remarkable suppression of the excited-state double-protontransfer in the 7-azaindole dimer due to substitution of the dimethylamino groupstudied by electronic spectroscopy in the gas phase” Chem. Phys. Lett. 443, 194198 (2007)－ 49 －

fukui2012_01.indb 49

14.1.9 1:23:14 PM

Ⅱ 博士研究員 (2012)【氏名】 Terutaka Yoshizawa【職名】 (SPR) Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 303【直通電話】 075-711-7907【FAX】 075-711-4757【電子メールアドレス】 yoshizawa@fukui.kyoto-u.ac.jp【ホームページ】 http://www.users.iimc.kyoto-u.ac.jp/~z59354/【研究分野】 Theoretical chemistry【現在の研究課題】 Relativistic quantum chemical calculations of NMR shielding constants【研究内容キーワード】 NMR, DFT, Douglas–Kroll–Hess method, Transition metal complexes【学歴】 March 2006, Master of Sci., Graduate School of Science, Tokyo Metropolitan
University
March 2009, Doctor of Sci., Graduate School of Science and Engineering, Tokyo
Metropolitan University【学位】 Doctor of Science from Tokyo Metropolitan University【略歴】 Apr. 2009, Postdoctoral Fellow, Kyushu University
Jan. 2010, Postdoctoral Fellow, RIKEN
Apr. 2011, (SPR) Fellow, Kyoto University【主な著書、学術論文】 1. T. Yoshizawa and M. Hada, “Calculations of Frequency-Dependent Molecular
Magnetizabilities with Quasi-Relativistic Time-Dependent Generalized Unrestricted（過去 5 年以内）
Hartree-Fock Method”, J. Comput. Chem. 28, 740−747, (2007)
2. T. Yoshizawa and M. Hada, “Relativistic quantum-chemical calculations ofmagnetizabilities of noble gas atoms using the Douglas–Kroll–Hess method”,
Chem. Phys. Lett. 458, 223−226, (2008)
3. T. Yoshizawa and M. Hada, “Relativistic and Electron–Correlation Effects on
Magnetizabilities Investigated by the Douglas–Kroll–Hess Method and the SecondOrder Møller–Plesset Perturbation Theory”, J. Comput. Chem. 30, 2550−2566,(2009)
4. T. Yoshizawa and T. Nakajima, “Second-order generalized unrestricted Moller–
Plesset perturbation theory for the spin–orbit part of zero-field splitting tensors”,
Chem. Phys. Lett. 515, 296−301, (2011)
5. T. Yoshizawa and T. Nakajima, “A new computational scheme for the spin–orbit
part of zero-field splitting tensor” Chem. Phys. Lett. 549, 108–112, (2012)
6. T. Yoshizawa and S. Sakaki, “NMR shielding constants of CuX, AgX, and AuX (X= F, Cl, Br, and I) investigated by density functional theory based on the Douglas–
Kroll–Hess Hamiltonian” J. Comput. Chem. 34, 1013–1023, (2013)【学術関係の受賞など】 JSPS Research Fellowships for Young Scientists(DC) 2007-2009－ 50 －

fukui2012_01.indb 50

14.1.9 1:23:14 PM

Ⅱ 博士研究員 (2012)【氏名】 Wei Guan
【職名】 SPR Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 303【直通電話】 075-711-7907【電子メールアドレス】 guanw@fukui.kyoto-u.ac.jp【研究分野】 Computational Quantum Chemistry【現在の研究課題】 Nickel-Catalyzed Decarboxylative Cycloaddition with Alkynes【研究内容キーワード】 Decarboxylaton, Cycloaddition, Charge Transfer, Nickel【学歴】 June 2008, Faculty of Chemistry, Northeast Normal University, P.R. China【学位】 Ph.D. in Physical Chemistry【略歴】 July 2009 - Jan. 2012: State Key Laboratory of Rare Earth Resource Utilization,
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences,
Changchun, P.R. China. Postdoc fellow in Prof. Zhijian Wu’s group.
July 2008 – Present: Faculty of Chemistry, Northeast Normal University, Changchun,
P.R. China. Research Associate in Prof. Zhongmin Su’s group. (On Study Leave)【所属学会】 Chinese Chemical Society membership【主な著書、学術論文】 1. Guan, W.; Yamabe, S.; Sakaki, S. Dalton Trans. 2013, 42, 8717−8728.
（過去 5 年以内）
2. Yamabe, S.; Guan, W.; Sakaki, S. J. Org. Chem. 2013, 78, 2527−2533.

3. Yamabe, S.; Guan, W.; Sakaki, S. Beilstein J. Org. Chem. 2013, 9, 185–196.

4. Yamabe, S.; Guan, W.; Sakaki, S. Org. Biomol. Chem. 2012, 10, 8007−8015.
5. Guan, W.; Wu, Z. J.; Su, Z. M. Dalton Trans. 2012, 41, 2798−2803.

【学術関係の受賞など】 China Postdoctoral Science Special Foundation 2010-2011－ 51 －

fukui2012_01.indb 51

14.1.9 1:23:14 PM

Ⅱ 博士研究員 (2012)【氏名】 Yue Chen
【職名】 SPR Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 303【直通電話】 075-711-7907【FAX】 075-711-7838【電子メールアドレス】 ychen@fukui.kyoto-u.ac.jp【ホームページ】 http://www.sakakigroup.fukui.kyoto-u.ac.jp/member_e/yuechen.html【研究分野】 Computational Chemistry【現在の研究課題】 Electronic Structure of Transition Metal Dioxygen Complex【研究内容キーワード】 Electronic Structure of Transition Metal and Lanthanide Complexes【学歴】 June 2012, College of Chemistry, Beijing Normal University【学位】 Doctor of Physical Chemistry from Beijing Normal University【略歴】 July. 2012, Postdoctoral Fellow, Kyoto University【主な著書、学術論文】 1. Chen, Yue; Liu, Shubin; Lei, Ming "Nature of Asynchronous Hydrogen Transfer in
Ketone Hydrogenation Catalyzed by Ru Complex" J. Phys. Chem. C, 112, 13524（過去 5 年以内）
13527 (2008)
2. Chen, Yue; Tang, Yanhui; Lei, Ming "A comparative study on the hydrogenation of
ketones catalyzed by diphosphine-diamine transition metal complexes using DFT
method" Dalton Trans., 2359-2364 (2009)
3. Chen, Yue; Tang, Yanhui; Liu, Shubin; Lei, Ming; Fang, Weihai "Mechanism and
Influence of Acid in Hydrogenation of Ketones by η6-Arene/N-Tosylethylenediamine
Ruthenium(II)" Organometallics, 28, 2078-2084 (2009)
4. Chen, Yue; Fang, Wei-Hai "Mechanism for the Light-Induced O2 Evolution fromH2O Promoted by Ru(II) PNN Complex: A DFT Study" J. Phys. Chem. A, 114,
10334-10338 (2010)
5. Yue Chen, Juan Han, Wei-Hai Fang "Mechanism of Water Oxidation to Molecular
Oxygen with Osmocene as Photocatalyst: A Theoretical Study" Inorg. Chem., 51,4938−4946 (2012)
6. Juan Han, Xuebo Chen, Lin Shen, Yue Chen, Weihai Fang, Haobin Wang "Energy
Transfer Tunes Phosphorescent color if single-Dopant White OLED" Chem. -Eur. J.,
17, 13971-13977 (2011)－ 52 －

fukui2012_01.indb 52

14.1.9 1:23:15 PM

Ⅱ 博士研究員 (2012)【氏名】 Sayyed Fareed Bhasha【職名】 SPR fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 303【直通電話】 075-711-7907【FAX】 075-711-7838【電子メールアドレス】 sayyedfb@fukui.kyoto-u.ac.jp【ホームページ】 http://www.sakakigroup.fukui.kyoto-u.ac.jp/member_e/bhasha.html【研究分野】 Computational Chemistry【現在の研究課題】 Organometallic reactions【研究内容キーワード】 Nickel catalysis, Carboxylation, Carbon dioxide activation【学歴】 January 2008, Master of Science, University of Pune
August 2013, Doctor of Science, University of Kerala【学位】 Doctor of Science from University of Kerala【主な著書、学術論文】 1. Suresh, C. H.; Sayyed, F. B. “Resonance Enhancement via Imidazole Substitution
Predicts New Cation Receptors”. J. Phys. Chem. A, 2013 (accepted for publication).
（過去 5 年以内）
2. Sayyed, F. B.; Suresh, C. H.  “Accurate Prediction of Cation-π Interaction Energy
Using Substituent Effects”. J. Phys. Chem. A 2012, 116, 5723–5732.

3. Sayyed, F. B.; Suresh, C. H. “Quantitative Assessment of Substituent Effects on
Cation-π Interactions Using Molecular Electrostatic Potential Topography”. J.
Phys. Chem. A 2011, 115, 9300–9307.
4. Sayyed, F. B.; Suresh, C. H.    “Substituent Effects in Cation-π Interactions: A
Unified View from Inductive, Resonance, and Through-Space Effects”. J. Phys.
Chem. A 2011, 115, 5660–5664.
5. Sayyed, F. B.; Suresh, C. H.; Gadre, S. R. “Appraisal of Through-Bond andThrough-Space Substituent Effects via Molecular Electrostatic Potential
Topography”. J. Phys. Chem. A 2010, 114, 12330–12333.

－ 53 －

fukui2012_01.indb 53

14.1.9 1:23:15 PM

Ⅱ 博士研究員 (2012)【氏名（ふりがな）】 松井

亨 （まついとおる）【職名】 日本学術振興会 特別研究員 (PD)【所属】 理化学研究所 計算科学研究機構【研究室】 量子系分子科学研究チーム【直通電話】 078-940-5812【電子メールアドレス】 toru.matsui@riken.jp【研究分野】 計算化学・理論化学【現在の研究課題】 酸化還元電位の計算【研究内容キーワード】 酸化還元電位・溶媒和モデル・金属クラスター【学歴】 2009年3月 東京大学大学院工学系研究科応用化学専攻博士課程修了【学位】 2009年 工学博士 (東京大学)【略歴】 2008年4月日本学術振興会 特別研究員 (DC)2010年4月 兵庫県立大学生命理学研究科 特任助教
2011年4月日本学術振興会 特別研究員 (PD)2013年1月 理化学研究所 計算科学研究機構 訪問研究員【所属学会】 日本化学会、日本分子科学会【主な著書、学術論文】 1. T. Matsui, Y. Kitagawa, M. Okumura, Y. Shigeta and S. Sakaki, "Consistent Scheme
for Computing Standard Hydrogen Electrode and Redox Potentials", Journal of（過去 5 年以内）
Computational Chemistry, 34, p. 21-26 (2013).
2. T. Matsui, T. Baba, K. Kamiya and Y. Shigeta, “An accurate density functional
theory based estimation of pKa values of polar residues combined with experimental
data: from amino acids to minimal proteins”, Physical Chemistry Chemical Physics,
14, p. 4181-4187 (2012).
3. T. Matsui, H. Miyachi, T. Baba and Y. Shigeta, “A Theoretical Study on Reaction
Scheme of Silver (I) Containing 5-Substituted Uracils Bridge Formation”, The
Journal of Physical Chemistry A, 115, p.8504-8510 (2011).
4. Y. Nakanishi, T. Matsui, Y. Kitagawa, Y. Shigeta, T. Saito, Y. Kataoka, T.
Kawakami, M. Okumura and K. Yamaguchi, “Electron Conductivity in Modified
Models of Artificial Metal-DNA Using Green's Function-Based Scattering Theory”,
Bulletin of Chemical Society of Japan, 84, p.366-375 (2011).
5. T. Matsui, A. Oshiyama and Y. Shigeta, “A Simple Scheme for pKa of 5-substituted
Uracils” Chemical Physics Letters, 502, p.238-242 (2011).
6. Y. Nakanishi, T. Matsui, Y. Shigeta, Y. Kitagawa, T. Saito, Y. Kataoka, T.
Kawakami, M. Okumura and K. Yamaguchi, “Sequence dependent proton-transfer
reaction in stacked GC pair III: The Influence of Proton Transfer to Conductivity“,International Journal of Quantum Chemistry, 110, p. 2221-2230 (2010).
7. K. Kamiya, T. Matsui, T. Sugimura and Y. Shigeta, “Theoretical Insight into
Stereoselective Reaction Mechanisms of 2,4-Pentanediol-Tethered Ketene-Olefin[2+2] Cycloaddition”, The Journal of Physical Chemistry A, 116, p.1168-1175(2012).
8. T. Matsui, H. Miyachi, Y. Shigeta and K. Hirao (2012) “Metal-Assisted Proton
Transfer in Guanine-Cytosine Pair: An Approach from Quantum Chemistry”, inSome Applications of Quantum Mechanics, ISBN 978-953-51-0059-1, edited byMohammad Reza Pahlavani, InTech, p. 167-188.
【学術関係の受賞など】 日本学術振興会 特別研究員 (DC2) 2008-2010, 日本学術振興会 特別研究員 (PD)2011-2013, 日本化学会第93春季年会 優秀講演賞(学術)－ 54 －

fukui2012_01.indb 54

14.1.9 1:23:15 PM

Ⅱ 博士研究員 (2012)【氏名（ふりがな）】 河津

励 （かわつつとむ）【職名】 分子科学研究所 特任研究員【所属】 総合研究部門【研究室】 福井謙一記念研究センター 206【直通電話】 075-711-7867【FAX】 075-781-4757【電子メールアドレス】 kawatsu@fukui.kyoto-u.ac.jp【ホームページ】 http://www.fukui.kyoto-u.ac.jp/ users/kawatsu/index.html【研究分野】 生物物理化学【現在の研究課題】 革命的ハイパフォーマンス・コンピューティング・インフラ (HPCI) の構築【研究内容キーワード】 電子移動、励起エネルギー移動、蛋白質科学、自由エネルギー計算【学歴】 1999年3月
2002年2月

名古屋大学理学研究科物質理学専攻博士前期課程修了
名古屋大学理学研究科物質理学専攻博士後期課程修了【学位】 2002年2月

理学博士 (名古屋大学)【略歴】 2002年3月
2005年9月
2006年11月
2010年4月
2011年10月
2012年4月

デューク大学化学科 ポスドク
ジョージア工科大学化学生化学科 ポスドク
京都大学福井謙一記念研究センター JSTフェロー
京都大学工学研究科合成・生物専攻 特定研究員
自然科学研究機構分子科学研究所 専門研究職員
自然科学研究機構分子科学研究所 特任研究員【所属学会】 American Physical Society、日本生物物理学会【主な著書、学術論文】 1. T. Kawatsu, “Review: Pathway analysis for peptide-mediated electronic coupling inthe super-exchange mechanism of ET and EET,” Pep. Sci. 2013, 100, 100-113.
（過去 5 年以内）
2. T. Kawatsu, J. Hasegawa, “Sequentially Coupled Hole–Electron Transfer Pathwaysfor Bridge-Mediated Triplet Excitation Energy Transfer,” J. Phys. Chem. C 2012,
116, 23252–23256.

3. T. Kawatsu, J. Hasegawa, K. Matsuda, “Singlet Excitation Energy Transfer
Mediated by Local Exciton Bridges,” J. Phys. Chem. C 2012, 116, 13865-13876.
4. T. Kawatsu, J. Hasegawa, “Excitation energy transfer in GFP-X-CFP model
peptides (X = amino acids): Direct Versus through-bridge energy transfers,” Int. J.
Quantum Chem. 2013, 113, 563-568 .
5. T. Kawatsu, J. Hasegawa, K. Matsuda, “Bridge-mediated excitation energy transfer
pathways through protein media: a Slater determinant-based electronic coupling
calculation combined with localized molecular orbitals,” J. Phys. Chem. A 2011,
115, 10814-10822.
6. J. Hasegawa, T. Kawatsu, K. Toyota, K. Matsuda, “Chemical-intuition based LMO
transformation simplifies excited-state wave functions of peptides,” Chem. Phys.
Lett. 2011, 508, 171-176.
7. T. Kawatsu, M. Lundberg, K. Morokuma, “Protein free energy corrections in
ONIOM QM:MM modeling: A case study for isopenicillin N synthesis (IPNS),” J.
Chem. Theory Comput. 2011, 7, 390-401.
8. M. Lundberg, T. Kawatsu, T. Vreven, M. J. Frisch and K. Morokuma, “Transition
states in the protein environment – ONIOM QM:MM modeling of isopenicillin N
synthesis,” J. Chem. Theory Comput. 2009, 5, 222-234.
－ 55 －

fukui2012_01.indb 55

14.1.9 1:23:15 PM

Ⅲ 研究広報活動 (2012)Ϫ ◊✲ᗈሗάື
㸯㸬⚟஭ㅬ୍グᛕ◊✲ࢭࣥࢱ࣮ࢩ࣏ࣥࢪ࣒࢘
第 10 �京都大学福井謙一記念研究センターシンポ��ム
日時2012 年(平成 24 年) 11 月 30 日

場

所

京都大学福井謙一記念研究センター（3F 大会議室）

講演

Weston T. Borden (University of North Texas)“Why Does Cyclobutane-1,2,3,4-tetraone
Have a Triplet Ground State？”
10:15―11:15
赤木和夫（京都大学工学研究科 教授）「不斉液晶反応場での高分子合成：
ヘリカル共役ポリマーのらせん制御と形態保持炭素化 」
11:30―12:30
榊茂好 (京都大学福井謙一記念研究センター リサーチリーダー）「金属錯体の分子物性と反応：電子状態に基づく微視的理解」 14:00―15:00
15:15―17:15

ポスターセッション― コーヒーブレイク ―17:30―19:00

懇親会（１F 多目的ルーム）－ 56 －

fukui2012_01.indb 56

14.1.9 1:23:16 PM

Ⅲ 研究広報活動 (2012)����������
第 10 �福井センターセ��ー
日時2012 年(平成 24 年) 3 月１6 日

場

所

京都大学福井謙一記念研究センター（3F 大会議室）

14:30～14:35

14:30－17:30

Opening by Professor Shigeyoshi Sakaki(Fukui Institute for Fundamental Chemistry)

14:35～15:30

Assistant Professor Satoshi Maeda (Hokkaido Univ.)“Development and Applications of Automated Reaction Path Search
Methods: The Global Reaction Route Mapping (GRRM) Strategy”

15:30 ～16:00

Dr. Miho Hatanaka(Fukui Institute for Fundamental Chemistry)“Mechanism

Mukaiyama

of

Aldol

Reaction

Catalyzed

byWater-Tolerant Lanthanide Lewis Acid - An Artificial Force Induced
Reaction Study”
Break
16:15～17:30

Professor Pradipta Bandyopadhyay(Jawaharlal Nehru Univ. India)“New Development in Monte Carlo Based Methods: Large
Water Cluster Optimization and Efficient Sampling”

������
当センター国際連携強化プロジェクトの一環として、教員が海外の研究機関を訪問し、研究所の運営に関して意見交換を行った。（資料編６を参照）

����������
高等学校�の����
(1) 畑中美穂 特定研究員
兵庫県立北摂三田高等学校
京都府立宮津高等学校

2012 年(平成 24 年) 9 月 13 日

2012 年(平成 24 年) 11 月 5 日－ 57 －

fukui2012_01.indb 57

14.1.9 1:23:16 PM

Ⅲ 研究広報活動 (2012)

タイトル「コンピュータで見る化学反応の世界」(2) 榊 茂好リサーチリーダー
京都府立南陽高等学校

2012 年(平成 24 年) 11 月 8 日

タイトル「理論化学、計算化学の面白さ」(3) 諸熊

奎治シニアリサーチフェロー

京都府立洛北高等学校

2012 年(平成 24 年) 11 月 16 日

タイトル「コンピュータで化学反応の世界を探る」

㸳㸬ᰤ ㄃
諸熊奎治シニアリサーチフェローは、複雑分子系の理論研究の発展に多大な貢献をしたとして、平成 24 年 11 月 5 日に文化功労者の顕彰を受けた。
（資料編８を参照）－ 58 －

fukui2012_01.indb 58

14.1.9 1:23:16 PM

Ⅳ 研究業績 (2012)

Ⅳ

研究業績

���

１．専任教員

��

�合研究部� ���（平成 24 年 9 月 30 日まで）
1. 今年度の研究の要約
生体関連分子の励起状態と機能に関する理論的研究䛆ጞ䜑䛻䛇㻌 これまで、アミノ酸などの周辺環境（以下、溶媒と呼ぶ）に応じて光吸収・発光エネル
ギーを大きく変化させる光機能性蛋白質について、理論化学計算を用いてメカニズムを解析してきた。色素や発色団を取り囲む溶媒分子の電子状態との相互作用、即ち量子化学的相互作用が、励起状態の準位に無視できない影響を与えることを見出している。溶媒との協同効果による化学現象の制御は、化学における基本的かつ重要なテーマであり、これを記述する理論化学を発展させる必要がある。我々は、励起状態における分子間相互作用の起源を解析するために、分子軌道の局在化手法を提案している。今年度は、局在化分子軌道を用いた解析を行い、エネルギー準位に大きな変化を与える幾つかのレチナール蛋白質における特異的な分子間相互作用を見出した。更には、溶媒効
果を定量的に記述できる波動関数の構造についても明らかにした。
また、励起エネルギーのトンネル移動経路の解析を行っており、特にブリッジを経由して起きる
励起エネルギー移動について、様々なブリッジを用いてトンネル確率の大きさを決定する要因を求めた。更に、一重項移動と三重項移動のトンネル移動経路の差異を理論的に明らかにした。
䛆ගᶵ⬟ᛶ⺮ⓑ㉁䛾ບ㉳≧ែ䛸ศᏊ㛫┦஫స⏝䛇㻌 周辺環境に応じて分子の励起エネルギー準位が変化する現象はソルバトクロミズムとして良く研究されてきた。我々はレチナール蛋白質、蛍光蛋白質、蛍ルシフェリンなどの光機能性蛋白質におけるカラー・チューニングの起源について、
QM(SAC-CI)/MM(AMBER)計算に基づく研究を行い、周辺環境の静電ポテンシャルが重要な役割を果たすことを明らかにしたが、他方で、周辺環境の電子状態が無視できない影響を与えることも見出している。バクテリオロドプシン(bR)及びメタノール溶液中におけるレチナール色素の第一励起状態について、約 6 Å 程度の距離にあるアミノ酸までを考慮した励起状態計算を行うと、周辺環境を点電荷モデルで記述した結果と比較して、bR では約 0.3 eV、MeOH では約 0.1 eV 励起エネルギーが減少する。この差 0.2 eV は、ソルバトクロミズムの物理化学的原理を議論する上では無視できない
寄与を与える。
我々は周辺環境の電子状態に由来する効果を解析するために局在化分子軌道を計算する手法を提案した。一電子軌道をフラグメント（アミノ酸残基やペプチド結合）へと帰属できるので、励起状態の波動関数の解析が明確になった。本研究の目的は、同局在化軌道を用いた解析を行い、凝集系における分子の励起状態の波動関数の構造を明らかにすることである。
周辺環境の効果が最も顕著であった bR について、局在化軌道を用いた解析結果について説明する。図 1 には第一励起状態の主配置に関与する分子軌道の一部を示す。最も主要な配置はレチナー
ル色素の HOMO（図 1a）から LUMO（図 1b）への一電子遷移であり、これに Tyr185 の HOMO（図 1c）－ 59 －

fukui2012_02.indb 59

14.1.9 1:44:08 PM

Ⅳ 研究業績 (2012)からレチナールの LUMO への CT 遷移が副配置として混合することが明らかになった。この結果は、レチナールの HOMO が Tyr の HOMO と相互作用し、非局在化することにより励起エネルギーが低下したことを意味する。
(a) MO1746: HOMO of PSB(b) MO5014: LUMO of PSB(c) MO1491: HOMO of Tyr185

図 1. bR の第一励起状態の波動関数に関与する局在化分子軌道。(a)Protonated retinal Schiff base (PSB)の HOMO
及び (b) LUMO。(c) Tyr185 の HOMO。

各フラグメントにおいて最大の CI 係数を抽出した。結果を図 2 に示す。
bR では主配置である PSB
における励起に加えて、Tyr185 から PSB への CT（及び逆 CT）励起、Tyr185 における局所励起が比較的大きな係数を持っている。他方で、MeOH 溶液中の場合は、レチナールから溶媒分子へのCT 励起が見られるが、bR ほど顕著な寄与が無いことが特徴的である。また、図 2a と 2b では、電子励起の寄与がレチナールから溶媒分子への CT 励起、その逆の CT 励起、エキシトン励起を表わす３つの直線上に偏って分布することが明確に分かる。この状況は他の系でも共通であり、周辺環
境の励起波動関数の構造を示唆している。
(b)

(a)

図 2. (a)bR 及び(b)MeOH 中のレチナール色素について、第一励起状態の波動関数をアミノ酸残基毎に分類し、最大の係数をプロットした。

図 3 には、各フラグメントについて励起波動関数のノルムを計算し、PSB からの距離に関して、プロットしたものを示す。bR において、距離約 4 Å 程度の第一溶媒和圏では CT 等の効果が顕著に見られ、軌道間相互作用の重要さが示唆された。それを超える領域では CT の寄与は減衰し、エキシトンの寄与が相対的に重要になる。遷移双極子モーメント間相互作用の長距離性が反映していると考えられる。
更に、励起エネルギーの分割解析を行った。結果
は波動関数の解析の時と同様であり、色素－アミノ酸の CT 励起と局所励起が重要であり、アミノ酸間CT の寄与は無視できる程度であった。また、Tyr185

図 3. 各フラグメントの局所励起配置、色素との CT 励起配置のノルムを、フラグメント―色素間距離についてプロットした。（右）第一溶媒和圏において主要な寄与を与える
フラグメント。

－ 60 －

fukui2012_02.indb 60

14.1.9 1:44:15 PM

Ⅳ 研究業績 (2012)

が主要な寄与をすることも確認することができた。
��������������������� �� ������������� 周辺環境の溶媒効果を考慮するために必要な波動関数の構造について、上述のように解析を行った。本研究では、新たに、水溶液中における s-trans-acrolein の n-π*励起状態と π-π*励起状態についても同様の解析を行った。
気相中の実験結果と比較すると、水溶液中では n-π*励起で 0.3 eV の青方シフト、π-π*励起で 0.5 eV
もの赤方シフトを示す。解析の結果、これまでの研究で得られた蛋白質中や溶液中のレチナール色
素での結果と同様に、周辺環境－色素間の CT 励起配置と周辺環境における局所励起配置が波動関数に寄与している。前者は色素波動関数が近傍のアミノ酸の領域へと非局在化する効果であり、後者は周辺環境の波動関数の分極効果を表している。また、周辺のアミノ酸間の CT 励起配置の寄与
は 非 常 に 小 さ い こ と が 明 ら か に な っ た 。 ONIOM 法 を 用 い て 、 SAC-CI 法 に よ り 計 算 し た
s-trans-acrolein の励起エネルギーに CIS 法による環境効果を補正したところ、n-π*、π-π*ともスペク
トルシフトに関する実験結果を良好に再現した。
次に、このような構造を持つ波動関数がソルバトクロミックシフトを再現できることを確認する必要がある。そこで、本研究では AO 駆動 CI プログラムを開発した。周辺環境を含んだ励起状態の波動関数における電子励起を制限し、算出される励起エネルギーへの影響を検討した。周辺のアミノ酸間の CT 励起配置は、数において全波動関数の大部分を占めるにも関わらず、0.02 eV 程度の誤差しか与えない。局在化軌道を用いた結果、アミノ酸間 CT 励起が数値的な意味で first-orderinteracting space から外れたことを示している。
�������������������������������� 三重項励起状態におけるエネ
ルギー移動は、光合成系における余剰エネルギーを散逸するための経路や、光力学療法における一重項
酸素生成過程に含まれる。エキシトン・カップリングにより駆動される一重項励起エネルギー移動とは異なり、Dexter 機構で示されたように、三重項励起エネルギー移動においては交換相互作用により駆動されると考えられている。従って、三重項励起エネルギー移動では、ブリッジの電子状態の寄与によりドナー(D)とアクセプター(A)の電子的カップリング(HDA)が増大するものと期待される。
本研究では、三重項エネルギー移動のトンネル経路を明らかにするために、局在化分子軌道を用いた解析手法を開発した。これを応用することより、三重項の場合のエネルギー移動経路の特徴を一重項の場合との比較の観点から明らかにした。
前述したように、ブリッジを経由する一重項励起
エネルギー移動は、Förster 型の相互作用が主要であるため、D-A 間の直接移動やブリッジ状態を一つ経由する移動経路が主要であった（図 4a）。つまり、
hole と electron 対が同時に移動する。これに対して三重項の場合では、Förster 型の相互作用が小さくなるため、複数のブリッジ状態を経由する
super-exchange 機構が主要となることが分かった。
これは行列要素の表式

 ia Ĥ  bj   i,j Fa,b   a,b Fi,j   ia | jb    ab | ij

図 4. 励起エネルギー移動におけるトンネル経路の概念図。(a) 一重項において主要であるエキシトン経由機構。(b) ホールと電子移動が逐次的にカップルする三重項励起エネルギー移動(CHET 機構)。

－ 61 －

fukui2012_02.indb 61

14.1.9 1:44:22 PM

Ⅳ 研究業績 (2012)において、軌道 i と a のスピンが異なるため、(ia|jb)=0 となるからである。図 6b に示したように、三重
項移動において特徴的であるのは、ホール移動と電子移動が逐次的に起きる点である。これは、上式において a=b や i=j のときに(ab|ij)の値が増大するからである。
我々はこのメカニズムを、sequentially coupledhole and electron transfer (CHET) 機構として提案した。電子移動やホール移動との関連性から、分子軌道を用いて三重項励起エネルギー移動を制御できる可能性がある。

��(1) J. Hasegawa,“Fragment-Based Configuration Interaction Wave Function to Calculate
Environmental Effect on Excited States in Proteins and Solutions”
Chem. Phys. Lett. 571(*), 77–81 (2013).
(2) S. Nishizawa, J. Hasegawa, K. Matsuda,“Theoretical Investigation of the β Value of the Phenylene and Phenylene
Ethynylene Units by Evaluating Exchange Interaction between Organic
Radicals”
Chem. Phys. Lett. 555(*), 187–190 (2013).
(3) T. Kawatsu and J. Hasegawa,“Excitation Energy Transfer in GFP-X-CFP Model Peptides (X=amino acids):
direct vs. through-bridge energy transfers”
Intern. J. Quantum. Chem. 113(4), 563-568 (2013).
(4) T. Kawatsu and J. Hasegawa,“Sequentially Coupled Hole-Electron Transfer Pathways for Bridge-MediatedTriplet Excitation Energy Transfer”
J. Phys. Chem. C 116(44), 23252–23256 (2012).
(5) J. Hasegawa, K. J. Fujimoto, and T. Kawatsu“A Configuration Interaction Picture for a Molecular Environment Using
Localized Molecular Orbitals: The Excited States of Retinal Proteins”
J. Chem. Theo. Comp. 8(11), 4452-4461 (2012).
(6) T. Kawatsu, K. Matsuda, and J. Hasegawa“Singlet Excitation Energy Transfer Mediated by Local Exciton Bridges”
J. Phys. Chem. C 116(26), 13865-13876 (2012).
(7) J. Hasegawa, K. Fujimoto, and H. Nakatsuji“Color tuning in human cone visual pigments: the role of the protein
environment”
Progress in Theoretical Chemistry and Physics 26, 489-502 (2012).
(8) T. Sakano, J. Hasegawa, K. Higashiguchi, and K. Matsuda,“Chronological Change from Face-On to Edge-On Ordering of Zinc
Tetraphenylporphyrin at Phenyloctane-HOPG Interface”－ 62 －

fukui2012_02.indb 62

14.1.9 1:44:24 PM

Ⅳ 研究業績 (2012)

Chem. Asian J. 7(2), 394-399 (2012).
(9) Y. Yamamoto, J. Hasegawa, and Y. Ito,
“Kinetic investigation on carbamate formation from the reaction of carbon
dioxide with amino acids in homogeneous aqueous solution”
J. Phys. Org. Chem. 25(3), 239-247 (2012).
2. 学会��
(1) J. Hasegawa,“Computational Chemistry for Complex Systems: Environmental Effect inProteins and Solutions”
The Fourth Joint Symposium of PCOSS-CRC, Hokkaido University, 2013.5.9(2) J. Hasegawa“Theoretical Study on the Color Tuning Mechanism of Photo-functional
Proteins: Excited States and Molecular interactions”
2012 HU - NU - SNU - NIMS/MANA Joint Symposium, ”Challenges in Advanced
Chemistry of Asia”, Hokkaido University, 2012.12.6-7(3) J. Hasegawa“Configuration Interaction in Quantum Chemistry”
MAterial Simulation in Petaflops era (MASP2012), Institute for Solid State
Physics, Univ. Tokyo, 2012.6.25(4) J. Hasegawa“Color-tuning in Photo-functional Proteins: Electronic Structure andInteractions”
The 17-th International Symposium on Bioluminescence and Chemiluminescence,
Guelph, Canada, 2012.5.28-6.2(5) 長谷川淳也「視物質・蛍光蛋白質におけるカラーチューニング：分子間相互作用の理論解析」
岡山（岡山大学） 2013/3/15(6) 長谷川淳也「光機能性生体分子の励起状態に関する量子化学」
第2回量子化学ウインタースクール～基礎理論と生体系の理論～TCCIウインターカ
レッジ：量子化学
岡崎（分子科学研究所） 2012/12/17-18(7) 長谷川淳也“Excited states and molecular interactions in photo-functional proteins”
シンポジウム”Photochemistry of Supra Functional Molecular Systems”光化学討論会 東京（東京工業大学）2012/9/12-14－ 63 －

fukui2012_02.indb 63

14.1.9 1:44:24 PM

Ⅳ 研究業績 (2012)中� ��
理論研究部������ 今年度の研究の��
今年度は遷移金属元素を含んだ機能性金属錯体の物性と梯子型π共役分子の固体中の光物性について研究を行った。
䛆ጞ䜑䛻䛇㻌
㻌 㻌 遷移金属元素を含んだ金属錯体は様々な配位子との組み合わせで、多様な構造や電子状態をとることができ、様々な機能が発現することがある。高スピン状態を保つ錯体は記憶素子に、発光性錯
体は発光素子などに応用できる可能性がある。これらの機能が発現する仕組みを理解することは機
能性金属錯体の制御や設計に繋がるため、機能の発現機構の理論的解明が求められている。今年度はシアノ架橋した 1 次元多核金属錯体の磁気異方性と多核金属錯体の固体中の発光を量子化学計算により明らかにした。
䛆䝅䜰䝜ᯫᶫ䛧䛯 㻝 ḟඖከ᰾㔠ᒓ㘒య䛾☢Ẽ␗᪉ᛶ䛻㛵䛩䜛◊✲䛇㻌 㻌
1 次元鎖錯体は金属中心のスピン同士の強磁性的な相互作用により、大きなスピン角運動量を持つ可能性がありメモリなどへの応用が期待されている。Figure 1 に示したシアノ架橋 1 次元鎖錯体 {ReCl4(CN)M(DMF)4(NC)} (M = Mn(1), Fe(2),Co(3)) は遷移金属の種類に依存して磁気的性質が大きく異なり、Fe 錯体では低温で磁気ヒステリシスを示す[1]。本研究では磁気的な性質の予測を目指し、1 次元鎖錯体を構成する

Figure 1. 1 次元鎖錯体

単一ユニットの磁気異方性の原因を明らかにすることを目的とした。
X 線解析から１次元鎖錯体は対称中心を持っており、配位子の配向の異なる 2 種類の構造がある
ことが分かっている。1 次元鎖錯体から金属二核部分を抜き出した計算モデル[(NC)ReCl4(CN)M(DMF)4(NC)]を用いて理論計算を行った。2 つの構造(A、B)の初期構造として X 線解析の構造を用いて、水素原子の位置のみを構造最適化した。遷移金属の基底関数には Christiansenによる基底関数と ECP、その他の原子には cc-pVDZ を用いた。スピン結合定数 J 値の計算はDFT(B3LYP)法、CASSCF 法と MCQDPT 法で行った。スピン軌道相互作用(SOC)と外部磁場の効果を考慮した計算も行い、
磁気異方性を予測した。
全ての計算は Gaussian 09 と GAMESS を使用した。
Table 1 に各錯体の J 値を示した。DFT 法では Mn 錯体の J 値は実験結果と良い一致を示した。しかし、Fe 錯体に関しては実験値の 1/7 程度の値しか示さず、Co 錯体に関しては 2 つの構造で異なる磁性を示した。また、CASSCF 法と MCQDPT 法では実験値を再現しなかった。擬縮退状態を持つ Fe 錯体と Co 錯体に対して、CASSCF 波動関数を用いてスピン-軌道相互作用(SOC)と磁場の効果を加味した計算を行った。Fe 錯体の A 構造(2A)の外部磁場 0.1T 下での温度磁化率曲線は Figure 2－ 64 －

fukui2012_02.indb 64

14.1.9 1:44:25 PM

Ⅳ 研究業績 (2012)に示す結果となった。2A はシアノ配位子方向である y 軸から磁場を印加した時に y 軸方向のスピン角運動量期待値を持つ電子状態が安定化されることで、低温で温度磁化率曲線が上昇することが分かった。逆に、2B, 3A, 3B は DMF 配位子から磁場を印加した時に低温で温度磁化率曲線が上昇することが分かった。磁気異方性の原因となる電子状態を調べたところ、擬縮退状態間の相互作用から予想される磁気異方性の方向と、温度磁化率曲線の上昇をもたらす磁場の印加方向はほとんど一致した。従って、CASSCF 法の結果を解析することで、磁気異方性の方向をあらかじめ予測することができることが本研究によって明らかになった。

χMT(cm3/mol・K)

6.0

Table 1. スピン結合定数 J (cm-1)
1A
1B
2A
Fe錯体
2B
3A
Co錯体
3B

Mn錯体

DFT法 CASSCF法 MCQDPT法 実験値[1]
-5.52
-0.46
-1.78
-5.4
-7.56
-0.59
-2.31
0.58
-0.17
-0.91
4.8
0.68
-0.14
-0.87
1.65
0.16
1.05
2.4
-1.39
0.28
-1.18

5.0
4.0
3.0
2.0

平均

1.0

y軸

0.0
0

100 200
温度(K)Figure 2. 2A の磁化率曲線

���錯体��体������������
2+� � 燐光性錯体は量子収率が高いため、発光デバイスへの応用が期待されている。最近、実験で報告された白金(II)錯体は Scheme 1 に示すような構造を持ち、固体中で特異な発光を示す[1]。本研究では、周囲の錯体やカウンターアニオンによる静電場の影響を点電荷と

H2
N

N
Pt

N
H2

N

Buckingham ポテンシャルで表現した固体モデルを用いて、気相中及び固体中の励起エネルギーと構造変化について理論的に検討した。

Scheme 1

Pt の基底関数には Christiansen による基底関数と有効内殻ポテンシャル、その他の原子については cc-pVDZ を用いた。BLYP 法、B3LYP 法、B3PW91 法、O3LYP 法、LC-BLYP 法、CAM-B3LYP
法を用いて、Mulliken と自然軌道解析(NAO)と静電ポテンシャル(ESP)フィッティングの 3 つの方法
により点電荷を決定した。固体モデルの汎関数と点電荷の依存性を調べるために、中心錯体の点電荷を X 線データ構造で分かっている隣接する錯体やカウンターイオンの位置に配置して、点電荷が自己無撞着するまで繰り返し計算を行った。固体中の基底状態と三重項励起状態の構造を予測するために、固体モデルに Buckingham ポテンシャルも加えて構造最適化した。
以上の計算は Gaussian 09
を用いて行った。
系の全エネルギーから点電荷同士の静電エネルギーを引いたものを、固体中の静電場による中心錯体の安定化エネルギーと考えて固体モデルを評価した。個々のモデルでは、点電荷と安定化エネ
ルギーは 5 回程度の繰り返し計算で収束した。固体モデルのサイズによって中心錯体の安定化エネルギーと軌道エネルギー準位は大きく変化し、モデルの選択が重要であることが分かった。次に、汎関数と点電荷の種類に対する依存性を調べる

Table 1. 固体中の錯体の安定化エネルギー(kcal mol-1)
計算方法

Mulliken

BLYP
567.4
B3LYP
568.8
CAM-B3LYP 569.0

NAO

ESP

569.8
570.6
571.7

567.6
568.4
568.8

－ 65 －

fukui2012_02.indb 65

14.1.9 1:44:25 PM

Ⅳ 研究業績 (2012)

ために、中心錯体 1 分子の周りに 49 個の錯体と 100 個の Cl-を配置した固体モデルを用いた。Table
1 に示したように、安定化エネルギーの汎関数と点電荷依存性は非常に小さいことが分かった。
B3LYP 法と NAO 電荷を用いた固体モデルで最適化した基底状態の安定構造は、Figure 3 に示すように気相中の構造と比較して折れ曲がり、X 線構造

真空中

固体モデル

Figure 3. 基底状態の最適化構造と良く一致した。
䛆ᩥ⊩䛇[1] Harris, T. D.; Bennett, M.V.; Clérac R.; Long J. R. J. Am. Chem. Soc. 2010, 132, 3980-3988.
[2] K. Umakoshi (private communication).
[3] H. Yamada, C. Xu, A. Wakamiya, S. Yamaguchi, Macromol Chem. Phys. 210, 904-916 (2009).

�� 論文(1) S. Akatsu, Y. Kanematsu, T. Kurihara, S. Sueyoshi, Y. Arikawa, M. Onishi, S. Ishizaka, N
Kitamura, Y. Nakao, S. Sakaki, K. Umakoshi,"Syntheses and Luminescent Properties of 3,5-Diphenylpyrazolato-Bridged Heteropolynuclear
Platinum Complexes. The Influence of Chloride Ligands on the Emission Energy Revealed by the
Systematic Replacement of Chloride Ligands by 3,5-Dimethylpyrazolate”
Inorg. Chem. 51, 7977-7992, (2012).
(2) Y. Nakajima, S. Sakaki, Y. Nakao, H. Suzuki,“Theoretical Study of Dihydrogen Activation by a Trinuclear Ruthenium μ3-Imido Complex”
Organometallics, 31, 5342–5348, (2012).
(3) Y. Hayashi, Y. Matano, K. Suda, Y. Kimura, Y. Nakao, H. Imahori,“Effects of Carbon–Metal–Carbon Linkages on the Optical, Photophysical, and Electrochemical
Properties of Phosphametallacycle-Linked Coplanar Porphyrin Dimers”
Chem. Eur. J. 18, 15972-15983 (2012).

�� 学会��
(1) 野口純樹、佐藤啓文、中尾嘉秀「オキサラト架橋した多核金属錯体の磁気異方性に関する理論的研究」
第15回理論化学討論会, 仙台市福祉プラザ, 2012年5月24日～26日, 1C2b(2) 野口純樹、佐藤啓文、中尾嘉秀「有機ラジカルを配位子とするCo(II)錯体の磁性に関する理論的研究」
第6回分子科学討論会, 東京大学本郷キャンパス, 2012年9月18日～21日, 2P120(3) 成田真弘、佐藤啓文、中尾嘉秀－ 66 －

fukui2012_02.indb 66

14.1.9 1:44:25 PM

Ⅳ 研究業績 (2012)「CPMDを用いた梯子型π共役化合物の発光に関する理論的研究」
第6回分子科学討論会, 東京大学本郷キャンパス, 2012年9月18日～21日, 4P089(4) 中尾嘉秀、山田哲士、馬越啓介「ピラゾラト架橋した白金二核金二核錯体の固体中の発光に関する理論的研究」
第62回錯体化学討論会, 富山大学五福キャンパス, 2012年9月21日～23日, 2Ba-01(5) 野口純樹、中尾嘉秀、佐藤啓文「Cr(III)、Co(II)のオキサラト架橋錯体の磁気異方性に関する理論的研究」
第62回錯体化学討論会, 富山大学五福キャンパス, 2012年9月21日～23日, 2Ba-07(6) 中尾嘉秀、竹中裕喜雄、佐藤啓文「第一原理分子動力学法によるサーモクロミック銅(II)錯体に関する理論的研究」
第62回錯体化学討論会, 富山大学五福キャンパス, 2012年9月21日～23日, 2Ba-08(7) 枡井基典、佐藤啓文、中尾嘉秀「第1周期遷移金属からなるシアノ架橋1次元鎖型錯体の磁気的性質に関する理論的研究」
日本化学会第93春季年会, 立命館大学, 2013年3月22日～25日, 1G3-54(8) 加藤諒佑、佐藤啓文、中尾嘉秀「燐光性白金(II)錯体の結晶中の発光に関する理論的研究」
日本化学会第93春季年会, 立命館大学, 2013年3月22日～25日, 1G3-55－ 67 －

fukui2012_02.indb 67

14.1.9 1:44:26 PM

Ⅳ 研究業績 (2012)

International Relationship Office�������
�����

��

��

Program-specific Associate Professor Toshimasa ISHIDA

1. Summary of the research of the year
(1) A Nonadiabatic Ab Initio Dynamics Study on Rhodopsin and its Analog Isorhodopsin
Rhodopsin (Rh) has 11-cis retinal as chromophore and is the photosensitive chemical found on theoutersegment of rod-like cells in the retina, the light-sensing structure of the eye. Isorhodopsin(isoRh) is an Rh analogue that contains 9-cis retinal embedded in the same opsin environment. Bothare known to yield bathorhodopsin (bathoRh), a photoisomer that contains all-trans retinal, via
cis-trans isomerization of the 11 or 9 position upon absorption of a photon. Despite their similarity,
the photoisomerization period and quantum yield is largely different. Rhodopsin photoisomerization
is experimentally known to be faster (tRh = 200 fs, tisoRh = 600 fs) and more efficient (quantum yield:
ΦRh = 0.65, ΦisoRh = 0.22). We carried out non-adiabatic ab initio dynamics calculations on the twomolecules. We have already reported that the reaction times and quantum yields are qualitatively
reproduced.
Rhodopsin is reported to givebathorhodopsin only while isorhodopsin
yieldsabyproduct.

Therigorous

selectivity in rhodopsin would be anotherreasonwhyrhodopsinisselected

biologically.

Comparison

with

our

previous opsin-free investigations reveals
that opsin tends to confine the twist of
the active dihedral to only one direction
and funnels transitions into the vicinity

Figure 1 Isomerization schemes in (a) Weiss-Warshel
Model and (b) from the analysis of actural trajectories.

of minimum energy conical intersections (MECI). The twist-confinement totally blocks
simultaneous twisting of ϕ9 and ϕ11 (=C10–C11=C12–C13=) and enhance the quantum yields. The
opposite rotation of ϕ9 and ϕ11 (‘wring-a-wet-towel’ motion) takes place upon photoexcitation,
which also does without opsin. The wring-a-wet-towel motion is dynamically enhanced incomparison with the one expected from locations of the MECI.
Weiss and Warshel proposed a model for cis-trans photoisomerization in 1979. They assumed
that a trajectory goes back and forth around the crossing point in the excited state. In their scheme,
if the transition takes place when the trajectory goes forth, the product is generated and if it does

－ 68 －

fukui2012_02.indb 68

14.1.9 1:44:27 PM

Ⅳ 研究業績 (2012)

when the trajectory go back, the ground state reactant is regenerated. In order to check if theirscheme is applicable to the present systems, we counted how many trajectories make turns before
transitions for Rh. If their argument is correct, the number of turns should be strongly correlated tothe compound generated: if the number of turns is even (odd), it should results in the product(reactant). It is found, however, that the ratio of the generated compounds expected from thenumber of turns were 58.3%, which means that the correlation is weak because 50% corresponds tono correlation. Moreover, it is found that the transition probability for the first passing over thetransition region (corresponding to no turns) is 0.95. Thus, the first access to the crossing point
almost determines the fate of the trajectory. Thus, the present simulation reveals that the
Weiss-Warshel model for cis-trans photoisomerization is not applicable for rhodopsin because thebranching ratio after transition is crucial.
(2) Photochemical dynamics of indolylmaleimide derivatives
On-the-fly nonadiabatic ab initio molecular dynamics simulations have been carried out forthree ionic species of indolylmaleimides (3-(1H-3-indolyl)-2,5-dihydro-1H-2,5-pyrroledione, IM) toclarify the mechanisms of photochemical reactions. The results are obtained for (i) a monovalentanion with a deprotonated indole NH group (IM-’), (ii) a monovalent anion with a deprotonatedmaleimide NH group (IM-’’) and (iii) a divalent anion with doubly deprotonated indole and themaleimide NH groups (IM2-). Quantum chemical calculations are treated at the three state averaged
complete-active space self-consistent field level for 6 electrons in 5 orbitals with the cc-pVDZ basis
set (CAS (6, 5) SCF/cc-pVDZ). Molecular dynamics simulations are performed with electronically
nonadiabatic transitions included using the Zhu–Nakamura version of the trajectory surface hopping(ZN-TSH) method. It is found that the nonadiabatic transitions occur accompanied by the stretchingand shrinking motions of the N(7)–C(8) bond in the case of IM-’ and the C(11)–N(12) bond in IM2rather than the twisting motion of the dihedral angle. We also found that the ultrafast S2  S1
nonadiabatic transitions occur through the conical intersection (CoIn) right after photoexcitation to
S2 in IM-’ and IM2-. Furthermore, the S1  S0 nonadiabatic transitions are found to take place inIM-’. It is concluded that IM2- would mainly contribute to the photoemission, because the S1 ← S0
and S2 ← S0 transitions of IM-’’ are dipole-forbidden transitions and, moreover, IM2- is found to be
the only species to stay in the S1 state without non-radiative decay.
(3) A model theoretical study on ligand exchange reactions of CooA

－ 69 －

fukui2012_02.indb 69

14.1.9 1:44:28 PM

Ⅳ 研究業績 (2012)

Rr-CooAisaCO-sensor heme protein,
where binding of COwith the heme group
stimulatesatranscriptional

activator

activity of CooA. In thisprocess,

the

heme

undergoes a series ofligand exchanges. In theferric form, the heme has
Cys75 and Pro2 as the
axial

ligands.

Inthereduced ferrous form, theheme has His77 instead

Figure 2 Kohn-Sham orbital energy diagram for free base porphyrin,

of Cys75 as an axial

R1, R1’, R2, and R2’ in the smaller model of Rr-CooA along withligand with Pro2. Only in

isodensity surface maps55 for key orbitals. Only occupied orbitals are

the reduced form, CooA

shown in the diagram. The red horizontal line corresponds tocan bind CO that replacesnon-bonding orbital localized at the sulfur atom of Cysteine

Pro2. Model calculations(n(S(Cys)). The blue and light blue lines correspond to highest

are

to

occupied Kohn-Sham orbital (HOKSO) (a1u) and the next HOKSO

ligand(a2u) in the free base porphyrin. The black lines stand for othercarriedout

elucidatetheexchange

reactions

of

CooA.

because the species have the open shell. Note that the energies of the

We

used

clustermodels that include thecenterorbitals. R1 and R1’ have α- and β-orbitals with different energies

iron

and

α-orbital in R1’ and doubly-occupied orbital in R2 are -0.249 and-0.221 hartree, therefore, below the range of energy shown.

theproximate ligand portions. The whole CooA protein was not dealt with in the present study because
the present modeling would give the characteristic of ligand exchange reactions more clearly.
Geometry optimization for reactants and products were carried out. We employed the ONIOM (ourown N-layered integrated molecular orbital and molecular mechanics) scheme, a quantum
mechanics/molecular mechanics (QM/MM) approach, for some computations. For the others,
quantum mechanical (QM) computations alone were performed. QM calculations were done at theB3LYP hybrid functional level. We used the B3LYP scheme in the present computation because
many calculations have been carried out at this level and accuracy/error at this level has been
established. The basis set used is the Hay-Wadt set and the corresponding effective core potential－ 70 －

fukui2012_02.indb 70

14.1.9 1:44:36 PM

Ⅳ 研究業績 (2012)

for iron and the 6-31G(d) basis set for the other elements. For MM calculations, universal force
field was employed.
The coordinated proline is found to be the neutral, protonated form. The ligand exchange ofcysteine for histidine is reproduced by a relatively small model. This exchange would be mainly due
to difference in stability of non-bonding sulfur p-orbital in Cys75 between the ferric and ferrous
states, which is shown in Figure 2.
The selectivity of gas molecules among CO, NO, and O2 in the proteins are explained byrelative stability of products for Rr-CooA. This is the case also for Ch-CooA, where the aminogroup of the N-terminus and a histidine are coordinated to the iron ion both in the ferric and ferrous
state. The ability to bind the gas molecules is a little stronger in Rr-CooA than in Ch-CooA. In theferric form of Rr-CooA, heme is deformed to a ruffled from whereas heme is planar in the ferrous
form, which leads to red-shifted Q-band in the former.
2. Original papers(1) Wilfredo Credo Chung, Shinkoh Nanbu, and Toshimasa Ishida“A QM/MM Trajectory Surface Hopping Approach to Photoisomerization of Rhodopsin andIsorhodopsin. The Origin of Faster and More Efficient Isomerization for Rhodopsin”,
J. Phys. Chem. B 2012, 116, 8009−8023.
(2) Tatsuhiro Murakami, Manabu Nakazono, Alexey Kondorskiy, Toshimasa Ishida and Shinkoh
Nanbu“Photochemical dynamics of indolylmaleimide derivatives”
Phys. Chem. Chem. Phys., 2012, 14, 11546–11555(3) Toshimasa Ishida and Shigetoshi Aono,“A model theoretical study on ligand exchange reactions of CooA”
Phys. Chem. Chem. Phys. 15, 6139-6148 (2013).
(4) Jun-ichi Aihara, Masakazu Makino, Toshimasa Ishida, and Jerry R. Dias
Analytical Study of Superaromaticity in Cycloarenes and Related Coronoid Hydrocarbons
J. Phys. Chem. A. in press

dx.doi.org/10.1021/jp4016678

3. Presentation at academic conferences(1) Wilfredo C. Chung、南部 伸孝、石田 俊正
A Nonadiabatic Ab Initio Dynamics Study on Rhodopsin and its Analog Isorhodopsin
第 9 回福井謙一記念研究センターシンポジウム(P42)2012 年 1 月 6 日

京都(2) 村上龍大、石田俊正、南部伸孝、－ 71 －

fukui2012_02.indb 71

14.1.9 1:44:41 PM

Ⅳ 研究業績 (2012)「インドリルマレイミドの光物理過程の非断熱力学」
日本化学会第 92 春季年会

(4A4-01)2012 年 3 月 28 日

日吉(3) CHUNG, Wilfredo Credo; ISHIDA, Toshimasa; NANBU, Shinkoh; NAKAMURA, Hiroki,“A non-adiabatic QM/MM trajectory approach to photoisomerization of rhodopsin andisorhodopsin. The origin of faster and more efficient isomerization in rhodopsin”,
28th Symposium on Chemical Kinetics and Dynamics (2E4), Kasuga, Fukuoka, June 7, 2012
(4) KOBAYASHI, Osamu; ISHIDA, Toshimasa; NANBU, Shinkoh,“Theoretical study of charge transfer and deactivation process of donor-acceptor type thiophene
derivatives”,
28th Symposium on Chemical Kinetics and Dynamics (2P16), Kasuga, Fukuoka, June 7, 2012
(5) OHTA, Ayumi; ISHIDA, Toshimasa; NANBU, Shinkoh”Theoretical study of selectivity mechanism on photoisomerization reaction between
cyclohexadiene and hexatriene”
28th Symposium on Chemical Kinetics and Dynamics (2P19), Kasuga, Fukuoka, June 7, 2012
(6) Wilfredo Credo Chung, Toshimasa Ishida,Shinkoh Nanbu and Hiroki Nakamura,“A QM/MM Trajectory Surface Hopping Approach to Photoisomerization of Rhodopsin andIsorhodopsin”,
The 14th International Congress of Quantum Chemistry(ICQC2012)(I.62), Boulder,

Colorado, USA. Jun. 25-30(2012)(7) 太田亜由美、石田俊正、南部伸孝、「シクロヘキサジエン、ヘキサトリエン間の光異性化反応における選択制の理論的研究」
第 6 回分子科学討論会 2012

3P088

東京、2012 年 9 月 20 日

(8) 小林理、赤間知子、石田俊正、南部伸孝
ドナーアクセプター型ポリチオフェン誘導体の電荷移動と失活過程」
第 6 回分子科学討論会 2012

3P111

東京、2012 年 9 月 20 日

(9) Wilfredo Credo Chung, 南部伸孝、石田俊正「ロドプシンとイソロドプシンの光応答性に関する非断熱 ab initio トラジェクトリ法
による理論的研究」
第 6 回分子科学討論会 2012

4A04 東京、2012 年 9 月 21 日

(10) 村上龍大、Kondorskiy Alexey、石田俊正、南部伸孝「蛍光性分子の光化学動力学」
第 6 回分子科学討論会 2012

4E16

東京、2012 年 9 月 21 日

(11) 北淑宏、南部伸孝、石田俊正「緑色蛍光タンパク質の光励起動力学：QM/MM 法による非断熱 ab initio 分子動力学」
第 6 回分子科学討論会 2012

4P124 東京、2012 年 9 月 21 日

(12) Wilfredo Credo Chung, Shinkoh Nanbu, and Toshimasa Ishida,－ 72 －

fukui2012_02.indb 72

14.1.9 1:44:41 PM

Ⅳ 研究業績 (2012)“A Non-adiabatic Trajectory Approach to Photoisomerization for Rhodopsin and Isorhodopsin.
The Origin of Faster and More Efficient Isomerization in Rhodopsin”
Congress on Computational Physics 2012, Kobe, Oct. 15-18, 2012(13) 石田俊正、Wilfredo C. Chung、南部伸孝、青野重利”Theoretical studies on reactions in biomolecules: photoisomerization of rhodopsins

andligand exchange in CooA”
第１０回福井謙一記念研究センターシンポジウム

2012 年 11 月 30 日

京都

－ 73 －

fukui2012_02.indb 73

14.1.9 1:44:41 PM

Ⅳ 研究業績 (2012)

Hidekazu IKENO
Assistant Professor
1. Summary of the research of the year
Systematic ab-initio Multiplet Calculations of Transition Metal L2,3 XANES
Molecules and molecular systems which consist of transition metal element, organic moiety, The
spectral shape 3d transition metal (M) L2,3 x-ray absorption near-edge structure (XANES) is dominated by
the multiplet structures, since the strong electronic correlations among spatially localized 3d electrons andthe 2p core-hole play a central role. In order to simulate the multiplet structures in M-L2,3 XANES, we havedeveloped an ab initio charge transfer multiplet (CTM) method for XANES[2,3,4]. This method is based on
the restricted active space configuration interaction (RASCI) method in quantum chemistry using fully
relativistic (four-component) molecular spinors. All relativistic effects, including the spin-orbit coupling at
the M-2p levels, are taken into account by solving Dirac equation. All possible Slater determinants,
corresponding to the electronic configurations, 2p63dn and 2p53dn+1 which will dominate the initial and final
states, respectively, are considered. In addition, theelectronic excitation from molecular spinors mainlycomposed of O-2p to those of M-3d, that is, chargetransfer, are also taken into account by taking O-2p
1 or 2.
In this study, the M-L2,3 XANES for divalent,trivalent and tetravalent M oxides (M=Ti-Ni) withvariouscrystalline

structuresarecalculated

systematically the ab initio CTM method. The effectsof the M-O covalent bonding and charge transfer
oxygen to M ions on the M-L2,3 XANES are
investigated in detail.
First, we have clearly specified that the M 2p-3d
and 3d-3d inter-electron interaction energies are
reduced by the covalent bonding between the M andoxygen ions, because the spatial distributions of M-3d
spinors are increased by the covalent bonding. Thisaffects the multiplet structures and the transition
probabilities in the M-L2,3 XANES. Then the effects ofcharge transfer on M L2,3-edges have discussed. In the

PACS (10-22 m2/atom)spinors as another RAS space with max hole number is

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

TiO

0.6
0.5
0.4
0.3
0.2
0.1
0

Ti2O3

2.0

SrTiO3

1.6
1.2
0.8
0.4
0

445

450

455

460

465

Energy (eV)

470

475

Fig. 1 Theoretical Ti-L2,3 XANES with (black line)
and without (gray line) charge transfer effects

ab initio CTM approach, the contribution of the charge-transferred configuration increased with increasing－ 74 －

fukui2012_02.indb 74

14.1.9 1:44:42 PM

Ⅳ 研究業績 (2012)atomic number and valency of M ions in the oxides. This tendency is similar to that of the covalent bonding
between M-3d and O-2p spinors. The stronger the covalency, the larger the influence of the CT on M-L2,3
XANES/ELNES.
Finally, The M-L2,3 XANES of M oxides were calculated systematically by the ab initio CTM
approaches. Figure 1 shows the theoretical Ti-L2,3 XANES spectra for Ti oxides, for instance. In the case ofdivalent oxides of Ti, V, Cr, Mn, and Fe, the spectral shapes were hardly affected by the CT; it was only
necessary to take the CT into account for divalent Ni oxides. The effects of the CT on L2,3-edges became
larger when the valency of the TM increased. The CT mainly contributed to the changes in peak intensities
and peak broadness and to the formation of satellite peaks.

Variations of Zr-L2,3 XANES in Zr oxides
Zr is an important element in the ceramic science. Many zirconium-bearing phases are used, e.g. fortransformation toughening of structural ceramics, in bioceramics, and as nucleation agents for the fabricationof glass ceramics. The identifications of the local atomic environment of Zr in ceramics is important for the
new development of materials. Among many techniques, X-ray absorption near-edge structure (XANES) is a
powerful technique to selectively observe the local environment of specific element in materials. In this work,
Zr-L2,3 XANES of tetravalent zirconium oxides are studied both theoretically and experimentally. The
influences of the coordination number and local symmetry of Zr on the spectral shapes are investigated.
Three polymorphs of ZrO2, namely, cubic ZrO2 (c-ZrO2), tetragonal ZrO2 (t-ZrO2), monoclinic ZrO2
(m-ZrO2), and orthorhombic SrZrO3 (o-SrZrO3) are examined. The coordination numbers and symmetries ofZr sites are different in these four compounds. The crystal structures of these four oxidic Zr compounds are
drawn in Fig. 2(a). The Zr-L2,3 XANES for these four Zr oxides were computed using the ab initio chargetransfer multiplet (CTM) method. The results obtained are shown in Fig. 2 (b). One can see that both L3- andL2-edges are mainly composed of two peaks as indicated by A and B Fig. 2 (b). In every compound, thespectral shapes of L3- and L2-edges are different. In particular, the difference in the A/B intensity ratios isclearly visible at both edges. As can be seen, the A/B intensity ratio is much smaller at the L3-edge than at
the L2-edge. This can be ascribed to the larger multiplet effects at the L3-edge.
In Fig. 2(b), clear differences in spectral shapes among the four compounds are evident, reflecting thedifference in the coordination number and in the symmetry around the Zr sites. The A/B intensity ratio isalso found to be very sensitive to the coordination number of Zr. As the coordination number of Zr decreases,
the A/B intensity ratio increases. The A/B intensity ratio at the Zr L3- and L2-edge XANES can therefore beused to roughly estimate the coordination number of Zr in such oxides. The Zr-L2,3 XANES of Zr oxides
were also measured using synchrotron light sources. The experimental results confirms our theoreticalprediction that the A/B intensity ratio at Zr L3- and L2-edges is sensitive to the coordination number of Zr.

－ 75 －

fukui2012_02.indb 75

14.1.9 1:44:42 PM

Ⅳ 研究業績 (2012)(a)c-ZrO2 (CN=8)t-ZrO2 (CN=8)m-ZrO2 (CN=7)

o-SrZrO3 (CN=6)

C
C

C

B

O
A

O

A

(b)

B

O

Zr L3 -edge

0.28

B

A

Zr L2 -edge

B
0.24

0.20

B

PACS (Mb)

A
A

0.16

0.12

0.08

0.04

0
2210

2215

2220

c-ZrO2 (CN=8)c-ZrO2 (CN=8)t-ZrO2 (CN=8)t-ZrO2 (CN=8)m-ZrO2 (CN=7)

m-ZrO2 (CN=7)

SrZrO3 (CN=6)

SrZrO3 (CN=6)2225

Energy (eV)2230

2235 2300

2305

2310

Energy (eV)

2315

2320

Figure 2 (a) Crystalline structures of Zr-oxides. (b) Theoretical Zr-L2,3 XANES of tetravalent Zr-oxides.

2. Original papers(1) Thomas Höche, and Hidekazu Ikeno, Marisa Mäder, Grant S. Henderson, and Robert I.R. Blyth,
Brian C. Sales, and Isao Tanaka
Vanadium L2,3 XANES experiments and first-principles multielectron calculations: Impact of
second-nearest neighboring cations on vanadium-bearing fresnoites
Am. Mineral. 98, 665-670 (2013).
(2) Hidekazu Ikeno, Michael Krause, Thomas Hoöhe, Christian Patzig, Yongfeng Hu, Antje Gawronski,
Isao Tanaka and Christian Rüssel
Variation of Zr-L2,3 XANES in tetravalent zirconium oxides
J. Phys.: Condens. Matter 25, 165505 (2013).

3. Presentation at academic conferences(1) Hidekazu Ikeno－ 76 －

fukui2012_02.indb 76

14.1.9 1:44:44 PM

Ⅳ 研究業績 (2012)“Systematic ab initio multiplet calculations for L2,3 XAS of 3d transition metal compounds”
Workshop on Fundamental Aspects of X-ray Spectroscopies, (Feb. 21-22, 2013, Utrecht, theNetherlands)(2) Hidekazu Ikeno and Teruyasu Mizoguchi“Theory of XANES/ELNES: from quasi-particle to many-particle”
19th WIEN2k WORKSHOP, (Sep 3-7, 2012, Tokyo, Japan)(3) Hidekazu Ikeno, Teruyasu Mizoguchi, and Isao Tanaka“Systematic Calculations of L2,3 x-ray absorption spectra for 3d Transition Metal Oxides by Ab
Initio Charge Transfer Multiplet Method”
The 15th International Conference on X-ray Absorption Fine Structure (XAFS15), (Jul 22-28, 2012,
Beijing, China)(4) Hidekazu Ikeno, Teruyasu Mizoguchi, and Isao Tanaka“Relativistic Configuration Interaction Calculations under the External Magnetic Field: Application
to XMCD”
XAFS theory workshop: XAFS theory and nano particles, (July 18-20, 2012, Chiba, Japan)(5) Hidekazu Ikeno, Teruyasu Mizoguchi, Yukinori Koyama, Zenpachi Ogumi, Yoshiharu Uchimoto,and Isao Tanaka“Theoretical Fingerprints of M-L2,3 XANES and ELNES for LiMO2 (M=Mn,Fe,Co,Ni) by ab initio
Multiplet Calculations”
The 3rd International Symposium on Advanced Microscopy and Theoretical Calculations (AMTC3),(May 9-11, 2012, Gifu, Japan)(6) 池野豪一「遷移金属 L2,3 white line の第一原理計算」
日本顕微鏡学会第 68 回学術講演会(2012 年 5 月 14 日〜16 日，つくば)(7) 池野豪一「3d 遷移金属化合物における L2,3 端 X 線吸収スペクトルの第一原理計算」
第 3 回 CMSI 研究会(2012 年 12 月 3 日〜5 日)

4. Others(1) 池野豪一，田中功「六方晶フェライトにおけるMössbauerパラメータの第一原理計算」
第10回福井センターシンポジウム (2012年11月30日，京都)－ 77 －

fukui2012_02.indb 77

14.1.9 1:44:46 PM

Ⅳ 研究業績 (2012)

２．シニアリサーチフェロー

Shigeru NAGASE
Senior Research Fellow

1. Summary of the research of 2012(a) Lead-Lead Double Bonds Stabilized by Dative Carbene Ligands
Carbon-carbon double bonds play an important role in many fields of chemistry. As a new type of
double bonds between the heavier atoms, diatomic molecules stabilized by the coordination of dative
N-heterocyclic carbenes (:L) are of interest currently. The synthesis and isolation have been performed for
L:Si=Si:L and L:Ge=Ge:L (:L = :C[N(2,6-iPr2-C6H3)CH]2). The Si and Ge atoms are regarded as
being in a formal zero-oxidation state. The Si-Si and Ge-Ge bond distances compare well with typical doublebond distances of R2Si=SiR2 and R2Ge=GeR2. Because the heaviest Pb case remains unknown, theoretical
calculations were performed.

Fig. 1. (a) Optimized structure of L:Pb=Pb:L. (b) Donation of the lone pair of :L into the vacant 6p
orbital of the Pb atom (for simplicity, the 6s orbital of Pb is omitted).
The optimized structure of L:Pb=Pb:L is presented in Fig. 1a, which has C2h symmetry. Molecularorbital analysis shows that one  bond and one bond exist clearly between the Pb atoms, the Pb atoms
being doubly bonded. It is notable that the Pb-Pb bond distance of 2.833 Å is considerably shorter than the
shortest Pb-Pb double bond distance of 2.903 Å known to date and differs little from the Pb-Pb bond distanceof Pb2. As Fig. 1b shows, L:Pb=Pb:L is formed by the donation of the lone pair of L: into the vacant 6p
orbital on Pb. Therefore, the Pb-Pb-L bond angle of 93.0° is close to 90°. The electron donation from L:
makes the Pb atom negatively charged slightly (the charge on Pb is -0.17). The binding energy between Pb2(3g-) and 2L: is calculated to be 45.6 kcal/mol. It is expected that L:Pb=Pb:L is an interesting synthetic
target.

(b) Heaviest Analogues of Alkynes
The heavier analogues of alkynes, REER (E = Si, Ge, Sn, Pb), have attracted special interest in－ 78 －

fukui2012_02.indb 78

14.1.9 1:44:47 PM

Ⅳ 研究業績 (2012)main-group element chemistry. Therefore, all the heavier analogues have been synthesized and isolated up to
now: RSiSiSiRSi (RSi = SiiPr{CH(SiMe3)2}2), BbtSiSiBbt (Bbt = C6H2-2,6-{CH(SiMe3)2}2-4-C(SiMe3)3),
Ar’GeGeAr’ (Ar’ = C6H3-2,6-(C6H3-2,6-iPr2)2), BbtGeGeBbt, Ar’SnSnAr’, and Ar*PbPbAr* (Ar* =C6H3-2,6-(C6H2-2,4,6-iPr3)2). However, X-ray crystal analysis and theoretical calculations revealed that the
Pb-Pb bond distance of the heaviest analogue, Ar*PbPbAr*, is much longer than typical Pb-Pb single bonddistances and no  bond exists between the Pb atoms. Therefore, it has been accepted that the heaviest Pb
analogues of alkynes take a singly bonded structure, unlike the Si, Ge, and Sn cases.
It is convenient to view REER as consisting of two ER components. ER has ground doublet and excitedquartet states. As E becomes heavier, theground doublet state becomes more stable
than the quartet state. Therefore, thedoublet-doublet

interaction

is

most

R

R

Pb

Two interaction modes (a and b) between
state are presented in Fig. 2. Mode aengenders a triply bonded structure because

RR

preferred for the heaviest case (E = Pb).
two PbR components in the ground doublet

R

R

Pb

R

a

Pb
R

Pb

b

Fig. 2. Two interaction modes between the doublet PbR

the donor-acceptor interaction of lone-pairelectrons is allowed to form two dative bonds between Pb atoms. Mode b engenders a singly bonded
structure because the lone pair of PbR does not participate in bonding. The lone-pair orbital of PbR is mostly
composed of the 6s orbital of Pb. Because of the so-called relativistic effect, the 6s orbital shrinks and isstabilized. Therefore, mode a may be expected to be less favorable than mode b.

Fig. 3. Singly and triply bonded structures optimized for Ar*PbPbAr*
The singly bonded structure of Ar*PbPbAr* determined by X-ray crystal analysis was optimized using
density functional theory calculations, as shown in Fig. 3 The optimized Pb-Pb bond distance agrees
reasonably well with the experimental value in the crystal structure, despite packing forces. The HOMO andLUMO of the singly bonded structure respectively correspond to in-plane antibonding in* and out-of-planebonding out orbitals. Interestingly, it was found that a triply bonded structure is located as an energy－ 79 －

fukui2012_02.indb 79

14.1.9 1:44:48 PM

Ⅳ 研究業績 (2012)minimum by switching the HOMO and LUMO, which is more stable than the singly bonded structure. The
observed UV-vis spectrum is well reproduced by calculations on the triply bonded structure, which confirm
that Ar*PbPbAr* takes a triply bonded structure in solution.
The Pb-Pb bond distance of 3.071Å calculated for the triply bonded structure of Ar*Pb-PbAr* is longer
than the Pb-Pb single bond distance of 2.844 Å in Ph3PbPbPh3. For REER, we have suggested thatelectropositive silyl groups shorten the E-E bond distance. Several bulky silyl groups were tested using
density functional calculations. It was found that the Pb-Pb bond distance of 2.696Å calculated for
RSiPbPbRSi (RSi = SiiPr{CH(SiMe3)2}2) is remarkably shorter than the Pb-Pb single bond distance of 2.844
Å in Ph3Pb-PbPh3. In addition, the Pb-Pb bond distance is considerably shorter than the shortest Pb-Pb
double bond distance of 2.903 Å known to date for Si(SiMe3)3MesPb=PbSi(SiMe3)3Mes (Mes =C6H2-2,4,6-Me3). However, the triply bonded structure was calculated to be 4.3 kcal/mol less stable than the
singly bonded structure (Pb-Pb = 3.080Å). We are still searching for good substituent groups that stabilize atriply bonded structure with a sufficiently short Pb-Pb bond.
(c) Short Bonds between Transition Metals
The most common coordination numbers for transition metal complexes are four, five, and six. As noveltransition metal complexes with an unsupported two-coordinate metal, R*MFe(5-C5H5)(CO)2 (M = Fe, Mn,
Cr; R* = C6H-2,6-Ar2-3,5-iPr2 where Ar= C6H2-2,5,6-iPr3) were synthesized andisolated. As is shown in Fig. 4, the
bulky

R*

group

surrounds

thetwo-coordinate M atom and blocks theformation of any third bond to M. The
metal-metal bond distances are much
shorter than those of the known
unsupported complexes.
We

have

predicted

that,

for

example, the Fe-Fe bond distance isgreatly

shortened

inthebicyclic

four-membered ring presented in Fig. 5a. It is remarkable that the Fe-Fe bond distance of 2.045 Å is much
shorter than the currently known shortest Fe-Fe
bond distance of 2.127 Å. This bond shortening

Et

H2Sn

Fe

assisted by two heavier main group atoms suchFe

as Sn was very recently corroborated in the joint
research with experiment for the bicyclic
four-membered Ru2Sn2 ring complex presented
in Fig. 5b. The Ru-Ru bond distance of 2.343 Å
determined by X-ray crustal analysis agrees

SnH2
Cp

Cp
Cp = 5-C5H5

a

Et

Et
Et

Sn

Et

Et

Ru Sn
Ru Cp* Et

Et

Cp*
Cp* = 5-C5Me5bFig. 5. Bicyclic four-membered ring complex.

well with the calculated value of 2.363 Å. It is shorter than the Ru-Ru distance of 2.449-2.469 Å in the－ 80 －

fukui2012_02.indb 80

14.1.9 1:44:49 PM

Ⅳ 研究業績 (2012)

related bridge complexes, for which it is assumed that the two Ru atoms are triply bonded. As shown in Fig.
6, localized molecular orbital analysis reveals that one clear  bond exists between the Ru atoms, while two
three-centered  orbitals are delocalized over each of the three-membered Ru2Sn rings, which make animportant contribution to Ru-Ru bonding. As a result, the Ru-Ru bond has a somewhat multiple-bondcharacter, as indicated by the bond order of 1.3. It is also predicted that the Ru-Ru bond distance in thebicyclic four-membered ring is shortened further in the bicyclic six-membered Ru2Sn4 ring, although theshortening does not take place for the corresponding Ru2C4 ring.

Fig. 6. One orbital between Ru atoms and two three-centered orbitals delocalized over thethree-membered rings for the complex presented in Fig. 5.
As interesting compounds with heavier main group atoms and transition metals in their frameworks,
anionic iron complexes with a clear bond between an ate-type pentacoordinate Ge atom and an Fe Atomwere investigated. Since silicon versions of olefin metathesis are unknown, 18-electron titantium silylene
complexes were investigated, which have loosely bound and readily removable Lewis base ligands that areclassified as the Schrock-type silydenes.
(d) Nanocarbon Systems
We have performed theoretical calculations for tunable charge-transport properties of Ih-C80, linking
Lu3N@C80 to electron acceptors, metal-promoted restoration of defective graphene, fullerene genetic code,silylene-bridged Lu3N@Ih-C80, La@C82/-extended tetrathiafulvalene conjugate, violation of the isolated
pentagon rule for endohedral metallic carbide fullerenes, three Yb@C82 isomers cocrystallized with NiII
(octaethylporphyrin), intramolecular electron transfer in donor-acceptor conjugates of La2@C80 and TCAQ,
coordinative interactions between porphyrins and C60, La@C82, and La2@C80, MCD spectroscopy ofendohedral metallofullerenes, and Diels-Alder reactions of La@C82.

2. Original papers(1) H. Zheng, X. Zhao, W. -W. Wang, T. Yang, and S. Nagase, "Sc2@C70 Rather Than Sc2C2@C68: Density
Functional Theory Characterization of Metallofullerene Sc2C70", J. Chem. Phys., 137, 014308 (5 pages)(2012).

－ 81 －

fukui2012_02.indb 81

14.1.9 1:44:49 PM

Ⅳ 研究業績 (2012)(2) S. Sato, S. Seki, G. Luo, M. Suzuki, J. Lu, S. Nagase, and T. Akasaka, "Tunable Charge-Transport
Properties of Ih-C80 Endohedral Metallofullerenes: Investigation of La2@C80, Sc3N@C80, andSc3C2@C80", J. Am. Chem. Soc., 134, 11681-11686 (2012).
(3) L. Feng, M. Rudolf, S. Wolfrum, A. Troeger, Z. Slanina, T. Akasaka, S. Nagase, N. Martin, T. Ameri, C.
J. Brabec, and D. M. Guldi, "A Paradigmatic Change: Linking Fullerenes to Electron Acceptors", J. Am.
Chem. Soc., 134, 12190-12197 (2012).
(4) W. -W. Wang, J. -S. Dang, J. -J. Zheng, X. Zhao, E. Osawa, and S. Nagase, "Metal-Promoted
Restoration of Defective Graphene", J. Mater. Chem., 22, 16370-16375 (2012).
(5) J. -S. Dang, W. -W. Wang, J. -J. Zheng, X. Zhao, E. Osawa, and S. Nagase, "Fullerene Genetic Code:Inheritable Stability and Regioselective C2 Assembly", J. Phys. Chem. C, 116, 16233-16239 (2012).
(6) K. Sato, M. Kako, M. Suzuki, N. Mizorogi, T. Tsuchiya, M. M. Olmstead, A. L. Balch, T. Akasaka, and
S. Nagase, "Synthesis of Silylene-Bridged Endohedral Metallofullerene Lu 3N@Ih-C80", J. Am. Chem.
Soc., 134, 16033-16039 (2012).
(7) Y. Takano, S. Obuchi, N. Mizorogi, R. Carcia, M. A. Herranz, M. Rudolf, S. Wolfrum, D. M. Guldi, N.
Martin, S. Nagase, and T. Akasaka, "Stabilizing Ion and Radical Ion Pairs States in a Paramagnetic
Endohedral Metallofullerene/-Extended Tetrathiafulvalene Conjugate", J. Am. Chem. Soc., 134,
16103-16106 (2012).
(8) T. Yang, X. Zhao, and S. Nagase, "Structural Determination on Yb@C78 Reveals an Unexpected
Relationship of Yb@C2n (2n = 74-78)", J. Phys. Chem. C, 116, 21640-21645 (2012).
(9) T. Yang, X. Zhao, S. -T. Li, and S. Nagase, "Is the Isolated Pentagon Rule Always Satisfied for Metallic
Carbide Endohedral Fullerenes?", Inorg. Chem., 51, 11223-11225 (2012).
(10) Z. Slanina, F. Uhlik, S. -L. Lee, L. Adamowicz, T. Akasaka, and S. Nagase, "Stability Computations for
Isomers of La@Cn (n = 72, 74, 76)", Molecules, 17, 13146-13156 (2012).
(11) M. Suzuki, Z. Slanina, N. Mizorogi, X. Lu, S. Nagase, M. M. Olmstead, A. L. Balch, and T. Akasaka,"Single-Crystal X-ray Diffraction Study of Three Yb@C82 Isomers Cocrystallized with NiII
(octaethylporphyrin)", J. Am. Chem. Soc., 134, 18772-18778 (2012).
(12) Y. Takano, S. Obuchi, N. Mizorogi, R. Garcia, M. A. Herranz, M. Rudolf, D. M. Guldi, N. Martin, S.
Nagase, and T. Akasaka, "An Endohedral Metallofullerene as a Pure Electron Donor: IntramolecularElectron

Transfer

inDonor-Acceptor

Conjugatesof

La2@C80

and

11,11,12,12-Tetracyano-9,10-anthra-p-quinodimethane (TCAQ)", J. Am. Chem. Soc., 134, 19401-19408(2012).
(13) T. Tanikawa, M. Saito, J. -D. Guo, S. Nagase, and M. Minoura, "Synthesis, Structures, and Optical
Properties of Heterasumanenes Containing Group 14 Elements and Their Related Compounds", Eur. J.
Org. Chem., 7135-7142 (2012).
(14) K. Sato, M. Kako, N. Mizorogi, T. Tsuchiya, T. Akasaka, and S. Nagase, "Bis-Silylation of
Lu3N@Ih-C80: Considerable Variation in the Electronic Structures", Org. Lett., 14, 5908-5911 (2012).
(15) N. Kano, N. Yoshinari, Y. Shibata, M. Miyachi, T. Kawashima, M. Enomoto, A. Okazawa, N. Kojima,
J. -D. Guo, and S. Nagase, "Anionic Iron Complexes with a Bond between an Ate-Type
Pentacoordinated Germanium and an Iron Atom", Organometalics, 21, 8059-8062 (2012).

－ 82 －

fukui2012_02.indb 82

14.1.9 1:44:49 PM

Ⅳ 研究業績 (2012)(16) T. Tsuchiya, M. Rudolf, S. Wolfrum, S. G. Radhakrishnan, R. Aoyama, Y. Yokosawa, A. Oshima, T.
Akasaka, S. Nagase, and D. M. Guldi, "Coordinative Interactions between Porphyrins and C60, La@C82,
and La2@C80", Chem. -Eur. J., 19, 558-565 (2013).
(17) L. Feng, M. Suzuki, N. Mizorogi, X. Lu, M. Yamada, T. Akasaka, and S. Nagase, "Mapping the Metal
Positions inside Spherical C80 Cages: Crystallographic and Theoretical Studies of Ce2@D5h-C80 and
Ce2@Ih-C80", Chem. -Eur. J., 19, 988-993 (2013).
(18) W. -W. Wang, J. -S. Dang, J. -J. Zheng, X. Zhao, and S. Nagase, "Selective Growth of Fullerenes from
C60 to C70: Inherent Geometrical Connectivity Hidden in Discrete Experimental Evidence", J. Phys.
Chem. C, 117, 2349-2357 (2013).
(19) T. Yang, X. Zhao, and S. Nagase, "Quantum Chemical Insight of the Dimetallic Sulfide Endohedral
Fullerene Sc2S@C70: Does It Possess the Conventional D5h Cage?", Chem. Eur. J., 19, 2649-2654(2013).
(20) M. Yamada, Z. Slanina, N. Mizorogi, A. Muranaka, Y. Maeda, S. Nagase, T. Akasaka, and N.
Kobayashi, "Application of MCD Spectroscopy and TD-DFT to Endohedral Metallofullerenes for
Characterization of their Electronic Transitions", Phys. Chem. Chem. Phys., 15, 3593-3601 (2013).
(21) V. Y. Lee, S. Aoki, T. Yokoyama, S. Horiguchi, A. Sekiguchi, H. Gornitzka, J. –D. Guo, and S. Nagase,"Toward a Silicon Version of Metathesis: From Schrock-Type Titanium Silylidenes toSilatitanacyclobutenes", J. Am. Chem. Soc., 135, 2987-2990 (2013).
(22) Y. Morinaka, S. Sato, A. Wakamiya, H. Nikawa, N. Mizorogi, F. Tanabe, M. Murata, K. Komatsu, K.
Furukawa, T. Kato, S. Nagase, T. Akasaka, and Y. Murata, "X-Ray Observation of a Helium Atom andPlacing a Nitrogen Atom inside He@C60 and He@C70", Nat. Commun., 4, 1554 (5 pages) (2013).
(23) T. Kuwabara, M. Saito, J. –D. Guo, and S. Nagase, "Unexpected Formation of Ru2Sn2 Bicyclic
Four-Membered Ring Complexes with Butterfly and Inverse-Sandwich Structures", Inorg. Chem., 52,3585-3587 (2013).
(24) S. Sato, Y. Maeda, J. –D. Guo, M. Yamada, N. Mizorogi, S. Nagase, and T. Akasaka, "Mechanistic
Study of the Diels-Alder Reaction of Paramagnetic Endohedral Metallofullerene: Reaction of La@C82
with 1,2,3,4,5-Pentamethylcyclopentadiene", J. Am. Chem. Soc., 135, 5582-5587 (2013).

2. Review articles(1) X. Lu, L. Feng, T. Akasaka, and S. Nagase, "Current Statues and Future Developments of Endohedral
Metallofullerenes", Chem. Soc. Rev., 41, 7723-7760 (2012).
(2) Y. –P. Xie, X. Lu, T. Akasaka, and S. Nagase, "New Features in Coordination Chemistry: Valuable
Hints from X-Ray Analyses of Endohedral Metallofullerenes", Polyhedron, 52, 3-9 (2013).
(3) S. Nagase, "Multiple Bonds between Lead Atoms and Short Bonds between Transition Metals", Pure
Appl. Chem., 85, 649-659 (2013).

－ 83 －

fukui2012_02.indb 83

14.1.9 1:44:50 PM

Ⅳ 研究業績 (2012)

Keiji MOROKUMA
Senior Research Fellow, Kenichi Fukui Memorial Research Group 1
1. Summary of the Research of the Year
Theoretical and Computational Studies of Complex Molecular Systems
The goals of the research of this group are 1. to develop theoretical methods (such as ONIOM, GRRM) forcomplex systems, 2. to demonstrate that such methods can be used for simulations of structures, reactions anddynamics of complex systems and 3. to solve some of the important problems in each field. Our research is
supported in part by the Institute and in large fraction by a 5-year grant in the area of High Performance
Computing for Multi-Scale and Multi-Physics Phenomena from CREST (Core Research for Evolutional Scienceand Technology) program of JST (Japan Science and Technology Agency) that ended on March 31, 2012. With
several postdoctoral fellows and a few research assistants, as well as in collaboration with my group at Emory
University, the group of Prof. Stephan Irle of Nagoya University as well as Prof. Satoshi Maeda, AssistantProfessor at Hokkaido University, we have a strong team of theoretical/computational chemists working together
toward a common goal. Since detailed description on individual projects can be found in the reports ofpostdoctoral fellows, here the areas of studies and titles of individual projects are summarized.

I. Simulation of Reactions and Dynamics of Complex and Biomolecular Systems
In the area of simulation of complex and biomolecular systems, in recent years we have studied structuresand reactions of complex molecular and biomolecular systems. For complex molecular systems, our emphasis has
been catalyses, both transition metal catalysis and organic catalysis, with special attention to selectivity. In
addition to the standard TS optimization method, we extensively used the GRRM strategy (see research area III
below) to find reaction pathways. We expanded our theoretical studies of catalytic reactions that take place in thenano cavity created by the protein and nucleic acids. In our studies of the structures of intermediates andtransition states of enzymatic reactions, we explicitly included the effects of protein employing the ONIOM
QM/MM scheme.
Another research topic in complex systems is chemical reactions in excited electronic states. We have studied
potential energy surfaces of low-lying excited states for some organic and inorganic photochemical reactions, andelucidated rather complex reaction mechanisms involving different electronic states. Recently a most advanced
multiconfigurational ab initio method called DMRG (density matrix renormalization group) method, has beenused in collaboration with its developer, Prof. Yanai of Institute of Molecular Science, for calculations ofpotential energy surfaces of excited states of complex molecular systems.
a) Sp3–sp2 vs sp3–sp3 C–C Activation in Rh-Catalyzed Ring Opening of Benzocyclobutenol: A DFT Study(See research activities of Dr. Ding)b) Theoretical Studies of ACDC: Asymmetric Counteranion Directed Catalysis (See research activities of
Dr. Petrova)c) Theoretical Studies of PTC: Enentioselective Base-Free Phase-Transfer Catalysis (See research activities
of Dr. Petrova)d) Theoretical Modeling of Stereochemistry Control of Copper Catalysts Based on the Chirality of DNA(See research activities of Dr. Petrova)e) Theoretical Study of Asymmetric Hydration Catalyzed by DNA-based Artificial Enzyme
1－ 84 －

fukui2012_02.indb 84

14.1.9 1:44:50 PM

Ⅳ 研究業績 (2012)

Metalloenzymes (See research activities of Dr. Ke)f) Theoretical Study of Polymerization Catalyzed by Artificial Metalloenzymes (See research activities ofDr. Ke)g) QM/MM Structural and Spectroscopic Analysis of the Di-iron(II) and Di-iron(III) Ferroxidase Site in
M Ferritin (See research activities of Dr. Harris)h) Theoretical Studies of Reduction of NO in qNOR Enzyme (See research activities of Dr. Hatanaka)i) Reactivity of Hydrogen Atom Transfer (HAT) with Metal-Oxo and How Enzymes Facilitates theReaction (See research activities of Dr. Chung)j) Reaction Mechanism of Spiropyran-Merocyanine Photochromic Reaction (See research activities of Dr.
Liu)k) Theoretical Study on the Deactivation Path of Fluorescence (See research activities of Dr. Liu)l) Reaction Mechanism of Photo-induced Decarboxylation of the Photoactivatable Green FluorescentProtein: An ONIOM(QM:MM) Studym) Excited-State Proton Transfer Controls Irreversibility of Photoisomerization in Mononuclear
Ruthenium(II) Monoaquo Complexes: A DFT Study (See research activities of Dr. Ding)n) Chemiluminescence and Bioluminescence of Dioxetanones (See research activities of Dr. Chung)II. Simulation of Nanomaterials
In the area of simulation of nanomaterials, we continued our research efforts on quantum chemicalmolecular dynamics (QM/MD) computations of carbon nanostructure formation based on density functional tightbinding (DFTB). Our focus in the last few years has been on the growth dynamics of single-walled carbon
nanotube (SWCNT) and graphene, for which the growth mechanism is still poorly understood. The chirality
control in the CNT growth is one of the most important pending issues. We invented a theoretical method todefine the local chirality of irregular carbon nanotubes and used this to analyze mechanism of retention and lossof chirality during the growth of carbon nanotubes on transition metal clusters. We also addresses on the chirality
control in the CNT growth from organic templates. The nucleation and growth of graphenes on transition metal
surfaces have also been studied using a variety of model systems.
a) Effects of Molecular Dynamics Thermostats on Descriptions of Chemical Non-Equilibrium (See research
activities of Dr. Page)b) Optimization of a Genetic Algorithm for the Functionalization of Fullerenesc) The Dynamics of Local Chirality during SWCNT Growth: Armchair versus Zigzag Nanotubesd) Quantum Chemical Molecular Dynamics Simulations for Chirality-Controlled SWCNT Growth (Seeresearch activities of Dr. Kim)e) SWCNT Growth from Chiral Carbon Nanorings: Prediction of Chirality and Diameter Influence on
Growth Ratesf) Theoretical Insights into Chirality-Controlled SWCNT Growth from a Cycloparaphenylene Templateg) Temperature Dependence of Catalyst-Free Chirality-Controlled Single-Walled Carbon Nanotube
Growth from Organic Templates (See research activities of Dr. Haibei Li)h) Revealing the Dual Role of Hydrogen for Growth Inhibition and Defect Healing in Polycyclic Aromatic
Hydrocarbon Formation: QM/MD Simulations (See research activities of Dr. Haibei Li)i) Coupled Cluster and Density Functional Theory Calculations of Atomic Hydrogen Chemisorption on
Pyrene and Coronene as Model Systems for Graphene Hydrogenationj) Sub-Surface Nucleation of Graphene Precursers near a Ni(111) Step Edge
2
－ 85 －

fukui2012_02.indb 85

14.1.9 1:44:50 PM

Ⅳ 研究業績 (2012)k) Graphene Nucleation on Transition Metal Surfaces (See research activities of Dr. Page)l) Simulated IR/Raman Spectra of Graphene and Graphene Oxide (See research activities of Dr. Page)

III. Method Developments and Applications
In collaboration with Profs. Koichi Ohno and Satoshi Maeda, combining the two methods of potential energy
search we have developed before, the ADDF (adiabatic downward distortion following) method and the AFIR
(artificial force-induced reaction (AFIR) method, we have developed the Global Reaction Route Mapping(GRRM) strategy. These methods allow determination of all the reaction pathways, including intermediates andtransition states as well as minim energy conical intersections and seam of crossing, of complex reaction systems
without any guess. The strategy includes expanding the applicability to complex molecular systems by using
micro-iteration techniques. The GRRM strategy has been actively applied to homogenous catalysis systems suchas transition metal catalysts and organic catalysts without transition metals, for which the research area I above
should also be referred to. The GRRM strategy has been particularly powerful in finding reaction pathways ofphoto-activated molecules, in which multiple pathways involving various electronically excited sates andcrossings between them can effectively be located using the GRRM strategy.
a) Systematic Exploration of the Mechanism of Chemical Reactions: the Global Reaction Route Mapping(GRRM) Strategy by the ADDF and AFIR Methodsb) Exploring Potential Energy Surfaces of Large Systems with Artificial Force Induced Reaction in
Combination with ONIOM and Microiterationc) Automated Exploration of Photolytic Channels of HCOOH: Conformational Memory via Excited
State Roamingd) Global Ab Initio Potential Energy Surfaces for Low-lying Doublet States of NO3e) Theoretical Study on the Photodissociation of Methylamine Involving S1, T1, and S0 States (See research
activities of Dr. Xiao)f) Photodissociation of CH3NO2 (See research activities of Dr. Isegawa)g) Aqueous Mukaiyama-Aldol Reaction Catalyzed by Lanthanide Trication (See research activities of Dr.
Hatanaka)

Original papers

1. P. S. Krstic, J. P. Allain, C. N. Taylor, J. Dadras, S. Maeda, K. Morokuma, J. Jakowski, A. Allouche, and C. H.
Skinner, Deuterium Uptake in Magnetic Fusion Devices with Lithium Conditioned Carbon Walls, Phys. Rev. Lett.,
110, 105001/1-5, 2013.
2. B. Fu, J. M. Bowman, H. Xiao, S. Maeda, and K. Morokuma, Quassiclassical Trajectory Studies of the
Photodissociation Dynamics of NO3 from the D0 and D1 Potential Energy Surfaces, J. Chem. Theo. Comp., 9,893-900, 2013.
3. K. R. S. Chandrakumar, A. J. Page, S. Irle and K. Morokuma, Carbon Coating Precedes SWCNT Nucleation on
Silicon Nanoparticles: Insights from QM/MD Simulations, J. Phys. Chem. C, 117, 4238-4244, 2013.
4. S. Maeda, K. Ohno and K, Morokuma, Systematic Exploration of the Mechanism of Chemical Reactions: the Global
Reaction Route Mapping (GRRM) Strategy by the ADDF and AFIR Methods, Phys. Chem. Chem. Phys., 15,3683-3701, 2013.
5. A. J. Page, C.-P. Chou, B. Q. Pham, H. Witek, S. Irle and K. Morokuma, Quantum Chemical Investigation of
Epoxide and Ether Groups in Graphene Oxide and Their Vibrational Spectra, Phys. Chem. Chem. Phys., 15,3725-3735, 2013.
6. L. Ding, L. W. Chung, K. Morokuma, Reaction Mechanism of Photo-induced Decarboxylation of the
Photoactivatable Green Fluorescent Protein: An ONIOM(QM:MM) Study, J. Phys. Chem. B, 117, 1075-1084,
2013.

3－ 86 －

fukui2012_02.indb 86

14.1.9 1:44:50 PM

Ⅳ 研究業績 (2012)

7. K. R. S. Chandrakum ar, A. Puretzky, C. Rouleau, J. D. Readle, D. B. Geohegan, K. More, V. Krishnan, G. Duscher,
B. Sumpter, S. Irle, and K. Morokuma, High-Temperature Transformation of Fe-Decorated Single-Wall Carbon
Nanohorns to Nanooysters: A Combined Experimental and Theoretical Study, Nanoscale, 5, 1849-1857, 2013.
8. S. Maeda, E. Abe, M. Hatanaka, T. Taketsugu, and K. Morokuma, Exploring Potential Energy Surfaces of Large
Systems with Artificial Force Induced Reaction in Combination with ONIOM and Microiteration, J. Chem. Theo.
Comp., 5, 5058-5063, 2012.
9. A. J. Page, T. Isomoto, J. Knaup, S. Irle, and K. Morokuma, Effects of Molecular Dynamics Thermostats on
Descriptions of Chemical Non-Equilibrium, J. Chem. Theo. Comp., 8, 4019-4028, 2012.
10. A. Y. Timoshkin, and K. Morokuma, Novel group 13 Lewis superacids and 13-15 donor-acceptor cryptands forhydrogen activation: a theoretical study, Phys. Chem. Chem. Phys., 14, 14911-14916, 2012.
11. H.-B. Li, A. J. Page, S. Irle, and K. Morokuma, SWCNT Growth from Chiral Carbon Nanorings: Prediction of
Chirality and Diameter Influence on Growth Rates, J . Am. Chem. Soc., 134, 15887-15896, 2012.
12. P. S. Krstic, J. P. Allai, A. Allouched, J, Jakowski, J. Dadras, C. N. Taylor, Z. Yang, K. Morokuma, and S. Maeda,
Dynamics of deuterium retention and sputtering of Li-C-O surfaces, Fusion Eng. Design, 87, 1732-1736, 2012.
13. Z. Ke, S. Abe, T. Ueno, and K. Morokuma, Catalytic Mechanism in Artificial Metalloenzyme: QM/MM Study of
Phenylacetylene Polymerization by Rhodium Complex Encapsulated in apo-Ferritin, J. Am. Chem. Soc., 134,
15418-15429, 2012.
14. H. Xiao, S. Maeda and K. Morokuma, Global Ab Initio Potential Energy Surfaces for Low-lying Doublet States ofNO3, J. Chem. Theo. Comp., 8, 2600-2605, 2012.
15. S. Sekharan, K. Katayama, H. Kandori and K. Morokuma, The “OH-Site” Rule for Seeing Red and Green, J. Am.
Chem. Soc., 134, 10706-10712, 2012.
16. W. Treesuwan, H. Hirao, K. Morokuma, and S. Hannongbua, Characteristic vibration patterns and protein bindingof odor compounds from bread baking volatiles: Density functional, ONIOM study and principal component
analysis (PCA), J. Mol. Model., 18, 2227-2240, 2012.
17. Y. Wang, H.-J. Qian, K. Morokuma, and S. Irle, Coupled Cluster and Density Functional Theory Calculations ofAtomic Hydrogen Chemisorption on Pyrene and Coronene as Model Systems for Graphene Hydrogenation, J. Phys.
Chem. A, 116, 7154-7160, 2012
18. K. P. O’Halloran, C. Zhao, N. S. Ando, A. J. Schultz, T. F. Koetzle, P. M. B. Piccoli, B. Hedman, K. O. Hodgson,
E. Bobyr, M. L. Kirk, S. Knottenbelt, E. C. Depperman, B. Stein, T. M. Anderson, R. Cao, Y. V. Geletii, K. I.
Hardcastle, D. G. Musaev, W. A. Neiwert, X. Fang, K. Morokuma, S. Wu, P. Koegerler and C. L. Hill, Revisiting
the Polyoxometalate-Based Late-Transition-Metal-Oxo Complexes: The “Oxo Wall” Stands, Inorg. Chem., 51,
7025-7031, 2012.
19. S. Maeda, T. Taketsugu and K. Morokuma, Automated Exploration of Photolytic Channels of HCOOH:
Conformational Memory via Excited State Roaming, J. Phys. Chem. Lett., 3, 1900-1907, 2012.
20. H.-B. Li, A. J. Page, Y. Wang, S. Irle, and K. Morokuma, Sub-Surface Nucleation of Graphene Precursers near aNi(111) Step Edge, Chem. Comm., 48, 7937-7939, 2012.
21. J. Kim, A. J. Page, S. Irle, and K. Morokuma, The Dynamics of Local Chirality during SWCNT Growth: Armchairversus Zigzag Nanotubes, J. Am. Chem. Soc., 134, 9311-9319, 2012J.
22. Jakowski, S. Irle, B. Sumpter, and K. Morokuma, Modeling charge transfer in fullerene collisions via real timeelectron dynamics simulations, J. Phys. Chem. Lett., 3, 1536-1542, 2012.
23. M. A. Addicoat, A. J. Page, Z. E. Brain, L. Flack, K. Morokuma and S. Irle, Optimization of a Genetic Algorithm
for the Functionalization of Fullerenes, J. Chem. Theo. Comp., 8, 1841-1851, 2012.
24. J. Jakowski. S. Irle and K. Morokuma, Time-dependent quantum dynamical simulations of C2 condensation under
extreme conditions, Phys. Chem. Chem. Phys., 14, 6266-6272, 2012.
25. V. P. Ananikov, N. V. Orlov, S. S. Zalesskiy, I. P. Beletskaya,.V. N. Khrustalev, K. Morokuma and D. G. Musaev,
Catalytic Adaptive Recognition of Thiol (SH) and Selenol (SeH) Groups Towards Synthesis of Functionalized
Vinyl Monomers, J. Am. Chem. Soc., 134, 6637-3349, 2012.
26. H.-B. Li, A. J. Page, S. Irle, and K. Morokuma, Theoretical Insights into Chirality-Controlled SWCNT Growthfrom a Cycloparaphenylene Template, ChemPhysChem, 13, 1479-1485, 2012.
27. M. N. Ryanzantsev A. Altun and K. Morokuma, Color Tuning in Rhodopsins: The Origin of the Spectral Shiftbetween the Chloride-bound and Anion-free Forms of Halorhodopsin, J. Am. Chem. Soc., 134, 5520-5523, 2012.

2. Review articles

1. S. Irle, A. J. Page, B. Saha, Y. Wang, K. R. S. Chandrakumar, Y. Nishimoto, H.-J. Qian, K. Morokuma, Atomistic
mechanism of carbon nanostructure self-assembly as predicted by QM/MD simulations, in eds. J. Leszczynski and
M. Shukla, “Practical Aspects of Computational Chemistry: An Overview of the Last Two Decades and Current
Trends”, 103-172 (2012): Springer-European Academy of Sciences. ISBN 978-94-007-0922-5

4－ 87 －

fukui2012_02.indb 87

14.1.9 1:44:50 PM

Ⅳ 研究業績 (2012)

4. Presentation at academic conferences and universities

1. Keiji Morokuma, “Fascinating World of Theory of Chemical Reactions”, Keynote Speaker, CRC International
Symposium in Strasbourg: Chemical Theory of Complex Systems, Strasbourg, France, March 7-8, 2013.
2. Keiji Morokuma, “Exciting World of Theoretical Studies of Chemical Reactions – From Gas Phase Reactions toNano Structures, Catalysts, and Enzymatic Reactions”, Departmental Invited Seminar, Department of Chemistry,
Miami University, Miami, FL, USA, February 15, 2013.
3. Keiji Morokuma. “Automatic Search of Potential Energy Surfaces for Saddles and Intersection”, Invited Speaker,
2013 Mesilla Chemistry Workshop on Dynamics for Chemical Reaction Pathways. Role of Non-Statistical Effects,
Las Cruces, NM, USA, February 10-12, 2013.
4. Keiji Morokuma, “Exciting World of Theoretical Studies of Chemical Reactions – From Gas Phase Reactions toNano Structures, Catalysts, and Enzymatic Reactions”, Special Departmental Seminar for 65th Birthday Celebrationof Prof. J. M. Bowman, Department of Chemistry, Emory University, Atlanta, GA, USA, February 8, 2013.
5. K. Morokuma, “Multilevel simulations of biomolecular reactions”, Invited lecture, The second international
symposium on large-scale computational sciences: Nnao- and bio-simulations. Japan Society and Technology
Agency, Tokyo, November 8, 2012.
6. K. Morokuma, “New Fascinating World of Theory of Chemical Reactions”, Plenary Speaker, the 3rd International
Symposium of Theoretical Chemistry, USTHB, Alger, Algeria, October 14-17, 2012.
7. K. Morokuma, “New Paradigm in Exploration of Reaction Paths in Organometallic Catalysis”, Plenary Speaker,
International Conference "Catalysis in Organic Synthesis", (ICCOS-2012). Zelinsky Institute of Organic Chemistry,
Moscow, Russia, September 15-20, 2012.
8. Keiji Morokuma, “How much became understood about chemical reaction mechanisms of complex molecularsystems by theoretical and computational chemistry?”, Special seminar, Hokkaido Section, Chemical Society ofJapan, Hokkaido University, Japan, August 30, 2012.
9. Keiji Morokuma, “Exploring reaction pathways using automated reaction route finders”, Invited Speaker, 244th
American Chemical Society National Meeting, Philadelphia, PA, USA. August 19-23, 2012.
10. Keiji Morokuma, “Exciting World of Theoretical Studies of Chemical Reactions – From Gas Phase Reactions toNano Structures, Catalysts, and Enzymatic Reactions ” , Plenary Speaker, International Symposium on
Computational Sciences (ISCS) shanghai, China, August 13-14, 2012.
11. Keiji Morokuma, “Exciting World of Theoretical Studies of Chemical Reactions – From Gas Phase Reactions toNano Structures, Catalysts, and Enzymatic Reactions”, Departmental Invited Seminar, Institute of Theoretical
Chemistry, Nanjing University, Nanjing, China, August 10, 2012.
12. K. Morokuma,“Exciting World of Theoretical Studies of Chemical Reactions – From Gas Phase Reactions toNano Structures, Catalysts, and Enzymatic Reactions, Departmental Invited Seminar, Department of Chemistry,
Sun Yat-sen University, Guangzhou, China, August 7, 2012.
13. K. Morokuma, “Exploration of reaction pathways using automatic search methods; Quantum mechanicalmolecular dynamics simulations of formation of carbon nano structures; ONIOM(QM:MM) approaches tochemical reactions in protein environment”, Invited Speaker, 2012 Summer School on Theoretical Chemistry,
South China Normal University, Guangzhou, China, August 6, 2012.
14. K. Morokuma, “Mechanisms of Chemical Reactions of Organic and Biomolecular Systems”, Invited Speaker,
International Symposium on Quantum Mechanics and Molecular Dynamics of Organic and Biological Reactivity,
UCLA, USA, June 20-23, 2012.
15. K. Morokuma, “Exciting World of Theoretical Studies of Chemical Reactions – From Gas Phase Reactions toNano Structures, Catalysts, and Enzymatic Reactions”, Invited Speaker, International Symposium on Theoretical
Chemistry in Rio: Nascimento Conference, Rio de Janeiro, BR, June 11-12, 2012.
16. K. Morokuma, “Theoretical Studies on Dynamics, Mechanism and Active Species in Luminescence andPhotoconversion of Chromophores in Protein ” , Invited Speaker, the 17th International Symposium on
Bioluminescence and Chemiluminescence, Guelph, Canada, May 28 - June 2, 2012.
17. K. Morokuma, “Two Stories of Chemical Reactions. 1. Exploring Reaction Pathways Using Automated Reaction
Route Finders. 2. Nucleation, Growth and Healing Processes of Single-Walled Carbon Nanotubes”, Invited Speaker,
AFOSR Contractors’ Meeting on Molecular Dynamics and Theoretical Chemistry, Arlington, VA, USA, May
23-25, 2012.

5. Public talks

1. Let’s Explore the World of Chemical Reactions Using Computer (in Japanese), University Moc Lectures, Rakuhoku
High School, Kyoto, November 16, 2012.
5－ 88 －

fukui2012_02.indb 88

14.1.9 1:44:51 PM

Ⅳ 研究業績 (2012)

３．リサーチリーダー

Shigeyoshi SAKAKI

Research Leader, Kenichi Fukui Memorial Research Groups II
1. Summary of the research of 2012
Molecules and molecular systems which consist of transition metal element, organic moiety,non-transition metal element, and hypervalent species are attractive research targets in wide areas ofchemistry. Actually, some of those molecules play important roles as metal enzymes, molecular catalysts,
and molecular devices such as photo-sensitizer, molecular switch, luminescence material etc. Theirfunctions deeply relate to their electronic structures. In this regard, we need to know the electronic
structure of the complex system including transition metal element.
At the same time, those complex systems are interesting and challenging research targets from the pointof view of theoretical/computational chemistry, because their electronic structures are not simple but
complicated in many cases. In particular, transition metal complexes bearing large correlation effects arechallenging research target even nowadays. Also, the post Hartree-Fock calculations of very big systems
like metal-organic-framework and molecular crystal are still challenging. Our group is theoreticallyinvestigating those complex systems bearing complicated electronic structure.
This year, we theoretically investigated (i) two-step evaluation method of binding energy and potential
energy surface of van der Waals complexes, (ii) proposal of QM/MM approach to molecular crystal,(iii) CASPT2 study of inverted sandwich complexes of 4d metals, (iv) theoretical study of abnormal
three-coordinate Pt disilyl complexes, and (v) 3D-RISM-SCF study of hydrolysis of cis- and trans-platine.
We wish to report summary of them.
(i) Two-Step Evaluation Method of Binding Energy and Potential Energy Surface of van der
Waals Complexes
Evaluation of intermolecular distance and binding energy of van der Waals complex/cluster at
ab initio level of theory are computationally demanding when many monomers are involved.
Starting from MP2 energy, we reached a two-step evaluation method of binding energy of van der
Waals complex/cluster through reasonable approximations;(1)
BE(MP2) = BE(HF) + ΣMi ΣMj {BE(Mi-Mj)(MP2) - BE(Mi-Mj)(HF)}
BE(MP2.5) = BE(HF) + ΣMi ΣMj {BE(Mi-Mj)(MP2.5) - BE(Mi-Mj)(HF)}(2)(3)
BE(MP2.5) = BE(MP2) + ΣMi ΣMj {BE(Mi-Mj)(MP2.5) - BE(Mi-Mj)(MP2)}
where HF represents the Hartree-Fock calculation and Mi, Mj etc. are interacting monomers.
The first term is the usual binding energy of the complex/cluster evaluated at the HF level. The
second term is the sum of the differences in two-body binding energy between the correlated and HF
levels of theory. This equation can be obtained by taking an reasonable approximation that thethree-center and four-center two-electron integrals are small. This equation was applied to

Figure 1. Comparison of Binding energy between reference value and the approximated value witheqs. 1 to3－ 89 －

fukui2012_02.indb 89

14.1.9 1:44:51 PM

Ⅳ 研究業績 (2012)various van der Waals complexes consisting of
up-to-four monomers at MP2 and MP2.5 levels oftheory.

We found that this method is capable ofproviding precise estimate of the binding energy andreproducing well the potential energy surface of vander Waals complexes/clusters; the maximum error of
the binding energy is less than 1 kcal/mol and 1% in
most cases except for several limited cases.
These equations are also useful for geometry
optimization of molecular clusters shown in Scheme 1.

Scheme 1. Cluster complexes examined here.

The intermolecular distance is reproduced well by these approximate equations, as shown in Figure
2.

Figure 2. Comparison between optimized inter-molecular distance calculated with the approximate
methods and the usual MP2 to MP2.5 methods.

(ii) Proposal of new QM/MM approach for geometry optimization of periodic molecular crystal:
Self-consistent point charge representation for crystalline effect on target QM molecule
Post Hartree-Fock calculation of molecular crystal is one of the important targets fortheoretical/computational study now, because many chemical issues have been reported in molecular
crystals; for instance, spin transition of transition metal complex, photo-absorption and photo-emission ofmolecules in crystal, chemical reaction in crystal and so on. Usually, periodic calculation with DFT method
is applied to such infinite systems. However, the use of
Lattice unit
functional is limited and also plane-wave basis sets are used inmany calculations. Considering that we need to use various
functional in DFT calculation and also the post Hartree-Fockmethod, we wish to propose a QM/MM method to analytically
optimize structure of periodic molecular crystal. Consideringthat the whole crystal consists of equivalent subunits, weconstruct the Fock matrix and evaluate the energy derivatives
under the condition that the MM charge distribution isTranslation
QM/MM
self-consistently determined by the corresponding QM subunit.
operationinteraction
The idea is schematically shown in Scheme 2.
Scheme 2. QM and MM parts in theThis QM/MM approach is applied to the periodic molecular
calculation of molecular crystal
crystals of the traditional O-coordinated system, Pt(CN)4 2(H2O),
and the untraditional H-interacted one, trans-PtCl2(NH3)(N-glycine) H2O. The obtained molecular structuresin crystal much better agree with the experimental ones than the optimized ones of the isolated cluster
calculation. Here, we wish to report computational results about trans-PtCl2(NH3)(N-glycine) H2O because－ 90 －

fukui2012_02.indb 90

14.1.9 1:44:53 PM

Ⅳ 研究業績 (2012)

the water molecule interacts with the Pt center through H atom. This is against our expectation that watermolecule interacts with the metal center through the O lone pair orbital. MP2-calculated geometry of
isolated system does not agree with the experimental Pt-H distance. On the other hand, the present
QM/MM approach of molecular crystal reproduces well the Pt-H distance.
(iii) Theoretical Study of Inverted Sandwich Type Complexes of 4d Transition Metal Elements:
Interesting Similarities to and Differences from 3d Transition Metal Complexes

Inverted sandwich type complexes (ISTCs) of 4d metals, -η6:η6-C6H6)[M(DDP)]2 (DDPH =2-{(2,6-diisopropylphenyl)amino}-4-{(2,6-diisopropylphenyl)imino}pent- 2-ene; M = Y, Zr, Nb,
Mo, and Tc), were investigated with DFT and MRMP2 methods, where a model ligand AIP (AIPH= (Z)-1-amino-3-imino-prop-1-ene) was mainly employed. When going to Nb (group V) from Y(group III) in periodic table, the spin multiplicity of the ground state increases in the order singlet,
triplet, and quintet for M = Y, Zr, and Nb, respectively, like 3d ISTCs reported recently. This isinterpreted with orbital diagram and number of d electrons. However, the spin multiplicity
decreases to either singlet or triplet in ISTC of Mo (group VI) and triplet in ISTC of Tc (group VII),
where MRMP2 method is employed because the DFT method is not useful here. These spin
multiplicities are much lower than the septetof ISTC of Cr and the nonet of that of Mn.
It is noted that when going from 3d to 4d
the position providing the maximum spin
multiplicity shifts to group V from group
VII. These differences arise from the sizeof the 4d orbital. Because of larger size of
4d orbital, the energy splitting between two Figure 3. Changes in spin multiplicity along theperiodic table in the 3d and 4d metals.
d orbitals of M(AIP) and that between thed and d orbitals are larger in the 4dcomplex than in the 3d complex. Thus, when occupation on the d orbital starts, the low spin state
becomes ground state, which occurs at group VI. Hence, the ISTC of Nb (group V) exhibits the
maximum spin multiplicity.
(iv) A Theoretical Study of Unusual Y-Shaped Three-coordinate Pt Complex: Pt(0) σ-Disilane Complex orPt(II) Disilyl Complex
The unusual Y-shaped structure of recently reported three-coordinate Pt complex Pt[NHC(Dip)2](SiMe2Ph)2(NHC = N-heterocyclic carbene, Dip = 2,6-diisopropylphenyl) was considered a snapshot of reductive eliminationof disilane. DFT study indicates that this structure arises
from strong trans-influence of extremely σ-donating
carbene and silyl ligands. Though this complex can beunderstood to be a Pt(II) disilyl complex bearing a
distorted geometry due to the Jahn-Teller effect, its 195Pt
NMR chemical shift is considerably different from thoseof Pt(II) complexes but close to those of typical Pt(0)complexes. Its Si···Si bonding interaction is about 50%
Scheme 3. Schematical representation of theof the usual Si-Si single bond energy. The interaction
interaction of the Si-Si -bond with the Pt d
between the Pt center and the (SiMe2Ph)2 moiety can be orbitals.
understood in terms of donation and back-donation－ 91 －

fukui2012_02.indb 91

14.1.9 1:44:54 PM

Ⅳ 研究業績 (2012)

interactions of the Si-Si σ-bonding and σ*-anti-bonding MOs with the Pt center. Thus, it is likely concluded that
this is a Pt(0) σ-disilane complex and a snapshot after the charge-transfer considerably occurs from two silylgroups to the Pt center. Phenyl anion, Ph and [R-Ar] (R-Ar = C6H3-2,6(C6H3-2,6-iPr2)2), and divalent carbon(0)ligand C(NHC)2 also provide the similar unusual Y-shaped structure. Three-coordinate digermyl, diboryl, andsilyl-boryl complexes of Pt and a disilyl complex of Pd are theoretically predicted to take the similar unusualY-shaped structure, when a strongly donating ligand coordinates with the metal center. In a trigonal bipyramidal Ir
disilyl complex Ir(SiR3)2(NHC)(PH3)2, the equatorial plane takes the similar unusual Y-shaped structure. These
results suggest that various snapshots can be shown for the reductive eliminations of the Ge-Ge, B-B, and B-Si
-bonds.
(v) Evaluation Procedure of Electrostatic Potential in 3D-RISM-SCF Method and Its Application to

Hydrolyses of cis- and trans-Platin Complexes
In 3D reference interaction site model self-consistent field (3D-RISM-SCF) method, switching
function was introduced to evaluate electrostatic potential (ESP) around solute to smoothly connect
the ESP directly calculated with solute electronic wavefunction and that approximately calculatedwith solute point charges. Hydrolyses of cis- and trans-platins, cis- and trans-PtCl2(NH3)2, were
investigated with this method. Solute geometries were optimized at DFT level with the M06-2X
functional and free energy changes were calculated at CCSD(T) level. In the first hydrolysis, thecalculated activation free energy is 20.8 kcal/mol for cis-platin and 20.3 kcal/mol for trans-platin,
which agree with the experimental and recently reported theoretical results. A Cl anion, which isformed by the first hydrolysis, somehow favorably exists in the first solvation shell as a counter
anion. The second hydrolysis occurs with similar activation free energy (20.9 kcal/mol) for cis-platinbut somewhat larger energy (23.2 kcal/mol) for trans-platin to afford cis- and trans-diaqua
complexes. The Cl counter anion in the first solvation shell little influences the activation freeenergy but somewhat decreases the endothermicity in both cis- and trans-platins. The present
3D-RISM-SCF method clearly displays the microscopic solvation structure and its changes in thehydrolysis, which are discussed in detail.
2. Original papers(1) Hisako Hashimoto, Fukuda Tetsuya, Hitomi Tobita, Mausumi Ray, and Shigeyoshi Sakaki“Formation of a Germylyne Complex: Dehydrogenation of a Hydrido(hydrogermylene)tungsten
Complex with Mesityl Isocyanate”
Angew. Chem., Int. Ed., 51, 2930-2933 (2012).
(2) Kentaro Kido, Hirofumi Sato, Shigeyoshi Sakaki"Systematic Assessment on Aqueous pK(a) and pK(b) of an Amino Acid Base on
RISM-SCF-SEDD Method: Toward First Principles Calculations”
Int. J. Quant. Chem., 112, 103-112 (2012).
(3) Milind Deshmukh, Shigeyoshi Sakaki,“Two-step evaluation of binding energy and potential energy surface of van der Waals complexes”
J. Compt. Chem.., 33, 617-628 (2012).
(4) Yusaku I. Kurokawa, Shigeysohi Sakaki,“Theoretical Study of Inverted Sandwich Type Complexes of 4d Transition Metal Elements:
Interesting Similarities to and Differences from 3d Transition Metal Complexes”
J. Phys. Chem. A, 116, 2292-2299 (2012).
(5) Guixiang Zeng, S. Sakaki,“Theoretical Study on the Transition-Metal Oxoboryl Complex: M-BO Bonding Nature,
Mechanism of the Formation Reaction, and Prediction of a New Oxoboryl Complex”
Inorg. Chem., 51, 4597-4605 (2012).

－ 92 －

fukui2012_02.indb 92

14.1.9 1:44:55 PM

Ⅳ 研究業績 (2012)(6) Ken Saito, Yoshinori Eishiro, Yoshihide Nakao, Hirofumi Sato, Shigeyoshi Sakaki,“Oscillator Strength of Symmetry-Forbidden d-d Absorption of Octahedral Transition Metal
Complex: Theoretical Evaluation”
Inorg. Chem., 51, 2785-2792 (2012).
(7) Noboru Takagi, Shigeyoshi Sakaki,“A Theoretical Study of an Unusual Y-Shaped Three-Coordinate Pt Complex: Pt(0) sigma-Disilane
Complex or Pt(II) Disilyl Complex?”
J. Am. Chem. Soc., 134, 11749-11759 (2012).
(8) Seiji Akatsu, Yasunori Kanematsu, Taka-aki Kurihara, Shota Sueyoshi, Yasuhiro Arikawa,
Masayoshi Onishi, Shoji Ishizaka, Noboru Kitamura, Yoshihide Nakao, Shigeyoshi Sakaki,
Keisuke Umakoshi,“Syntheses and Luminescent Properties of 3,5-Diphenylpyrazolato-Bridged Heteropolynuclear
Platinum Complexes. The Influence of Chloride Ligands on the Emission Energy Revealed by the
Systematic Replacement of Chloride Ligands by 3,5-Dimethylpyrazolate”
Inorg. Chem., 51, 7977-7992 (2012).
(8) Yumiko Nakajima, Shigeyoshi Sakaki, Yoshihide Nakao, HIroharu Suzuki“Theoretical Study of Dihydrogen Activation by a Trinuclear Ruthenium mu(3)-Imido Complex”
Organometallics, 31, 5342-5348 (2012).
(9) Shinji Aono, Shigeyoshi Sakaki,“Proposal of new QM/MM approach for geometry optimization of periodic molecular crystal:
Self-consistent point charge representation for crystalline effect on targetQM molecule”
Chem. Phys. Lett. 544, 77-82 (2012).
(10) Shinji Aono, Shigyeoshi Sakaki,“Evaluation Procedure of Electrostatic Potential in 3D-RISM-SCF Method and Its Application to
Hydrolyses of Cis- and Transplatin Complexes”
J. Phys. Chem. B, 116, 13045-13062 (2012).
(11) Atsushi Ishikawa, Yudai Tamura, Yoshihide Nakao, Hirofumi Sato, Shigeyoshi Sakaki,“Complicated Electronic Process of C-C sigma-Bond Activation of Cyclopropene by Ruthenium
and Iridium Complexes: Theoretical Study”
Organometallics, 31, 8189-8199 (2012).
3. Presentation at academic conferences(1) Shinya Tsukamoto, Shigeyoshi Sakaki,“A Theoretical Study for Solid-state Spin crossoverr of Ni(II) in N3S2 ligand field”, 14th
ICQC, Boulder, Corolad, USA, June 2012.
(2) Masayuki Nakagaki, Yusaku I. Kurokawa, Shigeyoshi Sakaki“CAS-PT2 and LMO-CAS Study of Spin States and Coordination Modes of N2 bridged
Inverted Sandwich Type Complexes”, 14th ICQC, Boulder, Corolad, USA, June 2012.
4. Others(1) 榊 茂好
“理論化学・計算化学は化学研究にどう役に立ったか？”
近畿化学協会第34期研修塾、2012年8月 大阪（大阪科学技術センター）(2) 榊 茂好
“理論化学・計算化学と実験化学のインタープレイ
Riken-Spring-8 放射光連携研究ワークショップ 平成２５年１月 東京(東京大学)(3) 榊 茂好“巨大分子系の計算化学 超大型計算機時代の理論化学の新展開 日本化学会編 10 章 錯体触媒
反応－魅力に満ちた遷移金属化学種の世界 pp.113-122 (2012).

(4) Shigeyoshi Sakaki“Practical Aspects of Computational Chemistry II, ED. by Jerzy Leszczynski, Moj K. Shukla,
Splinger, Chap. 11, Theoretical Study of s-Bonf Activation Reactions and Catalytic Reactions by
Transition Metal Complexes, pp.391-470. (2012).

－ 93 －

fukui2012_02.indb 93

14.1.9 1:44:55 PM

Ⅳ 研究業績 (2012)

４．博士研究員

Takafumi IWAKIFIFC Fellow

1. Summary of the research of the year
Study of DNA Double Strand Breaking Produced by Ionizing Radiations
Naked DNA suffers damage from various environmental triggers. Intense light is one of such triggers,which causes breaking of DNA strands directly or through free radical production. When a pair of
single-strand breakings occurs within 10 base pair distance, double-strand DNA is cut into two pieces
thoroughly. It is much more difficult to repair the double strand breaks than the single-strand breaks. Thus,
the double-strand breaking is regarded as amore serious problem in medical and life
science. Since DNA double-strand breaks(DSBs) represent a serious source of damage
for all living things, there have been many
quantitative studies of DSBs both in vivo andin vitro. Despite this fact, the processes thatlead to their production have not yet beenclearly understood, and there is no establishedtheory that can account for the statistics of theirproduction, in particular, the number of DSBs
per base pair per unit Gy, here denoted by P1,
which is the most important parameter forevaluating the degree of risk posed by DSBs.
Using the single-molecule observation

Figure 1: The number of double-strand breaks
per 100 kbp per unit Gy versus base-pairconcentration of DNA.

method with giant DNA molecules (166 kbp), we evaluated the number of DSBs caused by -ray irradiation
for wide ranges of -ray intensity and DNA concentration. In an investigated region, double-strand breaking
linearly scales to -ray intensity, which is not general in a much higher intensity region of -ray where double
strand breaking scales to the square of the intensity. From the experiment, we found that, in the dependenceof P1 to the DNA concentration, there are two characteristic regions (See Fig. 1). In a low DNA
concentration region, P1 is nearly constant to the DNA concentration. On the other hand, P1 is nearly
inversely proportional to the DNA concentration above a certain threshold. We calculate the probability tooccur double strand breaking on the basis of a simple model, which well accounts for the marked profile ofP1 over all measured region. Based on this argument, we show that it is necessary to consider thecharacteristics of giant DNA molecules as semiflexible polymers to interpret the intrinsic mechanism of
DSBs. This work was accepted as a regular article in The Journal of Chemical Physics.

－ 94 －

fukui2012_02.indb 94

14.1.9 1:44:56 PM

Ⅳ 研究業績 (2012)

Numerical Fluid Dynamics Study of a Heated Oil Droplet on Air-Water Interface
A centimeter-sized droplet of liquid paraffin on water can be accelerated by a laser irradiation. In thisscale of experiments, the origin of the migration force is attributable to the Marangoni effect: a surface
force arising from a local difference of surface tensions. For example, as shown in Fig. 2, irradiation of thelaser induces flows outside and inside the droplet by thermal Marangoni effect, which in turn influences atemperature distribution of the heated droplet. In actual experiments, we found that the presence/absence of
surfactant (SDS) changes the migration direction to the opposite side. Since this system has a low symmetry,
we performed a CFD simulation to analyze an essential mechanism of this change in the acceleration
direction.
Here, we performed a numerical simulation of thermal fluid on an irregular lattice with a finite volume
method. Several causes were assumed for the above-mentioned effect of SDS. For example, the differencein the shape of the droplet might have induced a different flow mode inside the droplet. Nonlinear effect of
the hydrodynamics might have promoted theappearance of the different modes in similar
experimental systems. These expectations were,
however, denied by a sequence of simulations. We
found that the migration direction changes due tothe temperature coefficients of surface tensionschanged by the presence/absence of SDS. The
Marangoni effect on an oil droplet on an air-waterinterface caused by local heating induces two typesof actions on the droplet. One is the viscous
friction force from an external flow induced bycaterpillar-like action of the droplet surface. This
force always accelerates the droplet to approach aheating spot. The other is the Young force arisingfrom a dynamical breaking of a surface tension
balance in a periphery of the droplet. This force isdetermined by the weight of the temperature
coefficient of surface tension in each of interfaces.
When the magnitude relation of the temperature
coefficients between air-water interface and oil
surfaces reverses, the Young force changes its
direction.
Thus, we simulated a thermal flow for two

Figure 2: Flow pattern and temperature
distribution of a paraffin droplet on pure water
heated by a laser irradiation.

typical sets of temperature coefficients of surface
tensions. Consequently, we obtained flow patterns and temperature distributions very similar toexperimentally obtained ones in the presence/absence of SDS, respectively, which rationalize that the－ 95 －

fukui2012_02.indb 95

14.1.9 1:44:56 PM

Ⅳ 研究業績 (2012)

above-mentioned mechanism is applicable to the interpretation of the experimentally observed effect of
SDS. This work is now submitted to a scientific journal through several revisions.

Study of the Dynamical Mechanism of the Self-Organization of the Tooth Germ
In a development process of a toothgerm, an epithelial layer grows resulting in its
invagination. A formation of an enamel knot is
accompanied with this process. The enamelknot is considered to be deeply involved withthe development process, but a detailed
mechanism of a shape formation of the tooth
germ has not been clarified. We started from avery simple numerical model of cell growth,and studied to what extent the simple physicalprocess can control the shape of the cell system.
We

performed

Brownian

dynamics

simulations of a coarse-grained system of cell
particles stochastically increasing with time. In
the simulations, we found that according to theproliferation rates of the surface layer and theinterior of the dental epithelial, the bucklingformation undergoes several courses (See Fig.
3). In particular, when the proliferation rate of
the surface layer is considerably larger than thatof the interior, the bending is not uniform, andthe plural buds are formed similarly to theactual development process. This fact suggests

Figure 3: Diagram of final state of a growing
numerical model teeth germ on a plane of
innerproliferation

rate

and

peripheral

proliferation rate.

that the formation of the enamel knot is governed by a rather simple mechanical process.
To get a further insight, we calculate the “free energy of time course” of the buckling process of anelastic continuous segment for the several given paths, and found that the shrinking speed of the end-to-end
distance determines the favored type of buckling. In fact, when this speed is faster, buckling along with agrowth of plural peaks is more favored. This well corresponds to the simulation result and also the actual
development process. At present, we continue a discussion about interpretation of these results andapplicability to an actual tooth development process. The manuscript is under preparation, which is to besubmitted to a scientific journal.

－ 96 －

fukui2012_02.indb 96

14.1.9 1:44:57 PM

Ⅳ 研究業績 (2012)

2. Original papers(1) Shunsuke F. Shimobayashi, Takafumi Iwaki, Toshiaki Mori, and Kenichi Yoshikawa,“Probability of double-strand breaks in genome-sized DNA by g-ray decreases markedly as
the DNA concentration increases”
J. Chem. Phys. Accepted.
3. Presentation at academic conferences(1) 岩城 貴史、“Path-Ensemble sampling for a folding transition of semiflexible polymer” (poster), 岩
城貴史, 日本物理学会 2012 年秋季大会, Yokohama, Sep. 21, 2012

－ 97 －

fukui2012_02.indb 97

14.1.9 1:44:57 PM

Ⅳ 研究業績 (2012)���行�ン�ー���ー
1. 今年度の研究の要�
今年度は溶液内における分子の光化学反応を解析するために、電子励起状態の自由エネルギー面を構築する新しい方法論の開発を行った。そして、時間依存密度汎関数法と積分方程式を組み合わせた計算手法を導入した。

�����

光化学反応を理論的に理解するためには、電子励起状態におけるポテンシャルの極小点、遷移状態、および複数のポテンシャル面の交差点を同定する必要がある。例えば、ポテンシャル極小点の分子構造は蛍光スペクトル、ポテンシャルの交差点は無輻射遷移に関する重要な情報を含んでいる。したがって、反応機構に関する重要な知見を得るためには、これらの位置関係を求める必要がある。
特に電子励起状態を記述するためには、電子相関を考慮した精密な電子状態計算の手法が求められる。

溶液内分子の記述には、溶媒効果を取り入れた電子状態計算が不可欠である。極性溶媒はイオン型の電荷分布をより安定化するため、気相中とは定性的に異なる反応機構を示すことがある。溶液内分子の記述には、ポテンシャル面よりも自由エネルギー面による議論が便利である。それは、溶媒
分子の自由度が莫大なものとなり、また局所的なポテンシャル極小点も多数存在するためである。
したがって自由エネルギーの計算では、溶媒分子の配置空間について十分な統計平均をとらなければならない。

���������������������������

本研究では、溶液内光化学反応を解析するために、電子励起状態の自由エネルギー面の計算手法を確立した。それは、時間依存密度汎関数法 (TDDFT) と溶媒和構造を分子論的に記述できる積分方
程式 (RISM) を組み合わせた方法である (TDDFT/RISM-SCF)。RISM-SCF 法[1][2]は、溶質分子の電子状態と溶媒の動径分布関数を self-consistent になるように決定するが、分子動力学シミュレーシ
ョンのような統計サンプリングが必要ないため計算コストが低くおさえられる。線形応答の枠内で－ 98 －

fukui2012_02.indb 98

14.1.9 1:45:00 PM

Ⅳ 研究業績 (2012)定式化することで、基底状態の平衡溶媒和の情報(RISM-DFT) だけで励起状態の自由エネルギーが求められるようにした (図 1)。さらに、電子励起状態の自由エネルギー及びその解析的微分法により自由エネルギー面の構築を図った。enol →keto 励起状態プロトン移動反応の例として、
ortho-hydroxybenzaldehyde (OHBA) のエネルギー
プロファイルを示す (図 2)。1Aʺ (nπ*) 状態では、溶媒効果はほとんど見られないのに対し、2Aʹ(ππ*) 状態では~0.1 eV の安定化が見られた。
図 1 RISM-TDDFT 法の計算スキーム
今後の予定として、線形応答近似の妥当性の検証が求められる。上で述べたように、線形応答の枠組みでは励起状態の電子状態が溶媒和構造に反映されない。例えば、光誘起電子移動反応のような溶媒和構造が大きく変化する場合、基底状態の溶媒和構造は良い参照系ではなくなる可能性がある。
この問題を回避するため、励起状態の電子分布を溶媒和構造に反映させる計算手法を開発中である。

䛆⁐ᾮෆ䛻䛚䛡䜛⮬⏤䜶䝛䝹䜼䞊㠃䛾஺ᕪ㡿ᇦ䛇㻌

本研究では、溶液内における自由エネルギーの交差点を決定する手法を確立した。自由エネルギー

図 2 OHBA のエネルギープロファイル
実線: アセトニトリル溶液

点線: 孤立系の交差領域は、溶液内における無輻射過程だけでなく、電子移動反応の活性化自由エネルギーを求め
るうえでも重要である。今回、計算手法として
spin-flip TDDFT (SFDFT) 法[3]と RISM-SCF 法を組み合わせた。SFDFT 法は、スピン反転励起に基づく
TDDFT 法であり、静的電子相関を部分的にではあるが取り入れることができる。そのため、この方法は気相中における円錐交差の探索に用いられてきた[4][5]。溶液内での自由エネルギーの交差は、自由エ

図 3 エチレンの分子構造(黒)孤立系、(灰)アセトニトリル溶液、(薄灰)水溶液－ 99 －

fukui2012_02.indb 99

14.1.9 1:45:03 PM

Ⅳ 研究業績 (2012)

ネルギーの極小点 (すなわち平衡溶媒和) から離れた非平衡領域でおこる。したがって、あらわに
溶媒和座標に依存する、非平衡自由エネルギーを採用した[6][7]。孤立系で用いられている交差点の探索法を拡張して、溶液内での自由エネルギー交差点の分子構造を決定した。テスト計算として、
交差領域でのエチレンの分子構造を求めた (図 3 および表 1)。溶媒効果により、C1-C2-H5 の角度が増加していることがわかる。これは、極性溶媒との相互作用により、分子内における大きな構造変化が溶液中では必要ないことを示唆している。

Gas

Acetonitrile

Waterr(C1-C2)

1.388

1.394

1.410

r(C2-H5)

1.144

1.120

1.109

∠C1-C2-H5

92

103

109

∠C1-C2-H6

112

104

109

∠H5-C2-H6

91

92

101

表 1 交差領域におけるエチレンの分子構造。
結合距離(Å)、結合角(度)。

䛆ᩥ⊩䛇㻌[1] S. Ten-no, F. Hirata, and S. Kato, J. Chem. Phys. 100, 7443 (1994).
[2] H. Sato, F. Hirata, and S. Kato, J. Chem. Phys. 105, 1546 (1996).
[3] Y. Shao, M. Head-Gordon, and A. I. Krylov, J. Chem. Phys. 118, 4807 (2003).
[4] N. Minezawa and M. S. Gordon, J. Phys. Chem. A 113, 12749 (2009).
[5] N. Minezawa and M. S. Gordon, J. Phys. Chem. A 115, 7901 (2011).
[6] S. Yamazaki and S. Kato, J. Chem. Phys. 123, 114510 (2005).
[7] T. Mori, K. Nakano, and S. Kato, J. Chem. Phys. 133, 064107 (2010).

�� ��(1) N. Minezawa and M. S. Gordon, “Optimizing conical intersections of solvated molecules: The
combined spin-flip density functional theory/effective fragment potential method”, J. Chem. Phys.
137, 034116 (2012).
(2) K. R. Brorsen, N. Minezawa, F. Xu, T. L. Windus, and M. S. Gordon, “Fragment molecular orbital
molecular dynamics with the fully analytic energy gradient”, J. Chem. Theory Comput. 8, 5008
(2012).

－ 100 －

fukui2012_02.indb 100

14.1.9 1:45:04 PM

Ⅳ 研究業績 (2012)(3) N. Minezawa, “Excited-state free energy surfaces in solution: Time-dependent density functional
theory/reference interaction site model self-consistent field method”, J. Chem. Phys., accepted.
(4) N. De Silva, N. Minezawa, and M. S. Gordon, “Excited state hydrogen atom transfer reaction insolvated 7-hydroxy-4-methylcoumarin”, J. Phys. Chem. B, submitted.

�� 学会��
(1) 嶺澤 範行「電子励起状態における自由エネルギー面の構築: RISM-TDDFT法」
第６回分子科学討論会(2) 原渕

祐・前田

東京 2012/09/18

理・武次

徹也・嶺澤

範行・諸熊

奎治

「GRRM法とSF-TDDFT法を組み合わせた最小エネルギー円錐交差構造自動探索: 大きな分子への適用へ向けて」
日本化学会第９３春季年会

滋賀 2013/03/23

�� �の�
(1) 嶺澤 範行「電子励起状態における自由エネルギー面: RISM-TDDFT法」
第10回京都大学福井謙一記念研究センターシンポジウム

京都 2012/11/30－ 101 －

fukui2012_02.indb 101

14.1.9 1:45:04 PM

Ⅳ 研究業績 (2012)

Ryuichi OKAMOTO
FIFC Fellow
1. Summary of the research of the year (3-5 pages, includes appropriate figures and tables)
Phase separation in a near-critical binary fluid mixture confined between symmetric parallel
platesWe investigate phase separation of near-critical binary mixtures between parallel symmetric wallsin the strong adsorption regime. We take into account the renormalization effect due to the criticalfluctuations using the recent local functional theory [Okamoto and Onuki, J. Chem. Phys. 136,
114704 (2012)]. In statics, a van der Waals loop is obtained in the relation between the averageorder parameter �ψ� in the film and the chemical potential when the temperature T is lower than
the film critical temperature Tcca (See Fig. 1). In dynamics, we lower T below the capillary
condensation line from above Tcca. We calculate the subsequent time development assuming nomass exchange between the film and the reservoir. In the early stage, the order parameter ψchanges only in the direction perpendicular to the walls. For sufficiently deep quenching, suchone-dimensional profiles become unstable with respect to the fluctuations varying in the lateral directions. The late-stage coarsening is then accelerated by the hydrodynamic interaction. A
pancake domain of the phase disfavored by the walls finally appears in the middle of the film (Fig.
2).

－ 102 －

fukui2012_02.indb 102

14.1.9 1:45:07 PM

Ⅳ 研究業績 (2012)

(c)

(b)

(a)

(D,0)
(x,y)=(D,D)

Fig. 2 Equilibrium two-phase state at τ/τD = −20 in a 2D × 2D × D system: Scaled order parameter ψ/ψD (a) in the xy plane at z=D/2 and (b)in the yz plane at x=D. (c) Scaled order paramter ψ/ψD along the z axis for (x,y) = (D,D) (blue bold line) and (D,0) (red bold line).

Drag coefficient of a rigid spherical particle in a binary fluid mixture: Effect of preferential
adsorption on the particle surface
We calculate the drag coefficient of a rigid spherical particle in an incompressible binary fluid
mixture. A weak preferential attraction is assumed between the particle surface and one of thefluid components, and the difference in the viscosity between the two components is neglected.
Using the Gaussian free-energy functional, we solve the hydrodynamic equation explicitly under
the condition that the particle moves with constant velocity. Near the particle surface, there
appears an “adsorption layer” of the preferred component of the mixture owing to the preferential
attraction. We find that the adsorption layer reduces the hydrodynamic flow near the particle fromthat in a one-component fluid having the same viscosity. As a result, the drag coefficient becomeslarger in a binary fluid mixture. Furthermore, we can show that the preferential attraction makes
the drag coefficient larger as the bulk correlation length becomes longer. The dependence of thedeviation from the Stokes law on the correlation length, when it is short, turns out to be muchsteeper than the previous estimates.
4

3

2

1

0
-4

-2

0

2

4

Fig. 3 The order paramter profile (gray gradation) and the deviation of the flow field from that in
one-component fluid (arrows) on x-z plane. The spherical particle moves along the z-axis
in negative direction.

－ 103 －

fukui2012_02.indb 103

14.1.9 1:45:09 PM

Ⅳ 研究業績 (2012)

2. Original papers(1) Shunsuke Yabunaka, Ryuichi Okamoto and Akira Onuki“Phase separation in a binary mixture confined between symmetric parallel plates:
Capillary condensation transition near the bulk critical point”
Phys. Rev. E 87(3), 032405 (2008).
(2) Ryuichi Okamoto, Youhei Fujitani and Shigeyuki Komura"Drag coefficient of a rigid spherical particle in a near-critical binary fluid mixture”
J. Phys. Soc. Jpn. accepted for publication.
3. Review article(1) R. Okamoto and A. Onuki:�“Solvation effects in soft matters",�Physical Society of Japan
67, 566 (2012) (in Japanese).
4. Presentation at academic conferences(1) Ryuichi Okamoto and Akira Onuki,“Solvation effects in soft matters” (oral)
18th Symposium on Thermophysical Properties, Boulder, CO, USA, June 25, 2012
(2) Ryuichi Okamoto and Akira Onuki“Solvation effects on wetting on an ionizable surface” (oral, in Japanese)
Physical Society of Japan 2012 autumn meeting, Yokohama, September 20, 2012
(3) Ryuichi Okamoto and Akira Onuki“Colloid interaction in a binary mixture solvent near criticality” (poster)
The 10th symposium of Fukui Institute for Fundamental Chemistry, Kyoto, Nov. 30, 2012.
(4) Ryuichi Okamoto and Akira Onuki“Nanobubble stabilized by a strongly hydrophobic solute” (poster)Self-Organization and Emergent Dynamics in Active Soft Matter, Kyoto, February 19,
2013(5) Ryuichi Okamoto and Akira Onuki“Stable nanobubbles induced by hydrophobic impurities” (oral, in Japanese)
Physical Society of Japan 2013 annual meeting, Higashi-Hiroshima, March 27, 2013

－ 104 －

fukui2012_02.indb 104

14.1.9 1:45:10 PM

Ⅳ 研究業績 (2012)

Takuya SAITOFIFC Fellow(From 1 Nov. 2012)
1. Summary of the research of the year
1. Stretching and Compression in driven polymer translocation
A single polymer transportation induced by local stimuli is a fundamental process found intechnology as well as biology. One of the most studied transport processes is “driven translocation”,
which is polymer passage through the pore with driving force from the cis- to the trans-sides.
In the weak force regime, the polymeric chain essentially retains the equilibrium shape in the bothsides. A large asymmetric deformation, however, takes place under the strong force, so that the cisor trans-side segments are governed by different kindsof dynamics. In the cis-side, all the chain does not
respond to local stimulus at once, and a portion of thosesegments is largely stretched. In the course of the
dynamics, the moving stretching domain grows throughtension propagation along the polymeric chain. On theother hand, in the trans-side, the passed segments arecompressed owing to the pushing by the force aroundpore so that those get decompressed outward. While thetension propagation dynamics has been recently
investigated, the non-equilibrium dynamics in thetrans-side is still elusive.
We investigated the driven translocation, taking
account of asymmetric dynamics in the cis-/trans- sides
with the help of the scaling argument.

Fig. 1 Schematic representation ofdriven polymer translocation.

Fast/ slow diffusion
The blob picture is used as a powerful method todescribe a large polymeric deformation. From theanalysis based on the blob, the segment currents arefound to be standardized as   f  p / p j ( x )   L( x )d ( x ) d  d    D0d ( x ) z  ,d  d d ( x ) .
 d (1)

－ 105 －

fukui2012_02.indb 105

14.1.9 1:45:10 PM

Ⅳ 研究業績 (2012)

The flow form suggests theremarkable difference, i.e., thedynamics in the cis- or trans-sides are
identified as fast or slow diffusion,respectively. Capturing the dominant
contribution yields the dynamical
equation of state for each side, which
represents
asymmetrictransport
characteristics. Using this, we obtainthe force fraction  (t ) in the course

Fig. 2 Plot of a fraction of pulling force in the course oftranslocation

 (t )  f c (t ) /[ f c (t )  f t (t )] (ID: ideal

chain, EV: excluded volume chain, ND: non-draiining,
FD: free-draining )..

of the translocation as shown in Fig. 2.
This indicates the pushing force in thetrans-side gets smaller with time, i.e.,the cis-side dynamics eventually
dominates.

2. Temporal distribution in driven polymer transportation
We investigate the temporal distribution of dynamic
processes in driven polymer transportation through stochastic
tension propagation along polymeric chain. An entire chain
does not respond to local stimulus at once, but a part of it does.
The moving domain grows accompanied with the tensile force
propagation along the random coiled chain so that the tension
path is stochastic (Fig. 3). The stochastic tension path resultsin the temporal distribution of the polymer transport.
We consider the process time for two cases; (1) translocation
occurs across a fixed pore and (2) stretching occurs by pulling
one of the chain ends. A scaling argument for the mean andstandard deviation of the process time are given by employing
the two-phase picture combined with stochastic propagation.
The two cases show remarkably different results. The
temporal distribution of the translocation remains even in theFig. 3 Schematic representation ofstochastic tension propagation along thelong-chain limit, unlike that found for the dynamics ofpolymer stretching.

chain.

－ 106 －

fukui2012_02.indb 106

14.1.9 1:45:10 PM

Ⅳ 研究業績 (2012)

3. Stretching dynamics
We study transient dynamics of a single polymer chain, whose one chain end is suddenly pulled by aconstant force. A rapidly developing technology of single macromolecule manipulation requires a paradigm
research for probing far-from-equilibrium responses of long flexible polymers.
We first obtain the exact analytical results through the Rouse model. To capture more realistic situations,the excluded volume and the hydrodynamic interactions are taken into account with the help of scalingarguments, which provides various nontrivial predictions such as the force-dependent friction constants. We
further find generalized dynamical equations of state to describe extension/friction laws in steady-state andthe tension propagation laws during the transient process. Our results predict that the manipulation protocols
make a crucial difference in the time evolutions of the dynamic friction. These remarkable results could beverified in experiments by manipulating macromolecules such as giant DNAs.

2. Original papers(1) Takuya Saito and Takahiro Sakaue, Phys. Rev. E 85, 061803 (2012).
“Process time distribution of driven polymer transport”.
(2) Takahiro Sakaue, Takuya Saito and Hirofumi Wada, Phys. Rev. E 86, 011804 (2012).
“Dragging a polymer in a viscous fluid: Steady state and transient”.

(3) 坂上貴洋、齋藤拓也, 日本物理學會誌67(10), 705-709, 2012-10-05.
「紐状分子の非平衡ダイナミクス：細孔通過現象を中心に」
3. Presentation at academic conferences(1) 齋藤拓也、坂上貴洋“高分子鎖輸送過程の時間分布:分布の広がりのスケーリング”
日本物理学会 2012 年秋季大会, 横浜国立大学 2012 年 9 月 18 日.
(2) 齋藤拓也、坂上貴洋“微細孔を通り抜ける高分子鎖のダイナミクス: 通り抜け時間の分布のスケーリング”
第十回京都大学福井謙一記念研究センターシンポジウム, 京都, 2012 年 11 月 30 日.
(3) 齋藤拓也、坂上貴洋“微細孔を通り抜ける高分子鎖のダイナミクス: 通過前後における鎖の伸張と圧縮”
日本物理学会第 68 回年次大会, 広島大学 東広島キャンパス, 2013 年 3 月 26 日.

－ 107 －

fukui2012_02.indb 107

14.1.9 1:45:10 PM

Ⅳ 研究業績 (2012)

Fu-Quan BAIFIFC Fellow(From 16 Apr. 2012)
1. Summary of the research of the year
electronic spectra, photophysical properties and potential energy surface conical intersectionof free-base porphyrin and meso-subsitituted free-base tetratertiary-butylporphyrin
Besides planar porphyrins, nonplanar porphyrins are synthesized and also commonly found in
biological systems. The out-of-plane distortion in a series of sterically-crowded porphyrins results in unusual
optical properties and enhanced radiationless decay of the 1(π, π*) excited state. In particular, macrocycle
distortions increase the rates of both the internal conversion and intersystem crossing decay pathways. The
distortion is induced either by linking steric interactions using peripheral substitution or by the introductionof central metal ions of suitable size into the porphyrin core. This raises the possibility that the excited-state
properties of the porphyrin may be adjusted step by step through introducing distortions into thistetrapyrroles skeleton. Not as the normal planar porphyrins with a minor difference in Q bands opticalabsorption (around 2.0 eV), fluorescence spectra as well as the 1(π, π*) lifetime of 10-15 ns, the perturbed
porphyrins, such as free-base tetratertiary-butylporphyrin (H2T(t-Bu)P), its absorption spectra are broader,
and there is bathochromic shifts by over 0.2~0.3 eV for absorptions and emissions following the conspicuous
Stokes shift. The 1(π, π*) lifetime are also extremely short based on its very low fluorescence quantum yield.
The Knowledge of spectroscopic behavior and the molecular structures is needed for a deeper understandingof the inherent processes in essence to find a cause-and-effect relationship. Recently, Marian group studied
the radiationless deactivation of lowest excited singlet state of planar free-base porphyrin (H2P) from
opening of unprotonated single pyrrole, excited-state proton transfer and vibronic spin-orbit coupling matrix
elements (SOCMEs) points of view. The out-of-plane distortion of the first excited singlet state of the H2P
caused a significant increase of the <T2 |Hso| S1>, <T1 |Hso| S1>, and <T1 |Hso| S0> spin–orbit coupling
matrix elements was concluded.
It is well known that the electronic spectra of H2P have two major absorption bands, namely the weak
Q band in the visible region (500–650 nm) and the strong B band (or Soret band) in the near-UV region(350–400 nm). The vertical excited state calculation from CAM-B3LYP ground state geometry by
TD-CAM-B3LYP, there is an overvaluation for the B band and higher band energies for H2P. Meanwhile,
the TD-B3LYP based on the B3LYP ground state geometry can give rather reasonable results. From B3LYP
geometry of H2P, few ab initio methods, SAC/SAC-CI (with different levels), Configuration
Interaction-singles (CIS) and with perturbative doubles correction (CIS(D)), second-order approximatedCoupled-Cluster model with the resolution of identity approximation (RICC2) and spin-component scaled
RICC2 (SCS-RICC2), were also adopted for achieving most accurate results. A summary of the singlet state
excitation energies for H2P was listed in Table 1.

－ 108 －

fukui2012_02.indb 108

14.1.9 1:45:11 PM

Ⅳ 研究業績 (2012)

Table 1. The singlet state excitation energies under different methods and the experimental spectra results of H2P.

CAM-B3LYP

B3LYP

SACCI(Level 1)

SACCI(Level 3)

CIS

CIS(D)RICC2

SCS-RICC2

Exptl. (eV)

2.20

2.26

1.67

1.69

2.39

2.46

2.30

2.13

Qx : 1.98

2.42

2.42

2.06

2.18

2.50

2.61

2.50

2.51

Qy : 2.42

3.55

3.30

3.41

3.41

4.44

4.13

4.38

3.45

B : 3.33

3.65

3.44

3.57

3.53

4.62

4.45

4.72

3.78

N : 3.65

4.26

3.79

4.13

4.19

5.23

4.97

5.23

4.38

L : 4.25~4.67

4.79

4.05

4.68

4.75

5.60

5.30

6.54

4.66

The photoabsorption, fluorescence, and phosphorescence energies and related π→π* states of H2P and
H2T(t-Bu)P and the corresponding transitions with dominant electric dipole oscillator strength values using
TD-DFT and SCS-RICC2 are reported in Table 2 and 3. From Table 2 and 3, one can see that theexperimental spectra are well reproduced by the present calculations but with some red shifts in wavelength
for the lowest energy absorption bands (ca. 0.10~0.15 eV for RICC2 result and 0.20~0.25 eV for TDDFT).
The differences between calculations and experimental data, especially the lowest excited states, not only
come from methods limitations, but also include the minor deviation between the optimized moleculargeometry and the experimentally observed results. Furthermore, the gratifying results have been achieved forthe fluorescence, especially the phosphorescence energies with almost reproduced completely (< 0.05 eV
error). Comparing with RICC2 results, the B3LYP is good at geometry optimization and same-spin state (S-Sor T-T) transition calculations but more underestimate the S-T states transition energies. Since thefluorescence and the lowest-absorption have the same symmetry and transition character for H2P and
H2T(t-Bu)P, the fluorescence may come from the lowest-energy absorptions. But the phosphorescencetransition character has changed greatly comparing with the lowest-T1-absorption for H2T(t-Bu)P. The
persistence of the substantial stokes shift and the transition character transformation for the H2T(t-Bu)P
suggests that an additional reorganization in the excited state dominates the behavior of H2T(t-Bu)P.
Table 2. Photoabsorption, fluorescence, and phosphorescence energies and related π→π* states of H2P.
State

TD-B3LYP/6-31+G(d,p)// TD-B3LYP/6-31+G(d,p)
Main configurations (|C| > 0.25)

SCS-CC2/def-SV(P) // TD-B3LYP/6-31+G(d,p)EE(f)

Main configurations (|C| > 0.25) aEE(f)+0.78 (80(5b1u)→83 (4b3g)) +0.58

2.13(81(2au)→82(4b2g))(1.67×10 )Exptl.

Photo absorption at the S0 minimum structure
S1+0.54 (81(5b1u)→83 (4b3g)) +0.46

2.26(80(2au)→82(4b2g))(<1.0×10 )-5

1.98 (Qx) in
-3

vapor
2.02 in
CHCl3

T1+0.64 (81(5b1u)→82(4b2g)) -0.32

1.48+0.93 (80(5b1u) →82(4b2g))

1.94+0.78 (80(5b1u)→83 (4b3g))-0.62

2.09(80(2au)→83 (4b3g))
Fluorescence at the S1 minimum structure
S1+0.55(81(5b1u)→82(4b2g)) +0.44

2.23(80(2au)→83 (4b3g))(1.10×10 )(81(2au)→82(4b2g))(2.09×10 )1.12+0.97 (80(5b1u) →82(4b2g))

1.55

-3

2.03 in EPA-4

Phosphorescence at the T1 minimum structure
T1+0.71(81(5b1u)→82(4b2g))

1.58 in
EPA:EtI－ 109 －

fukui2012_02.indb 109

14.1.9 1:45:11 PM

Ⅳ 研究業績 (2012)

Table 3. Photoabsorption, fluorescence, and phosphorescence energies and related π→π* states of H2T(t-Bu)P.
State

TD-B3LYP/6-31+G(d,p) // TD-B3LYP/6-31+G(d,p)

SCS-CC2/def-SV(P) // TD-B3LYP/6-31+G(d,p)EE(f)

Main configurations (|C| > 0.25) a

EE(f)Exptl.

+0.44 (145→146) +0.35 (145→147)

2.00+0.53 (144→146) +0.46 (145→147)

1.89

1.78 (Qx)-0.32 (144→147)(9.30×10-3)+0.52 (144→147) +0.44 (145→146)(1.22×10-3)+0.50 (145→146) -0.45 (145→147)

1.13+0.83 (144→146) -0.45 (144→147)

1.65

Main configurations (|C| > 0.25)
Photo absorption at the S0 minimum structure
S1
T1+0.26 (145→146)
Fluorescence at the S1 minimum structure
S1-0.49 (145→146) +0.31 (145→147)

1.92-0.32 (144→147)

1.72

0.63 (144→146) +0.64 (145→147)

1.81+0.34 (145→146)(4.68×10 )0.97 (145→146)

0.49

-3

Phosphorescence at the T1 minimum structure
T1-0.71 (145→146)-0.54

Respect to the dihedral angles of N4-C9-C10-C11 in H2T(t-Bu)P geometry are varied alteredremarkably at different electronic states, we calculated the vertical excitation potential energies change
curves in singlets and triplets for S0, S1 and T1 states along the alteration of the dihedral angles of
N4-C9-C10-C11. The Partial geometry optimization in each state was performed by DFT based on the fixed(N4-C9-C10-C11) in some degree. The vertical excitation energies calculations are under SCS-RICC2 level.
The results are drew in Figure 1-3.

Fig. 1 the vertical excitation energy profiles of H2T(t-Bu)P calculated at the ground state geometry as
function of the fixed different dihedral angle (N4-C9-C10-C11).

－ 110 －

fukui2012_02.indb 110

14.1.9 1:45:12 PM

Ⅳ 研究業績 (2012)

Fig. 2 the vertical excitation energy profiles of H2T(t-Bu)P calculated at the S1 geometry as function of the
fixed different dihedral angle (N4-C9-C10-C11).

Fig. 3 the vertical excitation energy profiles of H2T(t-Bu)P calculated at the T1 geometry as function of the
fixed different dihedral angle (N4-C9-C10-C11).
The various absorption bands of H2T(t-Bu)P have an bathochromic shift compared to those of H2P.
The Stokes shift in the spectrum of H2T(t-Bu)P is 2 times larger than that form H2P spectrum results due tothe obvious distortion of the H2T(t-Bu)P geometry in the ground state and lowest excited state. The lowest
triplet state excitation energy form RICC2 calculation is ca. 0.45 eV larger than the TD-B3LYP result andagree well with the spectra measurement for FBP, whereas the corresponding RICC2 value for triplet state
excitation energy of H2T(t-Bu)P under the TD-B3LYP first triplet excited state geometry is completely
different from the TD-B3LYP excitation energy, the RICC2 value is 0.49 eV at middle infra-red region, while－ 111 －

fukui2012_02.indb 111

14.1.9 1:45:12 PM

Ⅳ 研究業績 (2012)

the TD-B3LYP value is -0.54 eV meaning the lowest triplet state energy level lower than ground state energy
level on this molecular geometry. (Require further explanation). At the excited state relaxation process of
H2T(t-Bu)P molecule, there are more complicated intersections of potential energy surface between their
ground state and excited state as well as between different excited states. The phosphorescence of
H2T(t-Bu)P is ultrafast and a poor competition with nonradiative course (for example: S1→T2→T1→S0).
The state-averaged multi-configurational self-consistent field (SA-MCSCF) was used for finding the conicalintersection point geometry. The results of these studies indicate that the substantial bulky substituent
decorated at the porphyrin periphery has an innegligible effect on the geometries and electronic spectra of
H2P and H2T(t-Bu)P through the central porphyrin plan ruffling.

2. Original papers(1) Qi Cao, Jing Wang, Zhao-Shuo Tian*, Zai-Feng Xie*, Fu-Quan Bai*,“Theoretical investigation on the photophysical properties of N-heterocyclic carbene Ir(III) complexes (fpmb)xIr(bptz)3-x (x=1-2)”.
Journal of Computational Chemistry, 33(10), 1038-1046 (2012)(2) Fu-Quan Bai, Jian Wang, Bao-Hui Xia, Qing-Jiang Pan, Hong-Xing Zhang*,“DFT and TD-DFT study on the electronic structures and phosphorescent properties of
6-phenyl-2,2 '-bipyridine tridentate iridium(III) complexes and their isomer”.
Dalton Transactions, 41(27), 8441-8446 (2012).
(3) Danming Chao, Xiaoteng Jia, Fu-Quan Bai, Hongtao Liu, Lili Cui, Erik B. Berda*, CeWang*,“An efficient fluorescent sensor for redox active species based on novel poly(aryl ether)
containing electroactive pendant”.
Journal of Materials Chemistry, 22(7), 3028-3034 (2012).
(4) Fu-Quan Bai, Jun-ya Hasegawa,“Computational studies of electronic spectra, photophysical properties and potential energy
surface conical intersection of free-base porphyrin and meso-subsitituted free-basetetratertiary-butylporphyrin”
Manuscript in preparation.
3. Others (Participation)(1) The 2nd International Conference on Computational and Theoretical Nanoscience -ICCTN
2013. Hong Kong, China, Mar. 1~3, 2013.
(2) The 10th Fukui Center Seminar, Kyoto, Japan, Mar. 21, 2013.
(3) Supercomputer Workshop, Okazaki, Japan, Jan.22~23, 2013.
(4) The 10th Symposium of Fukui Institute for Fundamental Chemistry, Kyoto, Japan, Nov. 30,
2012.

－ 112 －

fukui2012_02.indb 112

14.1.9 1:45:12 PM

Ⅳ 研究業績 (2012)

Jing-Dong GUO
SPR Fellow
1.

Summary of the research of the year
I. Theoretical study of the reaction of Disilyne with RCN (R=Me, Ph).

The silicon-silicon triple-bond disilyne 1 was reported on Science journal in 2004 by Prof. Sekiguchigroup. To understand the nature of the pi bonds of the triple bond, the reactivity of the disilyne toward
nitrile (Scheme 1) was investigated in experiments by the same group.
Scheme 1. Reaction of Disilyne with RCN (R=Me, Ph).

To gain a mechanistic insight, we have performed density functional calculations for the reaction ofdisilyne using a SiH3 group instead of SiiPr[CH(SiMe3)2]2 with acetonitrile by using the Gaussian 03
program.

Figure 1. Potential energy profile for reaction of a simplified disilyne with acetonitrile (energy in kcal/mol;
R1=SiH3, R2=CH3).

－ 113 －

fukui2012_02.indb 113

14.1.9 1:45:12 PM

Ⅳ 研究業績 (2012)

Figure 1 shows the energy profile along the reaction path calculated at the B3PW91 level using the 6311+G(2df) basis set for Si and 6-31G(d) for all other atoms. The first step in the reaction is theinteraction between the in-plane LUMO (πin*) of disilyne and the HOMO (lone pair) of the nitrile,
resulting in σ-coordination to produce the disilyne-nitrile complex intermediate (Int1), in which thenitrile is coordinated to one of the Si centers, with a C-N bond length of 1.163 Å, which lies in the typicalN-C triple-bond range (1.160 Å). Following this, intramolecular nucleophilic attack of the anionic silicon
atom on the nitrile carbon atom affords the imine-bridged disilene intermediate (Int2), which is the resultof a formal [2 + 2] cycloaddition between disilyne and nitrile. The addition of a second nitrile proceeds
via a similar formal [2 + 2] cycloaddition to give a 2,6-diaza-1,4-disila-Dewar benzene-type intermediate(Int3), in which the regiochemistry is reflected by the polarization of the Si-Si bond of Int2 as a result of
the difference in electronegativities of the N atom and the C atom. On the other hand, a concerted
pathway via [2 + 2] cycloaddition was not found.
From the 2,6-diaza-1,4-disila-Dewar benzene-type intermediate (Int3) to the final product, triaza-1,4disilabicyclo[2.2.2]octa-2,5,7-triene derivatives, there are three possible pathways for the last step: path A(blue), where the pathway starts with a skeletal Si-Si bond splitting to give a 1,3-diaza-2,5-disilabenzene
intermediate, followed by addition of a third nitrile; path B (black), where the pathway starts with askeletal Si-Si bond being split with a coordinated nitrile as a ligand in the transition state; path C (purple),where the pathway starts with a skeletal Si-Si bond being split by the attack of a nitrile from above. As
shown in Figure 1, the pathway involving the 1,3-diaza-2,5-disilabenzene-type intermediate (Int4) is lesslikely. Pathways B and C, which both include a complex intermediate(Int5), would be possible; pathway
C is the most probable because the energy barrier of 12.9 kcal/mol is the lowest of the three (path A 17.2
kcal/mol, path B 14.3 kcal/mol), although the other two possibilities cannot be excluded.

II. Theoretical study of the reaction of GeAr#2 with NH3.
The reactivity of germanium (II) carbene analogue (GeAr#2, Ar#=C6H3-2,6-(C6H2-2,4,6-Me3)2, Me:
methyl group) toward NH3 (Scheme 2) was investigated by Prof. Power group. The reaction afforded
Ge(IV) tetravalent product but not Ge(II) arene eliminated product.

－ 114 －

fukui2012_02.indb 114

14.1.9 1:45:13 PM

Ⅳ 研究業績 (2012)

Scheme 2. Reaction of GeAr#2 with NH3.

To understand the phenomena observed in experiments, we carried out the calculations with thedensity functional theory (DFT) in the Gaussian 03 program.

Figure 2. Calculated energy and drawings of intermediates and transition states with selected distances (Å) andangles (deg) for the reaction of GeAr#2 with NH3 at the B3PW91 level.

The DFT calculations for the reaction of GeAr#2 with NH3 indicate that the pathway involving a single
NH3 molecule had a high energy barrier. Since excess NH3 was used in the experiment, the alternative
pathway involving the participation of a second NH3 molecule was considered in the calculations.
Calculated reaction pathways for the reactions of GeAr#2 and drawings of the intermediates and transition
state structures are provided in Figure 2. The initial step is the interaction of a lone pair on the nitrogen of
an NH3 molecule with the 4p orbital of Ge to form the intermediate (INT) Ar#2GeNH3 complex. In thepresence of excess ammonia, a second NH3 molecule solvates the complexed NH3 via intermolecular N--－ 115 －

fukui2012_02.indb 115

14.1.9 1:45:14 PM

Ⅳ 研究業績 (2012)

H interactions. The INT then transforms via either TS or TS’to Ar#H eliminated or oxidative addition
product respectively. The oxidative pathway (TS’) is considerably (5.7 kcal mol-1) lower in energy than
the alternative elimination pathway even though the eliminated product Ar#GeNH2 + Ar#H is much moreenergetically favored than Ar#2Ge(H)NH2. Therefore, the reaction of Ar#2Ge with NH3 is kineticallycontrolled by TS’ to form the Ge(IV) tetravalent product.

2.

Original papers:(1) Katsuhiko Takeuchi, Masaaki Ichinohe, Akira Sekiguchi, Jing-Dong Guo, and Shigeru
Nagase,“Reactivity of Disilyne RSiSiR (R=SiiPr[CH(SiMe3)2]2) toward Nitriles: Unexpected
Formation of Triaza-1,4-disilabicyclo-[2.2.2]octa-2,5,7-triene Derivatives”
Organometallics 28, 2658-2660(2009).
(2) Yang Peng, Jing-Dong Guo, Bobby D. Ellis, Zhongliang Zhu, James C. Fettinger,
Shigeru Nagase, and Philip P. Power,“Reaction of Hydrogen or Ammonia with Unsaturated Germanium or Tin Molecules
under Ambient Conditions: Oxidative Addition versus Arene Ellmination”
J. Am. Chem. Soc. 131, 16272-16282(2009).

－ 116 －

fukui2012_02.indb 116

14.1.9 1:45:14 PM

Ⅳ 研究業績 (2012)

Peng JINSPR Fellow(From 16 Apr. 2012)
1. Summary of the research of the year (3-5 pages, includes appropriate figures and tables)
Density functional theory study of fullerene–carbene Lewis acid–base adducts
When a Lewis base (LB) is combined with a Lewis acid (LA), a neutralization reaction takes place
to yield a Lewis adduct by the interaction of the HOMO of LB and the LUMO of LA. Various
carbon-based LBs have been reported; examples are enamines, ylides, and N-heterocyclic carbenes(NHCs). In contrast, carbon-based LAs have remained limited to date.
A recent experiment by Bazan and co-workers shows that C60 can act as an all-carbon LA in thereaction with a strongly dative NHC, 1,3-bis(diisopropylphenyl)imidazol-2-ylidene (IDipp), to yield the
Lewis IDippC60 adduct (Fig. 1a). X-ray structural data and B3LYP density functional calculations
show that the adduct has a CC single bond between C60 and IDipp, in sharp contrast to thecyclopropanation reaction that usually occurs between fullerenes and carbenes or carbene surrogates.
Charge distribution analysis reveals that almost one electron is transferred from IDipp to C60,
representing the formation of a zwitterionic adduct. Moreover, C 70 can react with IDipp to form asingle-bonded Lewis adduct in a highly selective manner (Fig. 1b). In this context, ascertaining the
major driving force for the formation of the novel Lewis adducts is important.
Here, we carried out density functional theory (DFT) calculations for IDippC60 and IDippC70 adducts
to expand the chemistry of fullerene-based LAs. The B3LYP/6-31G* optimized structure of IDippC60
almost has Cs symmetry. The bridging CC bondlength (RCC) is 1.542 Å, indicating the formationof a typical  single bond between IDippand C60(Fig. 1a). Intramolecular electron transfer (0.84 e)
takes place from IDipp to C60.
Apparently,

donoracceptor

interaction

between IDipp and C60 is responsible for thebinding of the adduct. Surprisingly, the energy
of formation (Ef) is only 1.6 kcal/mol at theB3LYP/6-31G* level. This small Ef value might
be attributed to the dominance of the steric
repulsion between the bulky IDipp (especiallythe diisopropylphenyl groups) and C60. To verify
this point, the much smaller Ih in Scheme 1 wastested as LB. The RCC distance of 1.504 Å

Fig. 1 Optimized structures of (a) IDippC60, (b)IDippC70, and (c) ICatcherC60.

calculated for IhC60 becomes shorter than that of 1.542 Å for IDippC60. However, the calculated Ef－ 117 －

fukui2012_02.indb 117

14.1.9 1:45:14 PM

Ⅳ 研究業績 (2012)

value of 10.8 kcal/mol is too small to explain
the irresistible formation of LBfullerene
adducts.
Therefore,

we

further

performed

calculations using the dispersion-corrected
B3LYP-D3 method. The Ef value of IhC60
was increased by 7.0 kcal/mol at theB3LYP-D3/6-31G* level. In contrast, the Efvalue of IDippC60 is much more increased
Scheme 1 Carbon-based Lewis bases studied in thiswork.

with the dispersion correction, which is as
large

as

30.6

kcal/molatthe

B3LYP-D3/6-31G* level and 27.8 kcal/mol

at the B3LYP-D3/6-311G(2d)//B3LYP-D3/6-31G* level. These results show the importance ofdispersion attractions between IDipp and C60. The RCC distance of 1.527 Å calculated for IDippC60 at
the B3LYP-D3/6-31G* level is closer to the distance of 1.502 Å observed for the crystal structure. The
nearest distance of 3.372 Å between the two phenyl ring centers of IDipp and C 60 suggests interactions between IDipp and C60. In addition, the shortest CHC60 distance of 2.680 Å suggests
CH(C60) interactions.
Fig. 2 shows the energy profile for direct formation of the IDippC60 adduct by donation of theelectron pair of IDipp to C60. In the initial step for the addition of IDipp to C60, an intermediate complexof IDipp and C60 is formed, which is more stabilized at the B3LYP-D3 level. The energy barrier from theintermediate to the final adduct is only 4.1 kcal/mol at the B3LYP-D3 level, indicating that the direct
addition of IDipp to C60 proceeds much easily. The energy barrier (12.9 kcal/mol) and exothermicity(1.6 kcal/mol) calculated at the B3LYP level are considerably larger and smaller, respectively,
suggesting that dispersion attractions play an important role in reducing the reaction barrier and in
making the reaction much more exothermic.

Fig. 2 Energy profiles (kcal/mol) and RCC distances (Å) calculated for the addition of IDipp to C60
at the B3LYP/6-31G* (black) and B3LYP-D3/6-31G* (red) levels.

－ 118 －

fukui2012_02.indb 118

14.1.9 1:45:15 PM

Ⅳ 研究業績 (2012)

In an attempt to check substituent groups surrounding the imidazole ring, the bulkier IDbup in
Scheme 1 was considered. The Ef value calculated for the IDbupC60 adduct was only 6.8 kcal/mol at
the B3LYP-D3/6-31G* level because of the steric repulsion caused by the bulkier t-Bu group.
To design stable LBfullerene adducts, it is important to enhance dispersion attractions. Therefore, we
considered ICatcher in Scheme 1. The RCC distance calculated for ICatcherC60 is 1.550 Å (Fig. 1c). The
shortest distance of 3.103 Å between the corannulene carbon atoms and C60 suggests the presence ofimportant  interactions. The electron transfer of 0.89 e from ICatcher to C60 reflects that the ICatcherC60
adduct is zwitterionic, as is IDippC60. It is interesting that the Ef value of 39.1 kcal/mol for ICatcherC60 islarger than that of 30.6 kcal/mol for IDippC60 because of more effective dispersion attractions.
The C70 (D5h) cage has five types of nonequivalent carbon atoms (denoted as 1–5 in Fig. 3). Therefore,
five adducts can be formed for the addition of IDipp to C70. It has been observed that IDipp attacks
carbon-1 selectively to yield adduct-1 (seeFig. 3). The RCC distance of 1.528 Åcalculated for adduct-1 at the B3LYP-D3
level is closer to the distance of 1.503 Åobserved in the crystal structure. Totalelectron transfer of 0.86 e from IDipp to C70
indicates

that

the

IDipp-C70

adductiszwitterionic, as is IDippC60. As Table 1
shows, dispersion attractions are responsible
for the binding of all IDippC70 adducts.
However,

both

B3LYP

and

B3LYP-D3

calculations show that adduct-1 is the mostFig. 3 Carbon sites, twofold degenerate LUMO, andstable, followed by the almost isoenergetic

pyramidal angles of C70 (D5h) as well as fiveadduct-2,

IDippC70 adducts.

adduct-5 being the most unstable. These

adduct-3,

andadduct-4,

withresults suggest that dispersion attractions
make no important contribution to the relative stability of the adducts. It is interesting to note that the
LUMO distribution of C70 is the largest on carbon-1. In addition, carbon-1 is the most highly locallystrained, as measured by the largest pyramidal angle of 11.9 o.

－ 119 －

fukui2012_02.indb 119

14.1.9 1:45:15 PM

Ⅳ 研究業績 (2012)

Table 1 RCC distances (Å) and energies of formation (Ef, kcal/mol) of five IDippC70 adducts calculated at theB3LYP/6-31G* and B3LYP-D3/6-31G* levels. Values in parentheses are relative energies.
RCC

Ef

B3LYP

B3LYP-D3

B3LYP

B3LYP-D3

adduct-1

1.540

1.528

5.4 (0.0)

33.9 (0.0)

adduct-2

1.542

1.530

0.2 (5.6)

28.1 (5.8)

adduct-3

1.549

1.537

0.4 (5.8)

28.3 (5.6)

adduct-4

1.549

1.535

1.6 (7.0)

29.2 (4.8)

adduct-5

1.562

1.547

13.0 (18.4) 17.8 (16.1)

In summary, we found that dispersion attractions are critical for the formation of novel carbon-based
LBfullerene adducts (IDippC60 and IDippC70) synthesized recently, although they play no importantrole in the selective formation. Results suggest that a double concave catcher with a tweezers structure(ICatcher) is an interesting carbon-based LB, which embraces fullerenes. The electronic properties,
geometries, and reactivities of ICatcherfullerene adducts can be controlled by introducing substitutiongroups on the corannulene carbons. Introduction of bulky substituent group may lead to newcarbon-based frustrated Lewis pairs. Further developments in the chemistry of carbon-based LA/LB
pairs are expected.

2. Original papers(1) Peng Jin and Shigeru Nagase“Density Functional Theory Study of Fullerene-Carbene Lewis Acid-Base Adducts: CriticalRole of Dispersion Interactions”
RSC Adv. 3(26), 10177-10180(2013).

－ 120 －

fukui2012_02.indb 120

14.1.9 1:45:16 PM

Ⅳ 研究業績 (2012)

Zhuofeng KE
FIFC Fellow, Fukui Kenchi Memorial Research Group 1(To 31 Aug. 2012)
1. Summary of the research of the year (3-5 pages, includes appropriate figures and tables)
I. Theoretical Study of Polymerization Catalyzed by Artificial Metalloenzymes.
One of the promising strategies is toincorporate a catalytic metal complex intoa host protein to construct an artificial
metalloenzyme to achieve novel catalytic
features in the well-defined “womb” ofprotein. Through genetic evolution of theproteincomponent
andchemicalscreening of the metal complex Figure 1. The overview mechanism of the polymerization ofcomponent, artificial metalloenzymes will PA in the studied artificial metalloenzyme system.
provide a new horizon for application and development of catalysis. However, it is highly
challenging to unveil the active site and exact reaction mechanism inside artificial metalloenzyme,
due to the complicated interactions between metal complex and protein, especially when the metal
complexes have variable geometries in binding sites, which is the bottleneck in its rational design.
Even with some X-ray crystal structures of catalytic precursors or intermediates we are still far fromunderstanding the catalysis process inside artificial metalloenzyme. In this study, we will clarify,
with QM/MM calculations, an example of the intricate reaction mechanism of the recently
developed artificial metalloenzyme system (Rh(nbd)·apo-Fr) for polymerization (Figure 1).

Figure 2. The binding sites and plausible active site that promote the polymerization in Rh(nbd)·apo-Fr.

Inspired by our previously studies computationally the detailed mechanism of polymerizationof PA catalyzed by the homogenous catalyst [Rh(nbd)Cl]2 without protein environment. (J. Am.
Chem. Soc. 2011, 133, 7926-7941), we evaluated various possible mechanisms for all binding sites
suggested by the X-ray crystal structure, i.e., sites A, B, and C (Figure 2). Our QM/MM studies
found that sites A, B, and C themselves are only precursors/intermediates, not true active sites for－ 121 －

fukui2012_02.indb 121

14.1.9 1:45:17 PM

Ⅳ 研究業績 (2012)

polymerizationofPA
insideRh(nbd)·apo-Fr. A new site D is suggested
to be the most plausible active site forpolymerization. This active site D isgenerated by extrusion of the RhI(PA)complex to a hydrophobic pocket near site
B after coordination of first monomer PA.
RhI insertion is the most plausible
polymerization mechanism. The metal
center does not recombine to His49 of site
B even after olefin insertion, remaining in
the hydrophobic pocket for further
propagation. Further ONIOM calculations
with 5Å solvated water shell guaranteed
the reliability of former optimized results
and conclusions.
The hydrophobic pocket of site D,
which is composed of hydrophobic typesof residues, Phe50 and Leu170, and thehydrocarbon side chain of Lys143, plays a
key role for the polymerization behavior
insideRh(nbd)·apo-Fr(Figure 3). The hydrophobic
active site D, nonpolar
4-fold channel, and otherhydrophobic residues nearby
constitutea
specific“hydrophobic region” foraccumulation, coordination,and insertion of PA during
polymerization.

Figure 3. The plausible active site in hydrophobic pocket near site
D and the 4-fold channel.
H

H

Ph

H

RhI

Ph
Rh

RhI
2.1-insertion

His
Ferritin

DI-3

Ph

H

Ph

His

Ferritin

Ferritin

DI-PCD

H
Ph

H

RhI
His
Ferritin

DI-3isoH

RhI
1,2-insertion

H

Ph

His
DI-TSD

H

H

I

Ph
RhI

His

His

Ferritin

Ferritin

DI-TSDiso

H
H
Ph

DI-PCDiso

Notably,The
ONIOM-EE
calculation
predicts a preference of
2,1-insertionover
1,2-insertionby
2.3 Figure 4. The regioselectivity of the polymerization of PA in the hydrophobic
kcal/mol (Figure 4), leading active site D of Rh(nbd)·apo-Fr.
to head-to-tail cis−trans PPA, suggesting that this hydrophobic active site D in the artificial－ 122 －

fukui2012_02.indb 122

14.1.9 1:45:18 PM

Ⅳ 研究業績 (2012)

metalloenzyme, Rh(nbd)·apo-Fr, wellretains the regio- and stereoselectivity
feature of Rh-catalyzed polymerization of
PA found without the protein, which wasobserved in the experimental studies.
The analysis of energy changes andtheir major components arising fromprotein environment for the extrusion ofRh(PA) complex from site B (BI-2) to site
D (DI-3), suggests that that the electrostatic
effect contributes the most (−25.0 kcal/mol)and the vdW effect contributes the second,
while polarization has some negative effect(11.5 kcal/mol) when the Rh(PA) complex
moves from site B to site D (Figure 5). The
vdW, electrostatic, and polarization effects

Figure 5. The analysis of energy changes andcomponents arising from protein enviroment: energy changes(E) for the extrusion of Rh(PA) complex from site B (BI-2) tosite D (DI-3); reaction barrier (E‡) of the RhI-insertion at
DI-TSD in the active site D (relative to DI-3); the selectivity(E‡) between 2,1-insertion and 1,2-insertion in site D. QM
is the deformation energy of the QM part. vdW, elect andpolar are the van der Waals, electrostatic and polarizationenergies of the protein environment, respectively.

Scheme 1. The overview mechanism of the polymerization of
PA in the studied artificial metalloenzyme system.
A

CB

Ferritin

PA coordination of PAA

re-combination

A

CB

Ferritin

D

Ph
RhI

-H elimination

Ph

H

RhI

pol

C B

FerritinH
polcoordination of PAA

C B

FerritinD

Ph

H-transf er

H

RhI

pol

active site D with ahydrophobic pocket

Ph

H

pol

D Ph
A CB
RhI
Ferritinfrom the protein environment to theselectivity are relatively small, that is why
the regioselectivity can be maintained insideprotein.
The overall reaction mechanism is

dissociation f rom
binding site D

HIS

their majoroxidative addition
reductive elimination

RhI-insertion

shown in Scheme 1. This study highlights
the importance of theoretical study inmechanistic understanding and rational
design of artificial metalloenzymes,
indicating that even with X-ray crystal
structures at hand we may still be far fromfully understanding the active site and thecatalytic
mechanismofartificial
metalloenzymes.

Our QM/MM study demonstrates an example of a complicated reaction mechanism of artificial
metalloenzymes. Binding sites from X-ray crystal structures do not always guarantee the true active
site for catalytic reaction of artificial metalloenzyme, especially when binding interactions of themetal complexes and protein can highly vary. Theoretical studies are essential in providing deeper
insights to the active site and the catalytic behavior of artificial metalloenzymes. The binding andactive sites are not always the same, which inspires us to believe that reactivity should be tuned
based on the true active site and binding sites, on the other hand, may serve as a useful tool in
improving the loading amount of catalyst. Furthermore, the hydrophobic or hydrophilic region of－ 123 －

fukui2012_02.indb 123

14.1.9 1:45:19 PM

Ⅳ 研究業績 (2012)

the protein may have a significant influence on catalysis design.
II. Theoretical Study of Asymmetric Hydration Catalyzed by DNA-based Artificial Enzyme.
Biomacromolecule, like DNA, based catalysts recently emerges as an attractive strategy to thesynthesis of enantiomerically purecompounds. Through recombination of
DNA and metal complexes with a
specific ligand, high stereoselectivity andrate enhancement had been achieved inseveral important applications, such as
Diels–Alder,Michaeladdition, Figure 6. The hypothesis for the origin of asymmetric hydration
Friedel–Crafts reactions and hydration catalyzed by DNA-based artificial enzyme.
reactions. A novel non-enzymatic
catalytic enantioselective hydration of enones was recently published by Ben L. Feringa, Gerard
Roelfes and co-workers. The chiral beta-hydroxy ketone product was obtained in up to 82%
enantiomeric excess. Importantly, this diastereospecific and enantioselective reaction had noequivalent in conventional homogeneous catalysis. Herein, our theoretical study aims to understandthe mechanism and the factors that controlling the enantioselectivity, which is of fundamental
important to the development of these types hybrid catalysis with DNA (Figure 6).
Previously, our results suggested that the
CuII complexes prefer five and six-coordinatedstructures with additional axial solvent ligands,
rather than a four-coordinated square planar
structure. The combination of docking and MD
simulation of the binding modes and binding
minor groove aggregationenergies of CuII complexes to DNA moleculessuggested that the intercalations insertion should
be more favorable than the minor groove
aggregations, and the intercalations prefer
specific layer of the base pairs (Figure 7).
As for the mechanism of hydration ofenones, our calculation suggested both theintercalation
1,4-addition and the 1,2-addition assisted by
Figure 7. The suggested binding modes of CuII
coordinated water are less feasible (barriers,
complexes to DNA molecules.
about 30 kcal/mol), However, the hydration
reaction barrier is only about 16 kcal/mol with the assistance of a deprotonated water. We
constructed the initial structures on the basis of binding modes form Docking and MD simulations.
Waters around the metal complex were removed, while water shell around the DNA was remained.

－ 124 －

fukui2012_02.indb 124

14.1.9 1:45:39 PM

Ⅳ 研究業績 (2012)

As shown in Figure 8, red part & one key phosphate, two additional water molecules were included
as reactants, also in QM part (DFT/SDD&6-31G*); Black part, MM (gaff); DNA helix & 5A watershell MM(amber).
Our preliminary QM/MM results found that in
the DNA microenvironment, the hydration ofenone undergoes a mechanism similar to that of adeprotonated aqueous copper complex, with areaction barrier of around 20 kcal/mol. Ourstudies imply that the acidity/basicity of thecoordinatedligandortheFigure 8. Modles in ONIOM calculations..
base-pair/phosphodiester linkage may play animportant role in the stereoselectivity, which is still under progress.
2. Original papers(1) Ke, Zhuofeng, Abe, S., Ueno, T., & Morokuma, Keiji. Catalytic Mechanism in Artificial
Metalloenzyme: QM/MM Study of Phenylacetylene Polymerization by Rhodium Complex
Encapsulated in apo-Ferritin. J. Am. Chem. Soc. 2012, 134, 15418−15429.

(2) Ye, R.-R., Ke Zhuofeng, Tan C.-P., He L., Ji L.-N. & Mao Z.-W.
Histone-Deacetylase-Targeted Fluorescent Ruthenium(II) Polypyridyl Complexes as Potent
Anticancer Agents. Chem. Eur. J. 19, 10160 – 10169 (2013)(3) Liu Y., Ma L., Chen W.-H.*, Park H., Ke Zhuofeng*, & Wang B.* Binding Mechanism and Synergetic
Effects of Xanthone Derivatives as Non-competitive α-Glucosidase Inhibitors: a Theoretical andExperimental Study. J. Phys. Chem. B. Accepted.

3. Presentation at academic conferences(1) Ke, Zhuofeng, Abe,S., Ueno, T., Morokuma, K. "Structural control mechanism in
Rh-catalyzed synthesis of pi-conjugated polymer in the nano cavity of apo-Ferritin ".

International Conference for Leading and Young Materials Scientists (IC-LYMS 2012),
Zhuhai, China. Dec. 16-20, 2012.
(2) Liu, Z., Liu, Y., Yang, C., Zhao, C., Ke, Zhuofeng*, The Strong Effect of Weak Interaction in
Asymmetric Organocatalysis. International Symposium on Organic Reaction Mechanism,
University Town Library of Shenzhen UTSZ, China. May. 8-9, 2013.

－ 125 －

fukui2012_02.indb 125

14.1.9 1:45:54 PM

Ⅳ 研究業績 (2012)

Joonghan KIM
FIFC Fellow, Fukui Kenichi Memorial Research Group 1(To 17 Aug. 2012)
1. Summary of the research of the year
Quantum Chemical Molecular Dynamics Simulations for Chirality-Controlled SWCNT GrowthSingle-walled carbon nanotube (SWCNT) has attracted much attention for electronic and opticalapplications due to its fascinating physical and chemical properties. SWCNT’s unique properties solely
depend on its chirality. Therefore, the control of the chirality is a prerequisite condition for further
applications. However, the chirality-controlled growth of SWCNT experimentally and theoretically has notbeen achieved yet due to its chaotic nature. Quantum chemical molecular dynamics (QM/MD) simulations
based on the self-consistent-charge density-functional tight-binding (SCC-DFTB) method to investigate thechirality-controlled growth of SWCNT have been performed. All simulated trajectories are analyzed using
recently developed time evolution local chirality index (TE-LOCI) method; the dynamics of local SWCNT
chirality have been monitored during the growth process. The final structures of all simulated trajectories at 1
ns are shown in Figure 1. As can be seen in Figure 1, the added C atoms are adsorbed onto the Fe38 surface or
located at the interface between SWCNT and Fe38 as the ingredient of SWCNT. Here we focus general
growth mechanism of AC SWCNT in the case of shooting C2 to the Fe38 surface. First, the added C2 isanchored onto the Fe38 surface. Since the electronic temperature (Te) is high (10000 K), the diffusion of C2
on the Fe38 surface is readily takes place. Generally, C2 remains with diffusion on the Fe38 surface for a long

Figure 1. Snapshots of trajectories from A to J following 1 ns (1000 ps) of QM/MD growth simulations.
Brown, black, white, and green spheres represent Fe, C, H, and added C atoms, respectively.

－ 126 －

fukui2012_02.indb 126

14.1.9 1:45:54 PM

Ⅳ 研究業績 (2012)

time. The diffusing C2 molecules meet another C2 on the Fe38 surface and subsequently make short polyyne
chains. In another case, the diffusing C2 is attached to the interface between SWCNT and Fe38; the one sideof C2 is connected to one of Fe atom of Fe38 and the other is connected to one of C atom of the hexagon edge.
Finally, the bond between C and Fe is broken and then a hexagon on the edge is formed. This is a basic
mechanism of forming hexagon in all simulated trajectories (see Figure 2); almost all hexagons have been
formed via this simple mechanism.

Figure 2. Reaction mechanism of formation of hexagon. The snapshots were extracted
from the trajectory J.
The added C2 molecule remains on Fe38 surface for a long time and frequently polyyne chains areformed. The retention time of polyyne chain on the surface is prolonged as the chain length of polyyne
increases. Hence, the concentration of carbon is accumulated on Fe38 surface. If it is over some thresholdvalue, a nucleation process on the catalyst surface takes place; long polyyne chains change to the polygons,in particular pentagon, via self-isomerization. As time passes, other polyyne chain or C2 unit are attached tothe pentagon; it eventually grows as another “cap”, carbon encapsulation. Another cap in the trajectory C(TrajC) have been reflected to increases of pentagons and hexagons. In addition, hexagon in the cap canpossesses the local chirality which differs from the original one (armchair, AC in this case). TE-LOCI
analysis of TrajC shows sudden broadness of standard deviation of the local chiral angles. The change ofchirality (broadening standard deviation) in TrajC is ascribed to the formation of hexagons in the cap. These
results indicate that occurring nucleation process hinders achievement of the chirality-controlled growth. To
prevent forming new cap structure or occurring nucleation process, the concentration of carbon on the
catalyst surface should be controlled. Continuous adding C2 on the Fe38 surface increase the concentration ofcarbon and eventually leads to occurrence of nucleation and growth of another cap. Therefore, we developed－ 127 －

fukui2012_02.indb 127

14.1.9 1:45:55 PM

Ⅳ 研究業績 (2012)

the method to maintain the concentration of carbon on the Fe38 surface to circumvent the occurrence of
nucleation and formation of another. These two unwanted occurrence have been greatly reduced using thismethod; only one trajectory, TrajC with another cap structure has been observed. According to these results,
keeping proper concentration of carbon on the catalyst surface should be one of prerequisites for a success ofthe chirality-controlled SWCNT growth.
In the earlier studies where C atom has been shot as a feedstock, formations of heptagon are
considerable; the simulated all trajectories contains heptagons even using slow supply. The formation of
heptagon at the edge region makes the chirality-controlled growth be more complex because heptagon at theedge changes the original chirality of SWCNT. The new added hexagon after formation of heptagon canpossess other chirality. The mechanism of formation heptagon in the supplying C atom is very simple. The
added C atom can readily be inserted into a hexagon due to very high reactivity of C atom. Thereby one
number of the preexisted hexagon decreases, in contrast, one number of heptagon increases. Thus, total
number of hexagons is smaller than that of starting SWCNT (20 in this case). This indicates that SWCNT
actually does not grow in the case of supplying C atom. In contrast, formations of heptagon are notconsiderable in this work where C2 has been added. In addition, it is note that no trajectory observed where
the number of hexagon is less than twenty which is the number of hexagon in the starting structure of

Figure 3. (a) SWCNT growth from (5,5) armchair fragment in trajectory J (TrajJ). Color scheme as in Figure
1. (b) Polygonal carbon ring populations of TrajJ. Blue, green, and red lines are pentagon, hexagon, andheptagon, respectively. (c) TE-LOCI analysis of SWCNT growth in TrajJ. The red dot is average of local
chiral angle and error bar denotes its standard deviation. (d) Local chiral angles of all hexagons in TrajJ at 1
ns. Red and blue bars denote original and added hexagons, respectively.

－ 128 －

fukui2012_02.indb 128

14.1.9 1:45:55 PM

Ⅳ 研究業績 (2012)

SWCNT. These results indicate that the supplementing C2 rather than C atom greatly reduce the formationsof heptagon and it can facilitate the actual growth of SWCNT. In addition, C2 was directed to the Fe38 surface
instead of the edge region between nanotube and Fe38. It also contribute to less formation of heptagon. If
adding C2 is directed to the edge where the reactions frequently occur, the possibility of defects formation
significantly increases. These results have been already observed in the preliminary simulations of theprevious study. According to these results, supplying C2 to the catalyst surface is more appropriate for
reducing defects formations, especially heptagon, thereby it will lead to achieve the chirality-controlled
growth.
Polygonal carbon ring populations of TrajJ in Figure 3(b) shows that the eight new hexagons havebeen added to the seed nanotube; total number of hexagons is twenty eight. In addition, no fluctuation isobserved in TE-LOCI plot (see Figure 3(c)). This indicates that the chirality is maintained during the growth
process up to 1 ns. Indeed, as can be seen in Figure 3(d), the local chiral angles of both preexisting andnewly added hexagons in the SWCNT at 1 ns are close to 30, chiral angle of AC SWCNT. It is noteworthy
that SWCNT in TrajJ shows a root growth. The five hexagons of the new eight hexagons formed from fiveC2 make a new one ring of SWCNT. The proper five new hexagons provide a new one ring of AC(5,5)
SWCNT. This result has not been ever achieved in the previous QM/MD simulations. In summary, TrajJ
shows actual growth of SWCNT with maintaining its original AC chirality viz. the chirality-controlled
growth. Therefore, TrajJ in this work strongly suggests the evidence that the chirality-controlled growth canbe achieved. Unfortunately, the SWCNT structure of TrajJ at 1 ns contains one pentagon at the edge region
between SWCNT and the Fe38 catalyst as shown in Figure 3(b). This pentagon formed at 215.72 ps andmaintained for ~400 ps. It eventually has been removed at 633.08 ps (it does not mean the healing because
the number of hexagon did not increase). However, the same kind of pentagon also formed at 618.64 ps andit remained up to 1 ns. This result implies that a removal of this kind of pentagon at the edge is very difficult
task. However, consequentially, one of two these pentagons has been removed due to the catalytic effect of
Fe38. Therefore, if the QM/MD simulation is performed persistingly, another remained pentagon at the edge
can be removed. Thereby SWCNT can grow without defects and change its original chirality, thechirality-controlled growth. According to these results, TrajJ shows the evidence of achieving thechirality-controlled SWCNT growth.

2. Original papers(1) Joonghan Kim, Alister J. Page, Stephan Irle, and Keiji Morokuma,“Dynamics of Local Chirality during SWCNT Growth: Armchair versus Zigzag
Nanotubes”, J. Am. Chem. Soc. 134, 9311 (2012)
3. Presentation at academic conferences(1) Joonghan Kim, Alister J. Page, Stephan Irle, and Keiji Morokuma“LOCI (Local Chirality Index) Method for Chirality-Controlled Growth of Single-Walled－ 129 －

fukui2012_02.indb 129

14.1.9 1:45:55 PM

Ⅳ 研究業績 (2012)

Carbon Nanotubes”
14th International Congress of Quantum Chemistry (ICQC), Boulder, Colorado, USA, June
26, 2012－ 130 －

fukui2012_02.indb 130

14.1.9 1:45:56 PM

Ⅳ 研究業績 (2012)

Alister PAGE
Fukui Fellow, Fukui Kenichi Memorial Research Group 1(To 30 Jun. 2012)

1.

Summary of the Research of the Year(A) Graphene Nucleation on Transition Metal Surfaces

Graphene is heralded as ‘the ultimate material’,due to its remarkable electronic, thermal andmechanical properties. It is these properties that are
the basis for many proposed graphene-based deviceson the nanoscale. Earlier reports of graphene
synthesis consisted of techniques such as mechanicalexfoliation of highly oriented pyrolytic graphite (the‘scotch-tape method’). However, chemical-vapor
deposition (CVD) synthesis of graphene, typicallyusing transition or noble metal catalysts, isincreasingly becoming the most likely candidate bywhich large-area graphene will be manufactured on
a commercial scale. In this respect, the Ni(111)
surface exhibits particular notoriety, with a numberof experimental demonstrations of graphene growthon Ni(111) reported in the literature. Cu is also an
increasingly popular catalyst, due to the fast growth
rates and large domain sizes that can be obtained byits use. Presumably the latter phenomena are driven
by the relatively weak carbon-metal interaction
strength and poor bulk carbon solubility in the caseof Cu. The former is also true, although to a lesser
extent, in the case of Ni. On the other hand, metal
surfaces such as Fe(111) exhibit notably lesscatalytic activity in the context of graphene
nucleation, and also yield smaller domain sizes. The
effect of the carbon-metal interaction strength on themechanism and kinetics of graphene growth istherefore implicated by these CVD studies. Similar
relationships have previously been observed in thecontext of carbon nanotube growth on transition
metal catalysts. The mechanism by which discrete
graphene precursor islands are converted into largearea graphene is itself unknown at present. We
performed
quantumchemicalsimulations
demonstrating graphene precursor formation on bcc(111) transition metal surfaces during the chemical
vapor deposition process. We observe that theexperimentally reported positive curvature ofgraphene precursors is a consequence of the naturaltendency towards pentagon formation during the
precursor self-assembly process. Density functional

Figure 1. Quantum chemical simulations show thatthe mechanism of graphene growth is determined by
the strength of the catalyst-carbon interaction, akin tocarbon nanotube growth.

theory calculations reveal that the stability of theseprecursors is driven by the dominance of metalcarbon σ bonding over metal-carbon π bonding at
the precursor edge (Table 1). These simulations
show that Fe(111) catalysts facilitate precursor
formation at lower carbon densities, and increaseprecursor stabilities. However, the stronger catalystcarbon interaction strength in the case of Fe(111)significantly promotes catalyst surface degradation.
The use of more weakly interacting catalysts, suchas Ni(111) and Cu(111), circumvents this issue.
However, QM/MD simulations of Ni(111) catalyzed
CVD show that graphene nucleation requires asignificantly higher carbon density, compared to thecase of Fe(111). We propose that the performance ofdifferent transition metals with respect to catalyzing
graphene growth, akin to carbon nanotube growth,correlates with the catalyst-carbon interaction
strength.

－ 131 －

fukui2012_02.indb 131

14.1.9 1:45:56 PM

Ⅳ 研究業績 (2012)

Table 1. Comparison of - and - bonding between graphene and Fe(111), Ni(111) and Cu(111) surfaces interms of binding energy (eV/carbon atom) and metal-carbon bond distances (Å, in parentheses). Binding
energy is defined here as (E[M(111)-graphene] – E[M(111)] – E[graphene])/nC, for n C atoms.

Fe

Ni


Cu

Fe

Ni

Cu

DFT

2.94 (1.91)

2.76 (1.86)

2.13 (1.95)

0.27 (2.04)

0.00 (3.58)

0.00 (3.76)

DFTB

2.68 (2.13)

2.96 (2.10)

1.82 (2.26)

0.14 (2.75)

0.05 (3.03)

0.06 (3.11)

Figure 2. Comparison of Clar (left), Kekule (middle) and DFTB (right) descriptions of oxidation of HGFs 1-11.
Bonds are color-coded according to the % of conjugation remaining in the structure (Clar/Kekule) or E(DFTB);DFTB data correspond to singlet-state HGF oxides. Asterisks on DFTB structures denote those positions at which
oxidation leads to ether formation. No triplet-state HGF oxide 1o-11o featured ether formation, for any oxygen
position (i.e. oxidation at all positions resulted in epoxide formation).

－ 132 －

fukui2012_02.indb 132

14.1.9 1:45:57 PM

Ⅳ 研究業績 (2012)(B) Simulated IR/Raman Spectra of Graphene and Graphene Oxide
Graphene and graphene oxide (GO) are currently at the forefront of modern materials science andtechnology. Yet it was over a century ago, in 1859, that Benjamin Brodie isolated GO for the first time
via the exfoliation of graphite oxide. The popularity of graphene and GO today stems from theiroutstanding physicochemical properties, which make their application in nanoscale electronic andoptical devices a potential reality. Proposed GO structures and their dynamic and chemical behavior
remain controversial. Perhaps the most popular structural proposal is that by Lerf and Klinowski, whichassumes epoxides and alcohols to be the main features in the graphene basal plane, leaving the carbon
�bond network intact. Conversely, the GO structure proposed by Dekany et al. is dominated by ether
and keto functional groups in the GO basal plane, assuming partial damage to the carbon �bond
network. Recent experiments suggest that oxidation results in both ether and epoxy groups in the GO
basal plane, with the ratio of epoxy and ether groups being dependent on the extent of functionalization.
Molecular dynamics simulations suggest that epoxide groups are able to migrate on the surface even at
300 K, while other investigations point to a‘kinetically constrained’ GO structure. Oxidative
linear unzipping of graphenes has been deemed
possible, but could not directly be confirmed inquantumchemicalmolecular
dynamics
simulations.
We performed a detailed analysis of thefactors influencing the oxidation of graphene
nanoflakes using conventional density functional
theory (DFT), the density-functional tightbinding (DFTB) method, graph theoreticalinvariants, and �Hückel theory. The relative
thermodynamic stability associated with thechemisorption of oxygen atoms at various
positions on hexagonal graphene flakes (HGFs)
of D6h-symmetry is determined by two factors –viz. the disruption to the -conjugation of the
HGF, and the geometrical deformation of the
HGF structure. The most thermodynamicallystable structure is achieved when the former
factor is minimized, and the latter factor issimultaneously maximized (Figure 2). Infrared(IR) spectra computed using DFT and DFTB
reveal a close correlation between the relative
thermodynamic stabilities of the oxidized HGF
structures and their IR spectral activities. The
most stable oxidized structures exhibit greatest
IR activity between 600 – 1800 cm-1, whereas
less stable oxidized structures exhibit little to no
activity in this region (Figure 3). This in itself
reflects experimental trends in the structural
evolution during the thermal reduction of GO.
Finally, we note that when geometricaldeformation was minimal, Hückel method andgraph-theory
based
topologicalinvariants
Figure 3.(a) – (e) IR spectra of isolated Clar-sextet species 1
effectively predicted the results gained from– 5 and 1o – 5o between 600 – 1800 cm-1. The IR spectra of
species with oxygen near the edge and center of the HGF are
density functional based methods, which are more
depicted in red and blue, respectively. Spectra in black arecomputationally expensive by two or three orders
those of the respective pristine HGFs. Position numbers areof magnitude. We believe this fact should remind
defined in Fig.1. Peak intensities (vertical axis) given in
the community of the physical insights that are
KM/mol, vibrational wavenumbers (horizontal axis) given in
made possible by the use of such conceptually-1cm .
simpletechniquesinthecontextofgraphene/SWCNT functionalization.
－ 133 －

fukui2012_02.indb 133

14.1.9 1:45:57 PM

Ⅳ 研究業績 (2012)(C) Effects of Molecular Dynamics Thermostats on Descriptions of Chemical NonEquilibrium
The performance of popular molecular dynamics (MD) thermostat algorithms in constant temperature
simulations of equilibrium systems is well known. This is not the case, however, in the context of nonequilibrium chemical systems, such as chemical reactions or nanoscale self-assembly processes. We haveinvestigated the effect of popular thermostat algorithms on the natural dynamics of a non-equilibrium,chemically reacting system. By comparing constant-temperature quantum mechanical MD (QM/MD)
simulations of carbon vapor condensation using velocity scaling, Berendsen, Andersen, Langevin and NoséHoover Chain thermostat algorithms with ‘natural’ NVE simulations, we have shown that efficienttemperature control and reliable reaction dynamics are mutually exclusive under conditions of chemical nonequilibrium, see Fig. 5. This problem may be circumvented, however, by placing the reactive system in an
inert He atmosphere which is itself described using NVT MD, see Fig. 6. We have demonstrated that both
realistic temperature control and dynamics consistent with natural NVE dynamics can then be obtained
simultaneously. In essence, the thermal energy created by the natural dynamics of the NVE subsystem isdrained by the thermostat acting on the NVT atmosphere, without adversely affecting the dynamics of thereactive system itself.

Fig 5. Comparison of time-dependent velocity
distributions of a reactive C2 system using (a) NVE
C2 and a Nosé-Hoover Chain thermostat coupled (b)strongly ( = 188.37 ps-1) and (c) weakly ( = 0.19
ps-1) to the degrees of freedom of the system. For
reference, time-dependent Maxwell-Boltzmann
velocity distributions at the corresponding NVE
MDsimulation temperatures are included in (a)(grey lines). Temperature control comes at the costof sacrificing a reliable description of the ‘natural’reaction dynamics.

Fig 6. Comparison of time-dependent velocity
distributions of a reactive C2 system using (a) NVE
C2, (b) NVE C2+He, and (c) NVE(C)-NVT(He)ensembles. For reference, time-dependent MaxwellBoltzmann velocity distributions at the corresponding
NVE MD simulation temperatures are included in (a)(grey lines). NVE/NVE(C)-NVT(He) simulations use
C:He=1:1. P(v) shown only take into account carbon
atom velocities.

－ 134 －

fukui2012_02.indb 134

14.1.9 1:45:58 PM

Ⅳ 研究業績 (2012)2.

Original Papers(1) H.-B. Li, A. J. Page, Y. Wang, S. Irle, K. Morokuma, “Sub-Surface Nucleation of Graphene Precursors
near a Ni(111) Step-Edge”, Chemical Communications, 48, 7937-7939 (2012).
(2) A. J. Page, T. Isomoto, J. Knaup, S. Irle, K. Morokuma, “Effects of Molecular Dynamics Thermostatson Non-Equilibrium Systems.”, Journal of Chemical Theory and Computation, 8, 4019-4028 (2012).
(3) H.-B. Li, A. J. Page, S. Irle, K. Morokuma, “SWCNT Growth from Chiral Carbon Nanorings: Prediction of
Chirality and Diameter Influence on Growth Rates”, Journal of the American Chemical Society, 134 1588715896 (2012).
(4) A. J. Page, C.-P. Chou, P. Q. Buu, H. Witek, S. Irle, K. Morokuma, “Quantum Chemical Investigationof Epoxide and Ether Groups in Grpahene Oxide and their Vibrational Spectra”, Physical Chemistry
Chemical Physics, 15, 3725-3735 (2012).
(5) K. R. S. Chandrakumar, A. J. Page, S. Irle, K. Morokuma, “Carbon Coating Precedes SWCNT
Nucleation on Silicon Nanoparticles: Insights from QM/MD Simulations”, Journal of Physical
Chemistry C, 117, 4238-4244 (2012).
(6) A. J. Page, Y. Wang, H.-B. Li, S. Irle, K. Morokuma, “Nucleation of Graphene Island Precursors on
Transition Metal Surfaces: Insights from Theoretical Simulations”, Journal of Physical Chemistry C,
Submitted.
(7) H.-B. Li, A. J. Page, S. Irle, K. Morokuma, “Revealing the Dual Role of Hydrogen for Defect Healing
and Growth Inhibition in Polycyclic Aromatic Hydrocarbon Formation with QM/MD Simulations”,
Journal of Physical Chemistry Letters, Submitted.

3.
(1)Book Chapters“Atomistic Mechanism of Carbon Nanostructure Self-Assembly as Predicted by QM/MD Simulations”
in Practical Aspects of Computational Chemistry: An Overview of the Last Two Decades and Current
Trends. S. Irle, A. J. Page, B. Saha, Y. Wang, K. R. S. Chandrakumar, Y. Nishimoto, H.-J. Qian, K.
Morokuma, Springer, New York, USA, In press. ISBN: 978-94-007-0918-8.

－ 135 －

fukui2012_02.indb 135

14.1.9 1:45:58 PM

Ⅳ 研究業績 (2012)

Miho HATANAKAFIFC Fellow, Fukui kenichi
FIFC
KenichiMemorial
MemorialResearch
ResearchGroup
Group11

1. Summary of the research of the fiscal year
1.1 Aqueous Mukaiyama Aldol reaction catalyzed by lanthanide tri cation

Organic chemical reactions in aqueous solution are getting much attention as a green
chemistry for the next generation. Among them, carbon-carbon bond forming reactions
catalyzed by water-tolerant Lewis acid is one of the most attractive reactions. Usually,
Lewis acid catalysts have to be used under strictly anhydrous conditions because they
are unstable and inactive with water. However, lanthanide triflates Ln(OTf)3 cancatalyze many carbon-carbon bond forming reactions, such as Mukaiyama Aldol
reaction (Scheme 1). However, these reactions achieved only for limited substrates
because of the lack of information about the reaction mechanism.

Scheme 1. Lanthanide triflate-catalyzed Mukaiyama Aldol reaction in aqueous media
To design more efficient and high stereoselective reactions, we need to understandthe detailed reaction mechanism, especially the role of lanthanide cation and water.
Though several experimental studies were reported to discuss the mechanism, there areremaining questions about the role of water. First question is why the yield of
Mukaiyama Aldol reaction catalyzed by Ln3+ in organic solvent dramatically increases
by addition of water. Second question is why diastereoselectivity changes fromanti-preference to syn-preference by addition of water. To answer these questions, thereaction mechanism as well as hydrous structures of Eu3+ and their stability is discussed
using dispersion corrected B3LYP-D3 theory.
The most stable Eu3+ species in aqueous media is Eu3+ coordinated by eight or ninewater molecules and that coordinated by eight water molecules and a benzaldehyde.
Therefore, Eu3+ coordinated by eight water molecules and an aldehyde is considered asa reactant below. The whole reaction pathways are explored by using automated explore－ 136 －

fukui2012_02.indb 136

14.1.9 1:45:58 PM

Ⅳ 研究業績 (2012)

method, called the artificial force induced reaction (AFIR)
method. To consider all the reaction pathways, reactions
between all the combinations of fragments shown in
Scheme 2 are considered.
The obtained reaction pathway is a step-by-stepreaction which starts from C-C bond formation followedby proton transfer from water to benzaldehyde andScheme 2. Fragmentation
for AFIR calculation

trymethyl silyl (TMS) dissociation promoted by nucleophilic attack of bulk watermolecules. The first question can be explained by the shape of reaction energy surface.
The product of C-C bond formation (Cmp2) is less stable than the reactant (Cmp1) andthe backward reaction barrier is only 1.2 kcal/mol, which means that the backward
reaction proceeds easily. The complex is well stabilized only after the TMS dissociation
by nucleophilic attack of water molecules. Therefore, TMS dissociation displaces theequilibrium between Cmp1 and Cmp2 and promotes the forward reaction. This TMS
dissociation does not proceed without water, which results in the low yield under theanhydrous condition.
Next, we focus on the C-C bond formation step to discuss the diastereoselectivity.
Because of the structural fluctuation around Eu3+ and different torsion around reactive
C-C bond, many TSs are expected for the same C-C bond formation step and a method
for search of all possible TSs is required. The AFIR method seems to be ideally suitedfor determination of many possible stereoselective TSs of complex and flexible organic
reactions. As shown in Figure 1, 91 and 74 unique TSs are obtained which produce synand anti-products, respectively by using AFIR method starting from random 437 initialstructures. Among them, the lower 17 TSs contribute to the diastereomeric ratio(syn:anti = 75%:25%) which shows a good agreement with the experimental ratio of
73%:27%. The second question mentioned above can be understood by comparison of
the lowest syn and anti-TSs. Though the lowest anti-TS has the lowest potential energy
because of the smallest steric repulsion, the destabilization by entropic effect for thelowest anti-TS is larger than that for the lowest syn-TS because of the less structuralfluctuation caused by hydrogen bond between TMS enol ether and coordination water.

－ 137 －

fukui2012_02.indb 137

14.1.9 1:45:59 PM

Ⅳ 研究業績 (2012)

That results in the higher Gibbs free energy of the anti-TS than that of the syn-TS. In
other words, anti-TS is destabilized because of coordination water molecules.
As shown above, the roles of water for this reaction are to stabilize the product bypromoting TMS dissociation by nucleophilic attack, and to supply a proton to aldehyde.
In addition, the entropic effect caused by coordination water around Eu3+ changes thediastereoselectivity.

Figure 1. The relative Gibbs free energy G (in kcal/mol) and dihedral angle  (in °) of TSs
for C-C bond forming step. TSs producing syn and anti-products are shown in (a) and (b),respectively.

1.2. Enantio-selective Ln3+ catalyzed Aqueous Mukaiyama Aldol reaction

The demerit of the reaction above is low
diastereoselectivity

mainlycausedbystructuralfluctuation of coordination water around Eu3+. To
solve this problem, Allen and coworkers designed a
new C2 symmetric ligand for Eu3+ which achieved ahighdiastereoselectiveandenantioselective

Mukaiyama Aldol reaction in aqueous media.
However, our optimized geometry of C2 symmetriccatalyst did not seem to control the stereoselectivity.
Therefore, to find other stable structures for thecatalyst, another automated explore method, called theanharmonic downward distortion following (ADDF)

Figure 2. The three most stablegeometries of the catalyst.

method was carried out which results in 26 unique geometries for local minima. As－ 138 －

fukui2012_02.indb 138

14.1.9 1:45:59 PM

Ⅳ 研究業績 (2012)

shown in Figure 2, we found not only C2 symmetric geometry but also distorted C1
symmetric geometries whose energetics were quasi-degenerated. As discussed in theprevious section, aldehyde coordinates to Eu3+ firstly and the following C-C bondformation is the diastereo and enantio-determining step. Firstly, we focus on thecoordination geometry of aldehyde and two water molecules, where the coordination
number of water is measured by luminescence-decay. Surprisingly, the coordination
structure can be categorized into only two groups regardless of different geometries of
the catalyst. The structural sampling of TSs for C-C bond is still calculating, so wecannot conclude the mechanism of the stereoselectivity. However, we can say two
important keys for this reaction. The first point is that asymmetric environments, suchas Cat2 and Cat3 in Figure 2, are generated by the structural fluctuation around Eu3+.
The second point is that what control the coordination structure of aldehyde are theoxygen atoms in the macro cyclic ring part and the carbonyl part by hydrogen bonds.
1.3. Reduction of NO in qNOR enzyme
Nitrous oxide reductase (NOR)
is a key enzyme for the reductionof NO which is a step in anaerobic
respiration process. Recently, the
X-ray structure of a new type ofNOR,

calledNOR(qNOR),

quinol-dependentwasreported,

whose geometry around two Fe
centers are slightly different fromanother NOR (cNOR). Figure 3

Figure 3. Reaction pathways for NO reduction

shows the obtained reaction pathways calculated by B3LYP method using a model complex.
The most favorable path is the cis:b3 mechanism whose rate determining step is the rotation of
five- membered ring step (Cmp6→Cmp9). In the case of the NO reduction mechanism in cNOR,
the reaction barrier of the rotation of five-membered ring is too high because of the smaller
space of the active site. In other words, the coordination structure around two Fe centers
controls the reaction even if they do not participate in the reaction itself.

－ 139 －

fukui2012_02.indb 139

14.1.9 1:45:59 PM

Ⅳ 研究業績 (2012)

2. Original Papers
1. S. Maeda, E. Abe, M. Hatanaka, T. Taketsugu, K. Morokuma, “Exploring Potential Energy
Surfaces of Large Systems with Artificial Force Induced Reaction Method in Combination
with ONIOM and Microiteration” J. Chem. Theory Comput. 8, pp5058-5063 (2012).
2. M. Hatanaka, S. Maeda and K. Morokuma, “Sampling of Transition States for Predicting
Diastereoselectivity Using Automated Search Method–Aqueous Lanthanide- Catalyzed
Mukaiyama Aldol Reaction”, J. Chem. Theory Comput. In press.
3. M. Hatanaka and K. Morokuma, “Role of water in Mukaiyama Aldol Reaction Catalyzed by
Lanthanide Lewis Acid”, Manuscript in preparation.
4. M. Hatanaka and K. Morokuma, “The mechanism of reduction of nitric oxide in cytochromec-dependent nitric oxide reductase (cNOR): A DFT study”, Manuscript in preparation.
3. Presentations at meetings
1.畑中美穂, 諸熊奎治, “DFT 法および ONIOM 法を用いた一酸化窒素還元酵素の反応機構に関する理論的”, 第 15 回理論化学討論会 2012 仙台, 2012/05/25.
2. Miho Hatanaka, Keiji Morokuma, “The mechanism of the reduction of nitric oxide inbacterial nitric oxide reductase: A DFT and ONIOM study” 14th International Congress of
Quantum Chemistry, Boulder, 2012/06/27.
3. 畑中美穂, 諸熊奎治, “一酸化窒素還元酵素 cNOR 及び qNOR における一酸化窒素還元反応機構の理論的研究”, 第 6 回分子科学討論会 2012 東京, 2012/09/21.
4. Others
1.畑中美穂, “コンピュータで見る化学反応の世界”, 理系インスパイアー講演会, 北摂三田高等学校, 2012/09/13.
2.畑中美穂, “コンピュータで見る化学反応の世界”, 子どもの知的好奇心をくすぐる
体験授業, 京都府立宮津高等学校, 2012,11/05.
3.畑中美穂, “新薬ができるまで―「化学」はこんなふうに新薬開発に関わっています―”, 人間科学類型特別授業, 北摂三田高等学校, 2013/01/10.
4. Miho Hatanaka, “Mechanism of Mukaiyama Aldol Reaction Catalyzed by Water-Tolerant
Lanthanide Lewis Acid - An Artificial Force Induced Reaction Study”, The 10th Fukui
Center Seminar, 2013/03/21－ 140 －

fukui2012_02.indb 140

14.1.9 1:46:00 PM

Ⅳ 研究業績 (2012)

Fengyi LIU
Research Fellow, Fukui Kenichi Memorial Research Group 1
1. Summary of the research of the year
Reaction Mechanism of Spiropyran-Merocyanine Photochromic Reaction
The photochromic reaction of Spiropyran-Merocyanine(SP-MC) photochromic reaction has been a hot but
challenging subject for theoretical chemists. Due to the dramatic changes of electronic structure during thering-open and ring-closure processes and highly flexible geometry of MC isomers, the potential energy
surfaces of SP-MC are complex. The efficient nonadiabatic path from excited- to ground state, including
crucial structures such as conical intersections and unusual intersystem crossing, have not been wellunderstood.

Figure 1. Spiropyran-Merocyanine photochromic reaction path and unsubstituted MC(H-MC), 6-NO2
MC(NO2-MC) and protonated MC(MCOH+).

Multiple reaction path explored in H-SP Photochromic reaction:
In this project, we carried out high-level multireference CASSCF and CASPT2 calculations toinvestigate the reaction mechanism of the photochromic ring-opening process of a spiropyran (BIPS).
The possible excited-state C-O (and C-N) bond cleavage pathways and efficient nonadiabatic path fromexcited- to ground state have been revealed. (1) The C–O bond dissociation in SP does not follow a
conical-intersection mechanism that has been proposed in a model study with a simplified benzopyran. The
CASSCF-optimized crossing points are actually avoided crossings with large S1-S0 energy gap at the CASPT2
level; thus, they could not act as efficient S1-to-S0 funnels. (2) C–O bond cleavage paths on S1 leading to both the
CCC (with respect to the configuration around α, β, γ in Figure 2) and TCC intermediates of merocyanine (MC)are barrierless, in line with the experimentally observed ultrafast formation of MC.

－ 141 －

fukui2012_02.indb 141

14.1.9 1:46:01 PM

Ⅳ 研究業績 (2012)

Figure 2. The MS-CASPT2//CASSCF (solid curve and symbols) and CASSCF (dash line with hollow symbols)
S1-MEP’s for ring-opening reaction of: (a) S1-MEPc: FC-SPc→ CCC(S1) path; (b) S1-MEPt: FC-SPt →TCC(S1)path and (c) S1-MEPCN: FC-SP → CICN path.

A low-energy hydrogen-out-of-plane (HOOP) valley on the (πσ*) surface was located not far fromthe C–O bond cleavage path and was suggested to be an efficient S1-to-S0 nonadiabatic decay channel.
Triggered by the active HOOP mode, the molecule can easily access the S1-HOOP valley and then maketransition to S0 surface through the narrow S1-S0 gap that exists in an extended region. Nonadiabatic decay
through a conical intersection on C–N dissociation path as well as the HOOP funnel is responsible for highinternal conversion yields of SP.
These findings shedding light on the complex mechanism of SP-MC interconversion provide
fundamental information for design spiropyran-based photochromic devices.
H-SP Photochromic reaction: High Accuracy Refinement by Multiconfigurational DensityMatrix
Renormalization Group Approach
Many problems in photochemistry, e.g., the spectroscopy and ground- and excited-state reaction of large
conjugated systems, demand large multireference active space, which are always beyond the reach of
convertional complete active space correlation methods. Recently, the density matrix renormalization group(DMRG) method has been able to solve many problems with active spaces much larger than are possible－ 142 －

fukui2012_02.indb 142

14.1.9 1:46:09 PM

Ⅳ 研究業績 (2012)

with traditional active space techniques, and can obtain near-exact solutions.
In this study, we applied the DMRG methods to the reaction mechanism of HSP with large active space(22e-in-20o, the active orbitals include all π/π* orbitals and σ/σ* of C–O and C–N). The DMRG-CASSCF
and DMRG-CASPT2 energies are obtained on top of the reaction path optimized by conventional CASSCF
and (12e-in-10o) active space, to accurately evaluate the energies of photo excitation, dissociation path andnonadiabatic crossing region.
Table 1. DMRG-CASSCF & CASPT2 Energies of Key Structures.
DMRG-SA3-CASSCF DMRG-SS-CASPT2
Structures

S

0

S

S

1

2

S

0

S

S

1

2

S -SPcresultsatthe

DMRG-CASPT20

CAM-B3LYP

1.4

111.4

115.1

0.0 106.8

109.9

B3LYP

1.5

109.7

113.7

0.0 104.9

108.7

CASSCF(12e,10o)

1.5

112.3

115.4

2.0 109.6

112.8

DMRG-SS-CASSCF 0.0

108.9

112.8

0.8 106.5

110.5

Ref: MOLCAS

129.7

131.8

0.0 111.6

113.1

0.0

In general, it is found the calculation

0

and

level

good

are

in

agreement with the ones obtained with
(12e-in-10o) active space. The only evident
differences are seen at the Frank-Condon
region;the

DMRG-CASPT2

S -SPtDMRG-CASSCF

DMRG-CASSCF
decreasetheandrelative

CAM-B3LYP

2.5

112.2

116.4

0.3 105.8

111.6

energies of excited-state PES, suggesting

CASSCF(12e,10o)

2.6

113.2

116.7

2.2 109.0

113.8

inadequate

DMRG-SS-CASSCF 1.1

109.6

114.0

1.3 105.2

112.1

conventional CASSCF (12e-in-10o). While

Ref: MOLCAS

129.0

131.9

0.3 111.1

113.9

0.0

S /S CIs
1

0

size

of

activespaceby

the relative energies along the reaction path,e.g., at the three crucial MECIs (Table 1)

CI(TSc)

63.8

67.3

101.5 68.7 53.2

94.0

Ref: MOLCAS

66.0

67.3

102.0 45.2 68.8

99.4

CI(TSt)

63.2

64.0

107.6 57.1 60.6

98.5

confirming

Ref: MOLCAS

72.4

72.6

116.7 42.4 69.1

105.8

“truncated” active space. In addition, theCI(CN)

65.7

68.3

118.5 70.4 59.6

119.0

dynamic effects in the HSP reaction are

Ref: MOLCAS

70.2

68.7

141.6 72.2 60.6

143.6

significant, at both the conventional- andare very similar (at different approaches),thereasonability

of

our

DMRG approaches. The findings here supported the reaction mechanism proposed in our conventional
CASSCF/CASPT2 study.

Theoretical Study on the Deactivation Path of Fluorescence
From photophysical and photochemical textbooks, it is well known that in a unimolecular process, theexcess energy taken up by photo excitation can be dissipated either as emission (fluorescence for S1 S0)－ 143 －

fukui2012_02.indb 143

14.1.9 1:46:13 PM

Ⅳ 研究業績 (2012)or by radiationless transition. The rate of the radiationless transition depends not only on the energy gap(therefore if the potential energy surfaces (PES) of the corresponding states intersect or are very close to eachother, the probability of radiationless transition is high), but also on the equilibrium geometries of the states
involved (i.e., in rigid π systems, the ground state and first excited state differ so little that the PESs arenearly parallel, radiationless transition is less likely). These two processes, in many systems, compete witheach other and determining the fluorescent/nonfluorenscent feature of the excited molecule.
Theoretical calculation of such systems involving multiple potential energy surfaces (PESs) and seams
of intersection among the PESs are often complicate. Recently, the global reaction route mapping (GRRM)
method has successfully been applied to automatically explore multiple PESs and tested to be a powerfultool to discovery nonadiabatic pathways. In this study, we explored the radiationless deactivation pathway ofsome fluorescent compound by combining GRRM with spin-flipping density functional methods. The results
are useful in explaining experimental findings as well as designing new high-yield fluorescent materials.

Figure 3. A unfavorable S1-to-S0 radiationless path revealed at SF-B3LYP/6-31G* level.
.

2. Original papers(1) Fengyi LIU, Keiji MOROKUMA,“Multiple Pathways for Primary Step of Spiropyran Photochromic Reaction: A－ 144 －

fukui2012_02.indb 144

14.1.9 1:46:20 PM

Ⅳ 研究業績 (2012)

CASPT2//CASSCF Study”,
J. Am. Chem. Soc., submitted.
(2) Fengyi LIU, Keiji MOROKUMA," Density Matrix Renormalization Group Study on Spiropyran Photochromic reaction”
manuscript in preparation.

－ 145 －

fukui2012_02.indb 145

14.1.9 1:46:24 PM

Ⅳ 研究業績 (2012)

Hongyan XIAO
Research Fellow, Fukui Kenichi Memorial Research Group 1(To 30 Sep. 2012)

1. Summary of the research of the year
I. Theoretical Study on the Photodissociation of Methylamine Involving S1, T1, and S0 States
Methylamine (CH3NH2) is the simplest primary amine, which plays an important role in various fields
of chemical science. Because of its simplicity and importance, the structural and spectroscopic properties,
photodissociation dynamics and pathways have been widely investigated. Furthermore, the photodissociationof CH3NH2 might provide helpful insights and implications in understanding photoinduced processes ofvarious compounds containing amine moieties.
CH3NH2 →H + CH3NH(1)→

H + CH2NH2(2)→

CH3 + NH2(3)→

H2 + CH3N

(4)

3 -

→ CH4 + NH (X Σ ) (5)However, till now some questions remain: whether pathway (4) goes through a four-center transition
state, which form of the product (CHNH2, CH2NH, or CH3N) pathway (4) mainly gives, whether pathway (5)is a primary channel occurring on the triplet state, whether pathway (5) undergoes roaming-mediatedintersystem crossing, and so on. To answer these questions further theoretical evidences are needed.
Therefore we performed a systematic CASPT2 reaction path search on the three lowest electronic states (S1,
T1, and S0) by the global reaction route mapping (GRRM) strategy utilizing the anharmonic downward
distortion following (ADDF) and artificial force induced reaction (AFIR) methods.

On the basis of obtained structures, we discuss the photodissociation mechanism of methylamine in theexperimental excitation wavelength range of 222-240 nm in detail. Especially, the T1 potential energy surface
was explored systematically for the first time. The N-H bond rupture is a primary channel on the S1 state.
Along the N-H dissociation path on S1, there is a low-energy conical intersection (CI), and through this CI
the system can go back to the S0 state; from the CI the system can directly dissociate to CH3NH + H or

－ 146 －

fukui2012_02.indb 146

14.1.9 1:46:24 PM

Ⅳ 研究業績 (2012)

reproduce the original CH3NH2 on S0. There is a seam of crossing between S0 and T1 in a partiallydissociated CH3---NH2 geometry, and through this seam the system may go up to the T1. On the T1 state, aroaming-like pathway giving CH4 + NH (X3Σ-) products was found, which would explain the recently
proposed intersystem crossing mediated roaming dynamics. In addition, H2 elimination pathways, channel(4), on the S0 and T1 PESs were searched systematically. Three forms of CH3N, i.e., CHNH2, CH2NH, andCH3N, can be generated by H2 elimination on the T1 state via roaming-like pathways, although these paths
are expected to play a minor role due to high energy barriers. On the S0 state, there are two preferential paths
giving CH2NH + H2 and CHNH2 + H2 through stepwise and concerted mechanisms, respectively.

II. Theoretical Study on Organocatalyzed Isomerization of Alkynoate to Allenoate
Chiral allenes are interesting chiral building blocks in synthetic organic chemistry. The development of
the catalytic enantioselective synthesis of chiral allenes has received considerable attention in the field oforganic synthesis. Enantioselective isomerization of alkynoates is one of the most atom-economical ways toaccess this motif. In experiment Prof. Takemoto group reported the isomerization of α-nonsubstituent(System 1) and α-substituent (System 2) of alkynoates into allenoates using benzothiadiazine organocatalyst,
respectively. It was found that the reaction in System 1 is reversible, while the reaction in System 2 isirreversible; the isomerization from (R)-alkynoate to (S)-allenoate is a fast path. They proposed the reaction
mechanism as follows.

up to 96% ee
catalyst

System 1. Isomerization of alkynoate to allenoate.

cat.
up to 86% ee
System 2. Isomerization of α-substituted alkynoate to trisubstituted allenoate.

6

Me

slow

5
1

Me

Me

2
3
4

A(S)

C

E(R)

fast
Me
Me

Me

B(R)

D

F(S)

The proposed reaction mechanism by Prof. Takemoto and co-workers.

－ 147 －

fukui2012_02.indb 147

14.1.9 1:46:25 PM

Ⅳ 研究業績 (2012)

In this study we used the B3LYP/6-31G* method to investigate the mechanisms of organocatalyzed
isomerization of alkynoate to allenoate. We also considered the solvent effect using PCM model, where THF
is as a solvent. Here, we take System 2 as example to elucidate reaction mechanism. Beginning from the four
initial complexes (substitute and catalyst) below, four pathways were explored, see Figure 2.

4 3

6

5

6

5

2

1

anti-R-com

2

3

4

anti-S-com

syn-R-com

syn-S-com

Figure 1. Four initial complexes in System 2.
anti-S-TS* [66.5]
syn-R-TS* [56.3]
syn-S-TS* [51.1]

syn-R-TS2[72.9]
anti-S-TS2[65.0]
syn-S-TS2 [51.5]
anti-R-TS2[27.9]

anti-S-IM2 [62.0]
syn-S-IM2 [50.5]
syn-R-IM2 [36.9]

syn-R-IM1 [56.3]
syn-S-IM1 [41.4]
anti-S-IM1 [38.3]
anti-R-IM1[22.1]

85.5

111.9

React-S+cat.[0.2]
React-R+cat.[0.0]React-S*+cat.[0.0]React-R+cat.[0.0]85.6

syn-R-TS1[67.5]
syn-S-TS1[55.4]
anti-S-TS1[54.7]
anti-R-TS1[54.3]

syn-S-com[-26.0]
anti-S-com[-31.3]
anti-R-com[-31.3]
syn-R-com[-31.4]

Prod-R+cat.[-26.1]
Prod-S+cat.[-26.1]
Prod-S*+cat.[-30.5]
Prod-R*+cat.[-30.5]

B3LYP/6-31G*-PCM//B3LYP/6-31G*-PCM
Energy unit: kJ/mol; solvent: THF

The fast path is from (R)-alkynoate
to (S)-allenoate, irreversible.

Figure 2. The potential energy surface of alkynoate to allenoate in System 2.
The results show that the isomerization process includes two hydrogen-transfer steps and one
conformational change. The fast path from R-alkynoate (anti-R-com) to S-allenoate (prod-S + cat) only
involves two hydrogen-tranfer steps mediated by benzothiadiazine catalyst. As shown in Figure 2, the pathfrom IM1 to TS2 is very import, so we in detail analyse the structures, molecular orbital overlap integrals,
charge distributions of IM1 and TS, and do energy decoposition analysis from IM1 to TS2. Hydrogen bondinteractions between substrate and catalyst play an important role in the overall reaction. Using the similar
method, we also studied the isomerization process in Systme I. On the whole, our computational results arein agreement with the experimental observations, proposed the isomerization mechanism of alkynoate to－ 148 －

fukui2012_02.indb 148

14.1.9 1:46:27 PM

Ⅳ 研究業績 (2012)

allenoate mediated by benzothiadiazine from theory.

2. Original papers(1) Hongyan Xiao, Satoshi Maeda and Keiji Morokuma“Global ab initio potential energy surfaces for low-lying doublet states of NO3”
J. Chem. Theory Comput. 8, 2600-2605 (2012)(2) Bina Fu, Joel M. Bowman, Hongyan Xiao, Satoshi Maeda and Keiji Morokuma“Quasiclassical trajectory studies of the photodissociation dynamics of NO3 from the D0
and D1 potential energy surfaces”
J. Chem. Theory Comput. 9, 893-900 (2013)(3) Hongyan Xiao, Satoshi Maeda and Keiji Morokuma“CASPT2 study of photodissociation pathways of ketene”
J. Phys. Chem. A in press (DOI: 10.1021/jp312719a)(4) Hongyan Xiao, Satoshi Maeda and Keiji Morokuma“Theoretical study on the photodissociation of methylamine involving S1, T1, and S0 states”
Submitted.
(5) Hongyan Xiao, Satoshi Maeda and Keiji Morokuma“Theoretical study on the photodissociation mechanism of nitric acid involving S3, S2, S1and S0 states”
Manuscript in preparation.
(6) Hongyan Xiao, Satoshi Maeda and Keiji Morokuma“Theoretical study on catalytic enantioselective mechanism of Passerini reaction”
Manuscript in preparation.

－ 149 －

fukui2012_02.indb 149

14.1.9 1:46:29 PM

Ⅳ 研究業績 (2012)

Lina DING
Research Fellow, Fukui Kenichi Memorial Research Group 1
1. Summary of the research of the year
P1. Excited-State Proton Transfer Controls Irreversibility of Photoisomerizationin Mononuclear Ruthenium(II) Monoaquo Complexes: A DFT Study
Photo-induced or photo-triggered isomerization can utilize photonic energy for selective
bond-breaking and bond-making reactions. This type of reactions between two or more
optically and electronically distinct isomers or meta-stable species have been observed in a
broad variety of molecules, including stilbene and its derivatives, rhodopsins, and fluorescence
proteins, as well as transition metal complexes including photochromic ruthenium(II)polypyridine sulfoxide and polypyridyl mononuclear ruthenium(II) aquo (PMRA) and otherruthenium(II) complexes. Except for ruthenium polypyridine sulfoxide complexes,
mechanistic studies on PMRA are scarce. The importance of photoisomerization in PMRA liesin the fact that the two isomers have different potential catalytic abilities for water oxidation
into molecular oxygen, one of the key reactions involved in solar energy conversion.

Scheme 1. Photoisomerization of trans-[Ru(tpy)(pynp)(OH2)]2+ (TA) tocis-[Ru(tpy)(pynp)(OH2)]2+ (CA), with atom and group labels.

Recently, an irreversible photo-isomerization of trans-[Ru(tpy)(pynp) (OH2)]2+ (TA) tocis-[Ru(tpy)(pynp)(OH2)]2+(CA)complex(tpy=

2,2′:6′,2′′-terpyridine;

pynp

=

2-(2-pyridyl)-1,8-naphthyridine, Scheme 1) has been observed and characterized byexperimental techniques, such as such as X-ray crystallographic analysis, NMR spectroscopy
and cyclic voltammetry. Importantly, the redox and water oxidation reactions were reported tobe significantly controlled by the photoisomerization. Yagi proposed a mechanism for the－ 150 －

fukui2012_02.indb 150

14.1.9 1:46:29 PM

Ⅳ 研究業績 (2012)

photoisomerization: visible-light irradiation of TA can generate a metal-ligand charge-transfer(MLCT) state which is followed by a metal-centered (MC) states, on which an aquo ligand
could dissociate to form a five-coordinate [Ru(tpy)(pynp)]2+ intermediate, and then a watermolecule re-coordinates to the metal center of the intermediate from the opposite side of the tpy
plane to form the CA isomer. The proposed Ru–O bond cleavage involved in the water
dissociation was implicated by the observed activation energy of the photoisomerization (41.7
kJ mol-1), which is similar to that for the water exchange in ruthenium aquo complexes(50.6-87.8 kJ mol-1). However, it is still a puzzle why the isomerization is irreversible.
In this study, we explored the photo-induced non-adiabatic isomerization paths between
trans-[Ru(tpy)(pynp)(H2O)]2+ (TA) and cis-[Ru(tpy)(pynp)(H2O)]2+ (CA) on the lowest triplet
and singlet states by density functional theory (DFT) calculations. Several minimum energy
crossing points (MSX) were located and characterized to connect the two adiabatic potential
energy surfaces (PESs) for non-adiabatic pathways. Interestingly, excited-state proton transfer(ESPT) occurred only in the minimum of TMLCT-CA with a stronger Ru(II)-OH bond suppress thetransition to TMC-CA and, thus, the adiabatic triplet pathway from CA to TA. The findings of thepresent study should shed light on the working mechanism of the irreversible isomerization
processes of PMRA.

P2. sp3–sp2 vs sp3–sp3 C–C Activation in Rh-Catalyzed Ring Opening of
Benzocyclobutenol: A DFT Study
Transition metal catalysis has made significant and continual contributions to thedevelopment of synthetic organic chemistry, which has opened the wide synthetic
applications of non-polar and highly inert -bonds such as C–H bonds. The recent evolution
has rendered it possible to cleave C–C single bonds in a catalytic manner and utilize them inorganic synthesis. However, the available means to cleave C–C bonds are still in its infancy
and generally rely on substrate-specific strategies such as ring strain, aromatization, chelatingor coordinating assistance to induce C−C bond cleavage.
Murakami has reported that a rhodium catalyst induces ring opening of cyclobutanols.
The ring-opening process has been extended to various reactions to restructure carbon
frameworks. Very recently, ring opening of benzocyclobutenols with site-selective cleavage－ 151 －

fukui2012_02.indb 151

14.1.9 1:46:29 PM

Ⅳ 研究業績 (2012)of the Csp3–Csp2 (“proximal” bond) (Scheme 1) was reported. The site-selective Csp3–Csp2 ring
opening is complementary to the Csp3–Csp3 bond (“distal” bond) ring opening induced byheating, photo irradiation, and treatment with a base to furnish reactive o-quinodimethanes.
Experimentally, the site-selectivity is significantly influenced by the ligands on the Rh(I) andthe solvent. A proposed mechanism for the ring-opening of benzocyclobutenols is via protontransfer followed by -carbon elimination, as shown in Scheme 2.
Scheme 1. Ring opening of benzocyclobutenols

Scheme 2. Plausible mechanism

Further investigations on the mechanism are highly desired to understand these reactions
in detail. Up to now, mechanistic investigations on the carbon−carbon bond activation by thetransition metal are quite square. To clarify the factors that influence carbon−carbon bondcleavage could be helpful for deeper understanding of the general area of carbon−carbon
activation and may lead to new methodology for restructuring carbon frameworks.
Theoretical studies would be very profitable toward this goal. Mechanistic picture including
the potential energy surfaces, energetic and the nature of equilibrium structures is very
important to describe the nature of reaction pathways. Unfortunately theoretical studies on thefield of carbon−carbon activation have been limited to the C–CN bond and some special
substrate.
In the present work, we systematically investigated the mechanism of Rh-catalyzed ring

－ 152 －

fukui2012_02.indb 152

14.1.9 1:46:30 PM

Ⅳ 研究業績 (2012)

opening of benzocyclobutenol by a density functional theory. The catalytic cycle has beenfound to include three steps: deprotonation of benzocyclobutenol to form Rh(I) alkoxide, C–C
bond cleavage (-carbon elimination), and water dissociation to form the product and toregenerate active catalyst. The present results successfully depict the mechanism of thesite-selectivity and explain well its ligands-dependency and solvent influence, which should
be useful for designing new catalysts and improving site-selectivity. The mechanistic picture
described by the present computational study provides deeper insight into understanding of
C–C bond cleavage.

2. Original Papers
Lina Ding, Lung Wa, Chung, Keiji Morokuma*,Excited-State Proton Transfer Controls Irreversibility of Photoisomerization in
Mononuclear Ruthenium(II) Monoaquo Complexes: A DFT Study, submitted(2)
Lina Ding, Naoki Ishida, Masahiro Murakami, and Keiji Morokuma*,3
sp –sp2 vs sp3–sp3 C–C Activation in Rh-Catalyzed Ring Opening of Benzocyclobut-enol: A DFT Study, To be submitted(3)
Lina Ding, Lung Wa Chung, Keiji Morokuma“Reaction Mechanism of Photoinduced Decarboxylation of the Photoactivatable Green
Fluorescent Protein: An ONIOM(QM:MM) Study”, J. Phys. Chem. B, 2013, 117 (4),1075–1084.

(1)

3. Presentation at academic conferences(1)

Lina Ding, Lung Wa Chung, Keiji Morokuma“QM/MM study on the Photoinduced decarboxylation mechanism of PhotoactivableGreen Fluorescent Protein”
7th Congress of the International Society for Theoretical Chemical Physics (4PP-62),
Tokyo, Sep. 2-8. 2011(2)
Lina Ding, Lung-Wa Chung, Keiji Morokuma.
“Theoretical Study on the Photoisomerization of Mononuclear Ruthenium(II)Monoaquo Complex,”
福井謙一博士ノーベル賞受賞 30 周年記念 京都, 2012, Jan.01(3)
Lina Ding, Naoki Ishida, Masahiro Murakami, and Keiji Morokuma*,“Ligands and Solvent Effects on the Site-Selectivity of Rh-Catalyzed-Ring-Opening of
Benzocyclobutenol: A Computational Study,”
The 10th FIFC Symposium, 2012, Nov. 30.

－ 153 －

fukui2012_02.indb 153

14.1.9 1:46:30 PM

Ⅳ 研究業績 (2012)

Hai-Bei LI
Research Fellow, Fukui Kenichi Memorial Research Group 1
1. Summary of the Research of the Year(A) Temperature Dependence of Catalyst-Free Chirality-Controlled
Single-Walled Carbon Nanotube Growth from Organic Templates
Traditional CNT growth methods, such as carbon-arc, laser evaporation, and catalytic
chemical vapor deposition (CCVD) are incapable of in situ control of (n, m) chirality during
CNT synthesis, primarily due to the high temperatures employed. Recently proposed
bottom-up strategy based upon organic synthetic methods represents a more realistic approach
towards chirality-controlled SWCNT growth. We have recently revealed the potential role of theethynyl (C2H) radical in low-temperature templated SWCNT growth. In the current work, weinvestigate the role of temperature on chirality-controlled SWCNT growth from organic templates.
We have taken [6]CPP  (6,6)-SWCNT growth as a model system, and SWCNT growth was
induced by C2H radical addition to the [6]CPP template at the temperatures of 300, 500, and 800
K. Figure 1 depicts the hexagon addition distributions for growth at 300, 500 and 800 K,
respectively, following 245 ps. It is evident that SWCNT growth, as measured by hexagon
addition, at 300 K is noticeably slower compared to that at 500 and 800 K. In 90% of 300 K
trajectories between four and seven new hexagons were added. Conversely, hexagon addition
distributions at 500 and 800 K shift noticeably towards higher hexagon populations: the number oftrajectories with four new hexagons decreases sharply, while the number of trajectories with 8 ~10 new hexagons increases. On average, 5.8, and 6.8 and 6.7 hexagons are added during thisperiod at 300, 500 and 800 K, respectively. While the average growth rates at 500 and 800 K are
essentially equal, hexagon addition distributions at these temperatures differ significantly,
suggesting a difference in growth mechanism. At higher temperature, terminating polyyne chains
and their supporting hexagonal rings exhibit larger vibrational and torsional motion. This on the
one hand, could potentially promote ring formation; this is certainly what a comparison ofhexagon addition distributions between 300 and 500 K suggests. On the other hand, this canpotentially promote instability in the SWCNT structure itself, which in turn results in irregular
growth rates and more defect formation.

－ 154 －

fukui2012_02.indb 154

14.1.9 1:46:30 PM

Ⅳ 研究業績 (2012)

Figure 1. Hexagon addition distributions at 300K, 500K, and 800K.
We have calculated reaction rate constants for the hexagon and pentagon addition during[6]CPP(6,6)SWCNT growth as a function of temperature according to the well-known
transition state theory. Figure 2 shows that reaction rates for pentagon defect formation exceed
those for hexagon formation. The kinetic advantage that defect formation holds over hexagon
formation is greatest at lower temperatures – presumably this has ramifications for
low-temperature strategies for chirality-controlled growth. While pentagon defect formation ismore favorable than hexagon formation, the thermodynamic stability of the latter product issignificantly greater than that for pentagon defect formation. Hexagon and pentagon formation
during SWCNT growth are therefore competitive processes. Reaction rate constants of hexagon
and pentagon formation (Figure 2b) increase with increasing temperature, and this is consistent
with QM/MD results showing faster growth at higher temperatures. Figure 2 also indicates that,higher temperature results in more pentagon defect formation during growth, which is consistent
with trends observed in QM/MD simulations.

Figure 2. (a) Reactive potential energy surface for hexagon and pentagon addition to [6]CPP
precursor via C2H insertion, energies presented are at 300K. (b) Temperature dependence of－ 155 －

fukui2012_02.indb 155

14.1.9 1:46:31 PM

Ⅳ 研究業績 (2012)

reaction rate constants k for hexagon and pentagon.

(B) Revealing the Dual Role of Hydrogen for Growth Inhibition and DefectHealing in Polycyclic Aromatic Hydrocarbon Formation: QM/MD Simulations
There is increasing concern about the formation of polycyclic aromatic hydrocarbons (PAHs)
during the combustion and pyrolysis of hydrocarbons, due to their harmful environmental effects.
We have previously performed quantum mechanical molecular dynamics (QM/MD) simulationsof PAH formation from high-temperature benzene combustion, varying the H/C ratios between 0.8
and 0.2. In the current work, we report the dual role played by hydrogen atoms during PAH
growth via the combustion or pyrolysis of hydrocarbons. Very high hydrogen densities lead to theinhibition of PAH growth. On the other hand, high hydrogen densities facilitate defect healing in
the growing PAH fragments and promote hexagon formation. We present the evolution of thelargest PAH fragments observed using H/C ratios of 0.6, 0.4, and 0.2 in Figure 1. The effect ofhydrogen density on both the ring condensation of edge carbon chains and enhanced defecthealing in the PAH structure is immediate. For the case of trajectory T1 at H/C=0.6 (Figure 1(a)),
at 131.8 ps the PAH structure exhibits a one-to-one mix of hexagons and defects (8 hexagons and5/3 pentagons/heptagons); small polyacetylene- or polyyne chains and methyl groups are also
bound to the edge of the PAH. By 590 ps, all ring defects have been healed in the PAH structure,
which now exhibits a hexagon-only structure. Defect healing is driven by the diffusion ofhydrogen atoms on the plane of the PAH structure; this diffusion correlates with repeated C-Hbond formation and cleavage. This healing role of hydrogen is clearly visible in Figure 1(a) for thecase of pentagon-heptagon pair defects. Four hydrogen atoms are initially bonded to carbon atomsof the fused pentagon/heptagon pair, alternately with respect to the plane of the PAH (275.5 ps).
The diffusion of one of these hydrogen atoms then induces the cleavage of C-C bond common to
the heptagon and pentagon (275.6 ps). Consequently, this leads to the local reorganization of the
PAH and the formation of an additional hexagon within the following 0.3 ps. A CH2 edge defect isalso formed during this period. On the other hand, all edge carbon atoms are terminated by at least
one hydrogen atom, in some cases some edge carbon atoms are doubly or even triplyhydrogenated. This gives rise to edge C-C single bonds; defects at the periphery of PAH are－ 156 －

fukui2012_02.indb 156

14.1.9 1:46:31 PM

Ⅳ 研究業績 (2012)

therefore more easily reconstructed compared to double or triple bonds. At H/C=0.4, the situationis very similar to that at H/C=0.6; after approximately 590 ps, the PAH fragments are dominatedby hexagons, as depicted in Figure 1(b). Indeed, in trajectory T2 only one pentagon exists in thelargest PAH fragment (denoted by the arrow). It is interesting to note that most defect rings resideat the periphery of the PAH at H/C=0.6 and 0.4, whereupon there is a high possibility of them
being converted into hexagons with the assistance of terminating hydrogen.

Figure 1. The evolution of the largest fragment in representative PAH formation trajectories at
H/C ratios of (a) 0.6, (b) 0.4, and (c) 0.2.

－ 157 －

fukui2012_02.indb 157

14.1.9 1:46:31 PM

Ⅳ 研究業績 (2012)

2. Original papers(1) H. B. Li, A. J. Page, A. M. Mebel, S. Irle, and K. Morokuma, “SWCNT Growth from
Chiral Carbon Nanorings: Prediction of Chirality and Diameter Influence on Growth Rates”,
J. Am. Chem. Soc. 134, 15887, 2012.

(2) H. B. Li, A. J. Page, A. M. Mebel, S. Irle, and K. Morokuma, “Revealing the Dual Role of
Hydrogen for Growth Inhibition and Defect Healing in Polycyclic Aromatic Hydrocarbon
Formation: QM/MD Simulations”, under revision.

(3) H. B. Li, A. J. Page, S. Irle and K. Morokuma, “Temperature Dependence of Catalyst-Free
Chirality-Controlled Single-Walled Carbon Nanotube Growth from Organic Templates”, to besubmitted.

3. Presentations at Academic Conferences
H. Li, S. Irle and K. Morokuma, “Nucleation of Graphene on Ni(111) Surface with low
subsurface carbon concentration”, 10th FIFC Symposium, Kyoto, Japan ( Nov. 30, 2012)－ 158 －

fukui2012_02.indb 158

14.1.9 1:46:31 PM

Ⅳ 研究業績 (2012)

Lung Wa CHUNG
Research Fellow, Fukui Kenichi Memorial Research Group 1
1. Summary of the research of the year
1a. Reactivity of Hydrogen Atom Transfer (HAT) with Metal-Oxo and How Enzymes Facilitates theReaction. Heme- and non-heme oxygenases and oxidases catalyze many important and efficient biochemical
oxidations. Several transient species, such as ferryl-oxo, ferric-hydroperoxo, ferric-peroxy andferric-superoxo, have been proposed or found to act as oxidants. In comparison, the reported HAT reactivity
in enzymes (such as sMMO) is much higher than synthetic model Fe=O complexes. Previously, I
theoretically and systematically compare reactivity of several key ferric-superoxo and ferryl-oxo model
complexes. Reactivity was found to correlate well with thermodynamic driving force and can increase withhigher electrophilicity of the oxidant. In addition, reactivity of the ferric-superoxo oxidants generally is notstronger than the ferryl-oxo ones.

Figure 1.
To further understand why enzymes can catalyze HAT much faster than the synthetic model complexes, I
designed and performed more extensive calculations by including many synthetic model complexes andseveral important metal-oxo species in enzymes (Figure 1). Again, the HAT reactivity was found toqualitatively correlate with thermodynamic driving force and BDE(FeO-H). Also, I generalized two
mechanistic pathways (Fe(IV)-oxo or Fe(III)-oxy) for HAT in these metal complexes (Scheme 1). However,the computed HAT barrier for the important metal-oxo species in enzymes is similar to or even higher thansome of the reactive ferryl-oxo model complexes, which is seemingly not consistent with the observed
reactivity. Different from the model complexes, the substrate usually enters the active site of the enzymes
before formation of the high-valent reactive metal-oxo species (e.g. TauD in Scheme 2). Therefore, entropy
effect for the formation of a precursor complex in the enzymes should be minor, while that in the model－ 159 －

fukui2012_02.indb 159

14.1.9 1:46:32 PM

Ⅳ 研究業績 (2012)

complexes becomes important and thus the HAT reactivity is reduced. As a result, combination of thereactive ferryl-oxo model complexes with supra-molecule which stabilizes the formation of the precursor
complexes could enhance HAT reactivity. On the other hand, since HAT reactivity is known to qualitatively
correlate with thermodynamic driving force and BDE(FeO-H), I proposed a decomposition scheme tounderstand origin of the driving force in more details (Table 1), in which exchange interactions of Fe is also
found to play a role in the reactivity.
Scheme 1.

Scheme 2.

Table 1

－ 160 －

fukui2012_02.indb 160

14.1.9 1:46:32 PM

Ⅳ 研究業績 (2012)

1b. Chemiluminescence and Bioluminescence of Dioxetanones: Firefly emission is a well-known
efficient bioluminescence. However, mystery of the efficient thermal generation of electronic excited statesstill remains unclear. Previously, I performed SA2-CASSCF and CASPT2 calculations with acomputationally feasible active space (12,12) to uncover an adiabatic transition state followed by a seam ofsloped conical intersection in the gas phase (Scheme 3). Recently, Liu used a slightly larger active space(16,13) or (18,15), and six-state CASSCF averaging (DZ basis sets) based on the CAM-B3LYP IRC pathway.
They proposed an additional conical intersection during the O-O bond cleavage. Unfortunately, complicatedelectronic structures involved in the reaction requires a much larger active space, which can only be treatedby new methods (e.g. density matrix renormalization group method (DMRG)). We collaborated with Prof.
Yanai (IMS) for his efficient DMRG code. I performed DMRG-CASSCF and DMRG-CASPT2 calculations
with very large active spaces (e.g. (30,26)) and TZ basis sets. These very high-level results qualitatively
support my previous proposed mechanism, but not support a recent proposed mechanism the additional
conical intersection (partly due to a too small active space). Geometry optimization of the reaction path withnovel DMRG-CASSCF analytic gradient is in progress.
Scheme 3.

－ 161 －

fukui2012_02.indb 161

14.1.9 1:46:32 PM

Ⅳ 研究業績 (2012)

Figure 2.

2. Original papers(1) Chung, L. W.; Hirao, H.; Li, X.; Morokuma, K. “The ONIOM Method: Its Foundation andApplications to Metalloenzymes and Photobiology”, Wiley Interdisciplinary Reviews: Comput. Mol.
Sci. 2012, 2, 327.
(2) Ding, L.; Chung, L. W.; Morokuma, K. “Reaction Mechanism of Photoinduced Decarboxylation of
the Photoactivatable Green Fluorescent Protein: An ONIOM(QM:MM) Study” J. Phys. Chem. B
2013, 117, 1075.
(3) Ding, L.; Chung, L. W.; Morokuma, K.* “Excited-State Proton Transfer Controls Irreversibility of
Photoisomerization in Mononuclear Ruthenium(II) Monoaquo Complexes: A DFT Study”,
Revision.
(4) “Reaction Mechanisms of Diversified Reactions in Hydroxypropylphosphonic Acid Epoxidase(HppE): Effect of Conformations of the Substrates”, Manuscript in preparation.

3. Presentation at academic conferences(1) Xin Li, Lung Wa Chung, Keiji Morokuma "Primary Events of Photodynamics of All-transRetinal Protonated Schiff Base in Bacteriorhodopsin, Methanol Solution and Gas Phase",
JST International Symposium on Multi-scale Simulation of Condensed-phase Reacting
Systems, Nagoya, May, 10, 2012.

－ 162 －

fukui2012_02.indb 162

14.1.9 1:46:32 PM

Ⅳ 研究業績 (2012)

Galina PETROVA
Research Fellow, Fukui Kenichi Memorial Research Group 1
1. Summary of the research of the year
All the topics discussed in the current report are proposed by experimental groups interested in gaining better
understanding on the mechanism of catalyzed reactions from different spheres of asymmetric organic catalysis.
The available experimental data are not sufficient or ambiguous in order to define the complicated reaction cycles
and thus, theoretical modeling of the systems can provide essential information about the reaction mechanisms
and the nature of the enantio(stereo) selectivity allowing further modifications of the catalysts and theexperimental conditions. The last two subjects despite the relatively early stage of the theoretical studies are good
example of the advantages of using the AFIR approach for transition state search for systems with flexible
structures, more than one active center and potential assisting groups and species easily available in vicinity to thereaction center.
Theoretical modeling of stereochemistry control of copper catalysts based on the chirality of DNA
At the first stages of this investigation we have been concentrated on gaining information about the detailed
structure of the supramolecular catalyst consisting of DNA fragment, Cu(II)-based complex and the reacting
species [Sugiyama et al. Chem. Commun. 2012]. We have applied a combination of docking, MD, and QMMM
simulations being able at the last stage to define the difference in the stability of the possible complexes and thereasons for these differences. Comparing the available for the moment structures at QMMM level (e.g. Fig. 1), it
can be concluded that the stability of the reactant complexes depends on several factors: (i) deformation of the
DNA double strand at the intercalation of the metal complex and rearrangement of the water surrounding, (ii)deformation of the metal complex due to changes in its initially π-π stacked structure, and (iii) the stabilizing
effect of interaction between the DNA and the complex originating from both electrostatical and dispersion
interactions. The structure with highest binding energy is pro-S1 complex intercalated between 6-7 base pairs of
the DNA with reactant oriented towards the major groove of the DNA. The high BE of the structure, -60.7
kcal/mol, is a result of relatively low deformation of the DNA (compared with most of the other structures) andhigh interaction energy. Interestingly the reactant molecule preserved its local stacking and the structure is a goodcandidate for a transition state search. Next in stability with BE around -40 kcal/mol are pro-S2 from the 6-7
bp/MajG series and pro-S2 and pro-R2 from the 5-6 bp/MinG series and while in the pro-S2 the metal complex
deviates from its initial intramolecular stacking structures which results in quite high interaction energy, thepro-R2 structure from the 5-6 bp/MinG is characterized with deformational changes similar to those observed in
the most stable conformer, pro-S1 in 6-7 bp/MajG but with much lower energy of interaction. The performed
analysis also shows that intercalation of the metal complex in the 6-7 base pairs layer with the reactant moiety
located in the minor groove of the DNA strand is basically unfavorable as two of the conformers of the complex,
pro-S2 and pro-R1, induce severe deformation of the DNA strand while in the case of pro-S1 structure theinteraction energy is insufficient to compensate the energy lost due to deformation of the sub-systems.

－ 163 －

fukui2012_02.indb 163

14.1.9 1:46:33 PM

Ⅳ 研究業績 (2012)

Figure 1. Structure of the supramolecular Cu/DNA complexes in case of intercalation between base pairs 6-7 withreactant located in the minor (a) or major (b) groove.
In order to check the effect of the DNA on the reaction mechanism we modeled transition states for the C-C bondformation for 5-6 MinG structures and the results confirm the high catalytic effect of DNA, lowering the barriers
for this stage by ca. 10 kcal/mol for both pro-R and pro-S species compared to the reaction catalyzed by the Cu(II)in the absence of DNA. The energy barriers for the formation of S or R intermediates remain very similar and it isdifficult to distinguish which structure will prevail. On the other hand, calculations both with and without DNA
show that the next step of the process,the

H-transfer

complicatedstage,

and

is

more

more
energydemanding. In order to check thepossibilities for direct participation of
the DNA fragment in the reaction we
intend to use AFIR - a novel
theoretical approach for automatedsearch of transitions states [Maeda,
Ohno,

Morokuma,

Phys.

Chem.

Chem. Phys. 2013].
ACDC: Asymmetric counteranion
directed catalysis
Another interesting problem also
related to organic catalysis is theasymmetriccatalytic

counteranion

directed

Hosomi-Sakurai

reaction

Figure 2. First step of the reaction cycle of ACDC Hosomi-Sakurai
reaction obtained by AFIR (pre-C: pre-catalyst, K – ketene, B –allyltrimethyl silane which is also the second reactant in the
Hosomi-Sacurai reaction).

applying chiral disulfonamide catalyst [List et al. Angew. Chem. Int. Ed. 2013; Chem. Eur. J. 2012]. Except for
the reaction cycle itself and the experimentally predicted TMS group shifting, it is also interesting to understandthe mechanism of formation of the silylated form of the asymmetric catalyst. By this reason we applied AFIR for－ 164 －

fukui2012_02.indb 164

14.1.9 1:46:33 PM

Ⅳ 研究業績 (2012)

automatic search of transitions states for the interaction between the pre-catalyst in its H-form and the possible
silylating agents in the system – the catalyst activator silyl ketene acetal and one of the reactants in the
Hosomi-Sakurai reaction, allyltrimethylsilane (See Figure 2). The AFIR approach combined with randomorientation of the reacting species allowed us to locate TS structures deferring on the conformation and on thenature of the interaction. The H-transfer from N atom of the pre-catalyst to the CH2 group of the silylating agentsis the most favorable path in both cases and for the ketene structure this process is barrierless while for thereactant allyltrimethylsilane it would require ca. 20 kcal/mol. The last observation is in good agreement with theexperimental observations according to the reaction can proceed enantioslectively with only allyltrimethylsilane tosilylate the catalyst but is very slow.
PTC: Enentioselective base-free phase-transfer catalysis
The conformational interconversion between homo- and heterochiral forms of a asymmetric phase transfer
quaternary ammonium bromide catalysts have been studied [Maruoka, Tetrahedron 2006]. In agreement with theexperimental data, the homo-form of the catalyst which shows better catalytic performance is found by 3.4
kcal/mol less stable than the heteroform. The barrier for conversion is estimated to 16.8 kcal/mol. Simple docking
experiments followed by QMMM optimization of the predicted structures have shown that the differences in the
catalytic activity of the two species can not be explained only on their structural specifics. By this reason, we areworking on modeling the reaction mechanism via AFIR in attempt to understand the effect of the water necessary
for the reaction to proceed.

2. Original papers
Galina Petrova, Zhuofeng Ke, Keiji Morokuma, Theoretical modeling of DNA-based copper catalysts:
structure and performance in intramolecular Friedel-Crafts reaction. In preparation.

3. Presentation at academic conferences
Galina P. Petrova, Lung Wa Chung, Keiji Morokuma“DFT and ONIOM modeling of fosfomycin biosynthesis catalyzed by HppE” (Poster presentation)
XIVth International Congress of Quantum Chemistry, Boulder, Colorado, USA (June 25-30, 2012)
Galina Petrova, Zhuofeng Ke, Keiji Morokuma (FIFC)“Theoretical modeling of DNA-based copper catalysts performance in intramolecular Friedel-Crafts
reaction” (Poster presentation)
10th FIFC Symposium, Kyoto, Japan (November 30, 2012)－ 165 －

fukui2012_02.indb 165

14.1.9 1:46:33 PM

Ⅳ 研究業績 (2012)

Travis HARRIS
Research Fellow, Fukui Kenichi Memorial Research Group 1
1. Summary of the research of the year
I. QM/MM Structural and Spectroscopic Analysis of the Di-iron(II) and Di-iron(III)
Ferroxidase Site in M Ferritin
Ferritins are cage-like proteins composed of 24 subunits that take up iron(II) and store it as an iron(III)oxide mineral core. A critical step is the ferroxidase reaction, in which oxygen reacts with a di-iron(II) site toform μ-oxo/hydroxo-bridged di-iron(III) products:
2Fe2+ + O2 + H2O  [Fe(III)–O–Fe(III)] + H2O2
Recently, crystal structures of copper(II)- and iron(III)-bound frog M ferritin at 2.8 Å resolution (active
sites shown in Figure 1) provided an opportunity for theoretical modeling of the reactant state and products.
The moderate resolution, partial occupancy of ferroxidase sites, and use of Fe(II) analogues in ferritin crystal
structures precludes a detailed description of the positions, binding modes, and protonation states of proteinand water-derived ligands by crystallography alone; complementary spectroscopic and theoretical studies arenecessary to define the structures of the Fe(II), Fe(III), and intermediate states.
QM/MM calculations were carried out using B3LYP/Amber using single subunit models. The QM
layer included the side chains of Glu23, Glu58, His61, Glu103, Gln137, Asp140, and, in the
Fe(II)-containing models, His54. The Cβ-Cα bond was the QM-MM boundary for each of these residues.
Atoms beyond 9 Å from either Fe center were fixed. To identify the structure of the 2Fe(II)-boundferroxidase site, we examined a series of models (R1-R11) shown in Figure 1. We found that no single model
can be definitively described as having the experimentally determined one square pyramidal and one trigonal
bipyramidal site. The distorted geometries and, in some cases, weak metal-ligand interactions present
difficulties in assigning the environments. However, models R4 and R6-R8 clearly have two five-coordinate
iron centers, and are thus good candidates for the Fe(II)-bound state. These models have Fe-Fe distance of
4.95 Å, 4.48 Å, 4.63 Å, and 4.35 Å, respectively; thus, R6-R8 are most consistent with the crystallographic
distance of 4.3 ± 0.4 Å.
The CD/MCD spectra of the Fe(II)-bound state, taken at 1.7 K, show features at 5025 cm-1, 7600 cm-1,
9900 cm-1, and 11150 cm-1 (see Figure 2), attributed to two d-d transitions at each iron center.1 The calculated
spectra of four models, R1 and R6-R8, are also plotted in Figure 2. None of the calculated spectra have thecorrect signs for all three features, but this is not unexpected; incorrect signs were also obtained in a study ofanother di-iron enzyme, Δ9 desaturase, using the same computational method. Based on the relative energiesof all four transitions, the spectrum of R6 agrees best with the experiment. A constant shift of -1000 cm-1
would result in very good energetic agreement for R6, as each transition would be within 500 cm-1 of thecorresponding experimental transition. Similar corrections for systematic error have been applied previously
for TD-DFT-based CD calculations－ 166 －

fukui2012_02.indb 166

14.1.9 1:46:34 PM

Ⅳ 研究業績 (2012)

Figure 1. (top) QM/MM-optimized di-Fe(II) models
and initial crystallographic structure, including
metal-metal distances. Only the QM layer is shown.
Ligand field geometries are given for (FeA,FeB) as
follows: TB, trigonal bipyramidal; SP, squarepyramidal; DO, distorted octahedral; DT, distorted
tetrahedral; 4/5C, four or five coordinate.
Figure 2. (right) Calculated CD spectra for four
di-Fe(II) models compared to the 1.7 K experimental
spectrum and deconvolution.1 The right axis (rotatory
strength) corresponds to the line spectra.

－ 167 －

04-3 gyoseki_kenkyuin2.indd 167

14.1.9 2:10:08 PM

Ⅳ 研究業績 (2012)

The di-Fe(III) products of the ferroxidase reaction have a short Fe-Fe distance of 3.05 Å that suggests
the presence of a bridging oxo or hydroxo ligand obscured by the electron density of the iron centers. The
Fe-Fe distances and Mössbauer parameters provide the best link to experiment, enabling the di-Fe(III) site
(i.e., ferroxidase reaction products) to be identified. The experimental Mössbauer spectrum is broad, and thefitting analysis required at least four quadrupole doublets, indicating variable ligand environments of the
products. Optimizations of a series of models led to four groups of structures, which were categorized by thenature of the bridging ligand(s): (1) single μ-hydroxo, (2) single μ-oxo, (3) double μ-hydroxo, or (4) double
μ-oxo/hydroxo. Table 1 shows that our models with various bridging ligands have distinct sets of Mössbauer
parameters, with differences on the order of 0.05 mm/s in δ, and/or 1 mm/s in ΔEQ. By contrast, theadditional hydrogen bonds and changes in protonation state of the H2OB1 ligand due to the additional water inmodels denoted (2) cause only small perturbations of ~0.01 mm/s in δ and 0.3 mm/s or less in ΔEQ. Thus, theexperimental quadrupole doublets (Table 1, exp(1-4)) can be attributed to species with different bridging
ligands.
Table 1. Calculated and experimental Mössbauer parameters and Fe-Fe distances for di-Fe(III) products
model

Fe-Fe

δ(FeA)

δ(FeB)|ΔEQ(FeA)||ΔEQ(FeB)|

μ-OH−

3.50

0.50

0.50

0.43

1.12

2−

μ-O (1)

3.32

0.51

0.50

1.95

1.56

μ-O2−(2)

3.35

0.51

0.50

1.77

1.43

2μ-OH (1)

3.07

0.56

0.51

0.49

1.25

2μ-OH−(2)

3.05

0.56

0.52

0.23

0.97

2μ-O /OH (1)

2.88

0.54

0.47

1.25

1.23

2μ-O2−/OH−(2)

2.88

0.55

0.47

1.33

0.94

2.85

0.57

0.51

1.21

1.26

−

2−

−

−

2μ-OH /O
exp(1)a

0.48

1.95

a

0.55

1.63

exp(3)a

0.48

1.17

a

0.52

0.63

exp(2)
exp(4)

a2−

crystallography

3.1 ± 0.1

EXAFS

2.99–3.00b

1-4 in parentheses refer to the four quadrupole doublets used to fit the experimental spectrum. They are notassigned specifically to FeA or FeB. b2.99 and 3.00 Å were found using two independent samples.
Based on the Mössbauer parameters in Table 1, exp(1) is assigned to a single di-Fe(III) model,
μ-O2-(1), while exp(2-4) are assigned to individual iron centers of 2μ-O2-/OH-(2) and 2μ-OH-(1). The Fe-Fe
distances are 3.32, 3.07, and 2.88 Å for μ-O2-(1), 2μ-OH-(1), and 2μ-O2-/OH-(2), respectively, and theexperimental distances, 3.1 ± 0.1 Å (crystallography) and 2.99-3.00 Å (EXAFS), are in the middle of thisrange. The EXAFS results represent an average over the products, while in the crystal structure some of the－ 168 －

fukui2012_02.indb 168

14.1.9 1:46:35 PM

Ⅳ 研究業績 (2012)variation in Fe-Fe distances between subunits may be due to the various products.
In this work, we identified the most likely structure of the di-Fe(II) site, and three Fe(III) dimers thatare produced simultaneously in different subunits of ferritin. These structures will be the basis of future
mechanistic studies aimed at understanding biomineralization in ferritin. Currently, we are applying themethods used here to identify a spectroscopically consistent structure of the peroxo intermediate. With the
key structures in hand we will be in position to explore the pathway connecting the di-Fe(II) state to theperoxo intermediate, and the branching mechanisms that lead to the multiple products found in this work.

II. Density Matrix Renormalization Group Calculations of Magnetic Exchange Coupling in
Dinuclear Transition Metal Complexes
Theoretical calculations of exchange couplings are indispensable in the fields of molecular magnet andmetalloenzyme research. The most accurate methods that are typically employed include complete active
space second-order perturbation theory (CASPT2) and difference dedicated configuration interaction (DDCI),
but for larger systems and those containing metals with high spin moment (e.g., iron), it is common to resort
to density functional theory. A promising approach is to use the density matrix renormalization group(DMRG) method, which can treat larger active spaces than in conventional CASSCF calculations. The
antiferromagnetically coupled (S = 0) oxo-bridged [Fe2OCl6]2- anion was selected as a model system to test
the applicability of DMRG for calculating magnetic interactions.
The exchange coupling constant, J, of the Heisenberg spin-Hamiltonian H = -2JSASB can be
determined from the spin-ladder of the following form:
E(S) – E(S-1) = -2JS
The J value derived from the lowest spin states, S = 0 and 1 are the most appropriate for comparison to the-117 cm-1 experimental value determined from temperature-dependent magnetic susceptibility, as the higher
spin states are not significantly populated. Furthermore, deviations from this Heisenberg behavior can occur
for higher spin states of antiferromagnetically coupled systems.
Table 2. J values for [Fe2OCl6]2calculated with various methods
M

J/cm-1

methodact. space

CASSCF(16,13)

-58.6

MRCI

(16,13)

-96.3

DMRG

(16,16)

512

-58.0

DMRG

(10,20)

256

-49.0

DMRG

(16,26)

1000-116.8exp.

-117

DMRG-CASSCF J values presented in Table 1 were
calculated using a triple-zeta ANO-RCC basis set with various
active spaces and M, which is the number of renormalized states.
DMRG calculations approach the CASSCF limit for the employed
active space as M increases, but they also become morecomputationallydemanding.

For

comparison,conventional

CASSCF and multi-reference configuration interaction (MRCI)
calculations were performed using the smallest active space,(16,13). This active space consists of 16 e in 10 Fe(3d) and 3 O(2p)orbitals. DMRG allows inclusion of “double shells,” which are theO(3p) or Fe(4d) virtual orbitals that are important for correlation. The (16,16) active space adds the oxygen
double shell to (16,13), while (10,20) includes just the Fe(3d,4d). The largest active space, (16,26), is
composed of Fe(3d,4d) and O(2p,3p). DMRG calculations converge at lower M for smaller active spaces;－ 169 －

fukui2012_02.indb 169

14.1.9 1:46:35 PM

Ⅳ 研究業績 (2012)

thus, 256 and 512 for (10,20) and (16,16) are sufficiently converged. The J value for
DMRG-CASSCF(16,26) (-116.8 cm-1) accurately reproduces the experimental value, -117 cm-1, while theconventional CASSCF(16,13) result is -58.6 cm-1. MRCI(16,13) (-96.3 cm-1) approaches the experiment, but
it is still less accurate than the large active space DMRG calculation. Addition of either the O(3p) or Fe(4d)double-shell orbitals alone does not improve the result; they both must be included.
DMRG pushes the theoretical boundaries for the study of multi-reference systems, allowing
unprecedented accuracy in the case described here. In future work this method will be applied to othermolecular magnets and metal-containing systems of biological significance.

2. Original papers(1) Harris, T. V.; Morokuma, K.
“QM/MM Structural and Spectroscopic Analysis of the Di-iron(II) and Di-iron(III)
Ferroxidase Site in M Ferritin”
Inorg. Chem. Submitted (2013).
5. Others(1) Harris, T. V.; Morokuma, K.
“ONIOM Study of the Ferritin Ferroxidase Reaction” (Poster)
10th FIFC Symposium (2012).

－ 170 －

fukui2012_02.indb 170

14.1.9 1:46:36 PM

Ⅳ 研究業績 (2012)��� ��
研究員 (2013 年 3 月 1 日から)
ニトロメタンの光解離
ニトロメタンは最も単純なニトロ化合物であるが、その複雑な電子構造のため、紫外線照射により始まるその解離過程は単純ではない。
実験においては、これらの光解離の生成物として、CH3, NO2, HNO, NOH, CH2O, CH3NO,
CH3O, NO, OH があげられている。しかしこれらの生成物は、実験者により、検出されたか否の結果が異なり、明確な反応機構を含めた実験における一致点は、まず、C-N 結合の解離により CH3
および NO2 が生成されるということのみである。
理論計算に関して、これまで、基底状態の熱的解離については多くの研究がなされてきたが、励起状態についての研究はその解離極限における遷移状態の求めることが容易ではないことから、いまだその解離機構は部分的にしか知られていない。特に、このような、複雑な電子構造系に対し、異なる同一スピン励起状態への遷移が可能な、conical intersection また、異なるスピン状態への遷移が可能な seam of crossing の役割を明らかにすることは重要である。近年では Arenas
らにより、その励起状態を含めた解離 (CH3NO2 CH3 + NO2, CH3NO2 CH3NO + O ) について調べられているが、(a) 彼らは、分子対称性を Cs に制約しているため、実像とは多少異なると考えられる。
また近年、この系の基底状態においては非常に興味深い解離過程として、Homayoon らが、
Roaming 過程のある異性化反応を経由した、解離過程を半古典的動力学計算により示した。(b) 分子解離における Roaming 過程はいくつかの分子で検証されており、たとえば、H2CO では基底状
態 (e)、 NO3 においては励起状態で (f) みられることがこれまで立証されている。
私たちの研究の目的は、193nm (148.1kcal/mol)の紫外線照射により始まる光解離過程を
より詳細な記述とともにその解離機構を明らかにすることである。上記の Roaming 過程が励起状態において見られるかも検証する。

解離機構を示すには、多くの critical points、すなわち、平衡状態、遷移状態(一次の鞍点)、conical intersection, 及び seam of crossing を求め、それらの相関を intrinsic reaction coordinate (IRC) により明示することが必要である。

近年、Maeda,

Morokuma, Ono らは遷移状態 を核座標に対する、電子のエネルギーの一次、二次微分を大量に計算することにより、リストアップするアルゴリズムを提案した。(c) すなわち、ある大域、もしくは局所的な最小値を出発点とし、派生的に遷移状態、そのほかの最小値を探索する方法である。また、彼らは artificial な力を、もとのフラグメント間の力に加え、フラグメント A―フラグメント B(ここで、フラグメントは、分子、原子である。) の反応における、遷移状態を求める方法も提案している。(d) 前者については、まったく未知の dissociation channel を導出する場合、後者は、前者において限られた計算時間の中で、得られなかった状態を推測とともに得るために用いられる。
両者を、有効に応用することで、電子エネルギーにおいて有利な分子解離の反応経路を探る。
����(a) J. F. Arenas, J. C. Otero, D. Pelaez, J. Soto, J. Chem. Phys. 122, 084324 (2005).
(b) Z. Homayoon, J. M. Bowman,(c) S. Maeda, K. Ohno,

J. Phys. Chem. A, XXX, XXXX (XXXX).

J. Phys. Chem. A, 109, 5742 (2005).

(d) S. Maeda, K. Morokuma,

J. Chem. Phys, 132, 241102 (2010).

(e) D. Townsend, S. A. Lahankar, S. K. Lee, S. D. Chambreau, A. G. Suits, X. Zhang, J.

Rheinecker, L. B. Harding, J. M. Bowman, Science, 306, 1158 (2004).
(f) H. Xiao, S. Maeda, K. Morokuma,

J. Phys. Chem. Lett, 2, 934 (2011).

－ 171 －

fukui2012_02.indb 171

14.1.9 1:46:36 PM

Ⅳ 研究業績 (2012)

Shinichi

YAMABESPR Fellow, Fukui Kenichi Memorial Research Group 2
1. Summary of the research of the year(1-1) A DFT study on the isomerizationof aspartyl

peptides to iso-aspartyl

ones

The isomerization reaction of a tetra-peptide, Ac-Gly-Asp-Gly-Gly-NHMe ->Ac-Gly-isoAsp-Gly-Gly-NHMe, was investigated by DFT calculations.
Thirteen water molecules were added to the peptide for simulating proton transfers during theisomerization. As a staring analysis, the number (m) of water molecules participating in readyproton transfers was examined by the use of a small model system,
H3C.NH.C(=O).CH2.CH2.COOH and (H2O)m. The m=2 stepwise path found to be of thesmallest activation free energy.
On the basis of this result, the first isomerization path of thetetra-peptide was obtained with four elementary processes. The m=2 proton transfer isinvolved in them. A different proton transfer gives the second isomerization path with six
elementary processes. The second path (with ionization) is more likely than the first one(without ionization). Formation of the five membered rings of the aminosuccinimidyl-residue
and anionic tetrahedral intermediates enhances the encapsulation of H3O+ through the woundtetra-peptide ring. The role of the hydrogen bonds on the encapsulation was discussed in termsof the optimized geometries of proton-transfer transition states and intermediates.

－ 172 －

fukui2012_02.indb 172

14.1.9 1:46:37 PM

Ⅳ 研究業績 (2012)(1-2) A DFT study on the acid-catalyzed hydrolysis of sucrose to glucose and fructose
The acid-catalyzed hydrolysis of sucrose to glucose and fructose was investigated by DFT
calculations. Protonations to three etheroxygen atoms of the sucrosemolecule,A,B,and C,D),werecompared. Three(B, the fructosyl-ringoxygen protonation;, C that to the bridge oxygen of theglycosidic bond for the glucosyl-oxygen cleavage; and D,protonation to that for thefructosyl-oxygen cleavage) gave the fragmentation. Paths B, C, and D were examined by the useof the sucrose molecule and H3O+(H2O)13. The path B needs a large activation energy, indicatingthat it is unlikely. The fragmentation transition state(TS1) of path C needs almost the sameactivation energy as that of path D. The isomerization TS of Int(C)→Int(D), TS(C→D), was also
obtained as a bypass route. The present calculations showed that the path via the fructosyl-oxygen
cleavage(D) is slightly(not absolutely) more favorable than that via the glucosyl-oxygen
cleavage(C).

(1-3) Analysis of the reaction paths in the Bamberger rearrangement
A Bamberger rearrangement of N-phenylhydroxylamine, Ph.N(OH)H, to p-aminophenol wasinvestigated by DFT calculations for the first time.

There has been a significant question as to why in somecases, for example where the nucleophile

only the 4(para)-isomer product is formed fromis water,phenylhydroxylamine, whereas in other cases, e.g., when chloride ion is present, both 2- and 4-chloro
isomers areformed.

By the present calculations,seemingly established as an intermediate , waswater cluster around it.

the nitrenium ion, C6H5.NH+, suggested andfound to be absent owing to the high nucleophilicity of the

A reaction of the monoprotonated system, Ph.N(OH)H + H3O+(H2O)n (n = 4 and14) was examined. However, the rate-determining transition states involving proton transfers were calculated
to have much larger activation energies than the experimental one.
+system, Ph.N(OH)H + (H3O )2(H2O)13, was traced.
was obtained.

A newmechanism ofNetx, a reaction of the diprotonatedAn activation energy similar to the experimental one

the rearrangement including the aniline dication-like transition

state was proposed.

－ 173 －

fukui2012_02.indb 173

14.1.9 1:46:37 PM

Ⅳ 研究業績 (2012)2

Original Papers(1) "How is the anionic tetrahedral intermediate involved
Peptides to iso-aspartyl ones?

in the isomerization of aspartyl

A DFT study on the tetra-peptide",

Shinichi Yamabe, Wei Guan and Shigeyoshi Sakaki
Org. Biomol. Chem., 2012,10, 8007-8015(2) "Presence or absence of a novel charge-transfer complex in the base-catalyzedhydrolysis of N-ethylbenzamide or ethyl benzoate",
Shinichi Yamabe, Wei Guan and Shigeyoshi Sakaki,
Beilstein J. Org. Chem. 2013, 9, 185-196.
(3) "Three Competitive Transition States at the Glycosidic Bond of Sucrose in Its
Acid-Catalyzed Hydrolysis",
Shinichi Yamabe, Wei Guan and Shigeyoshi Sakaki
J. Org. Chem., 2013, 78 (6),2527-2533.

(4) "An aniline dication-like transition state in the Bamberger rearrangement",
Shinichi Yamabe, Guixiang Zeng, Wei Guan and Shigeyoshi Sakaki
Beilstein J. Org. Chem. 2013, 9, 1073-1082.

3.Presentation at academic conference“Mechanism of the Nozoe azulene reaction“(B10),
S. Yamabe, T.Machiguchi, T. Hasegawa, T. Minato, S. Yamazaki,
and S. Sakaki,
Sept. 19, 2012,
The 23-rd Symposium on Physical Organic Chemistry,at Kyoto－ 174 －

fukui2012_02.indb 174

14.1.9 1:46:38 PM

Ⅳ 研究業績 (2012)

�方�

FIFC フェロー�� 今年度の研究の��
今年度は配位高分子におけるプロトン伝導性に関する研究を行った。
䛆ጞ䜑䛻䛇㻌
多孔性配位高分子と呼ばれる物質群が近年注目を集めている。この物質群は、金属イオンと有機配位子からなる空孔を有した多孔性材料であり、そのガス吸着能、選択的吸着、光応答性、ゲスト
応答性、触媒、磁性など多岐にわたる機能が注目を集め研究が行われている。最近、このような配位高分子は輸送システムとしての応用も注目を集め始めた。特にプロトン伝導に関する研究は、電極材料などデバイスなどへの応用が期待され、この数年で活発に研究が展開されている。このような伝導性に関する研究では、用いる骨格やプロトンのキャリアとなる化学種の組み合わせなどの探求とその伝導性の測定が活発である一方で、そのメカニズム、特に伝導経路については多くの場合は未解明な部分が多い。その理由としては、X 線などの実験測定ではプロトンの位置決定や、そのダイナミクスを追跡することが困難なためと考えられる。そこで、本研究ではそのような化合物として、最近報告された配位高分子、{[Zn(HPO4)(H2PO4)]·2ImH2]}n (1)（ImH: イミダゾール）に注目した。錯体 1 中には 2 種類のイミダゾールが存在する。一方のイミダゾール（dynamic ImH2+）
は温度上昇に伴い回転運動が誘起されることが X 線および固体 NMR から確認されている。その回転運動の発現とプロトン伝導度の上昇が同期していることも確認されている。もう一方のイミダゾール（static ImH2+）ではこのような回転運動の誘起などは起きない。そこで本研究では、この二つのイミダゾールにおける挙動の違いの原因、プロトン伝導経路の解明、イミダゾールの回転と伝導との相関の解明を目的とした。
䛆ィ⟬䚸⤖ᯝ䚸⪃ᐹ䛇㻌
本研究では錯体 1 の無限骨格に対する検討および、無限骨格から切り出したモデル
構造における検討を行った。
無 限 骨 格 の 計 算 に はSIESTA プログラムを用い、汎関数として PBE、基底関数として DZP を用いて構造最適化を行った。最適化構造をもとに切り出した構造について Gaussian 09 を用い（図１）無限骨格における最適化構造と実験構造の比較て、同様に PBE 汎関数で検－ 175 －

fukui2012_02.indb 175

14.1.9 1:46:38 PM

Ⅳ 研究業績 (2012)

討を行った。基底関数は、Zn については LAN2DZ を用い内核電子は ECP で置き換え、O については 6-31+G*、その他の原子については 6-31G**を用いた。
図１に無限骨格の最適化構造と実験構造の比較を示す。リン酸と亜鉛からなる骨格を構成する一次元鎖については実験値と良い一致を示した一方で、末端の水素および、一次元鎖から伸びる末端リン酸については
実験 構造とのズ レが大きい 。これは、 水素結合 やdynamic ImH2+の運動の影響と考えられる。この構造をもとに、static ImH2+の回転障壁をモデル構造における計算から見積もった。得られたポテンシャルカー
ブを図２に示す。最適化構造から static ImH2+は二つ（図２）Static ImH2+の回転障壁の水素結合を形成しており、この二つの水素結合を切断するエネルギーが回転障壁（約 17kcal/mol）と考えられる。Dynamic ImH2+も二つの水素結合で捕捉されているが、水素結合を形成している酸素の電荷が static ImH2+の場合は-0.66 e であるのに対し、dynamic ImH2+では-0.60 e であった。
また、形成している水素結合の角度も 180 度から大きくずれており、この電荷の違いと水素結合角度の違いが運動性の違いを生み出していると考えられる。Static ImH2+と同様に Dynamic ImH2+の回転によるエネルギーの変化を確認したところ、その回転障壁は 22 kcal/mol であったが、いく
つかの局所安定構造が得られた。この事から、dynamic ImH2+では骨格の構造緩和が寄与していることが示唆された。
そこで、無限骨格において、dynamic ImH2+の回転させた状態から構造最適化を行った。その結果を図３に示す。図３に示すように、いくつかの局所安定構造が得られた。さらに、報告されている結晶構造とは異なる状態に最安定構造が存在している可能性が示唆された。この最安定構造からの回転角度
が 142 度（実験構造に近い角度）と 178 度の位置での構造を図４に示す。イミダゾールの回転に伴い、 （図３）無限骨格中における dynamic ImH2
イミダゾール上の H2 が O1 に接近すると、O1 とH1 の距離が 1.036 Å から 1.282の回転に伴うエネルギー変化

Å へと変化し、向かいのリン酸
上の酸素 O2 と H1 の距離が1.148 Å へと変化していることが明らかとなった。このことから dynamic ImH2+ の回転によってリン酸間のプロトン移動が誘起されることが明らかとなった。この次のステップとしては
dynamic ImH2+からリン酸への（図４）Dynamic ImH2+の回転に伴うプロトンの移動

プロトンの移動が考えられ、このプロセスに関する検討を現在進めている。

－ 176 －

fukui2012_02.indb 176

14.1.9 1:46:38 PM

Ⅳ 研究業績 (2012)

2. 論�(1) Masakazu Higuchi, Kohei Nakamura, Satoshi Horike, Yuh Hijikata, Nobuhiro
Yanai, Tomohiro Fukushima, Jungeun Kim, Kenichi Kato, Masaki Takata, Daisuke
Watanabe, Shinji Ohshima, and Susumu Kitagawa“Design of flexible Lewis acidic sites in porous coordination polymers byusing the viologen”
Angew. Chem. Int. Ed., 51, 8369-8372 (2012)(2) Maw Lin Foo, Satoshi Horike, Tomohiro Fukushima, Yuh Hijikata, Yoshiki Kubota,
Masaki“Ligand-based solid solution approach to stabilization of sulphonic acidgroups in porous”
Dalton Trans., 41, 13791-13794 (2012)(3) Munehiro Inukai, Satoshi Horike, Daiki Umeyama, Yuh Hijikata, and Susumu
Kitagawa“Investigation of post-grafted groups of a porous coordination polymer andits proton conduction behavior”
Dalton Trans., 41, 13261-13263 (2012)(4) Shin-ichiro Noro, Yuh Hijikata, Munehiro Inukai, Tomohiro Fukushima, Satoshi
Horike, Masakazu Higuchi, Susumu Kitagawa, Tomoyuki Akutagawa, and Takayoshi
Nakamura“Highly selective CO2 adsorption accompanied with low-energy regeneration
in a two-dimensional Cu(II) porous coordination polymer with inorganic
fluorinated PF6- anions”
Inorg. Chem., 52, 280-285 (2013)(5) Satoshi Horike, Masayuki Sugimoto, Kanokwan Kongpatpanich, Yuh Hijikata,
Munehiro Inukai, Daiki Umeyama, Shinji Kitao, Makoto Seto, and Susumu Kitagawa“Fe2+ layered porous coordination polymers and soft encapsulation of guest
via redox activity”
J. Mater. Chem. A, 1, 3675-3679 (2013)(6) Yuh Hijikata, Satoshi Horike, Masayuki Sugimoto, Munehiro Inukai, Tomohiro
Fukushima, and Susumu Kitagawa“Pore design of two-dimensional coordination polymers toward selective
adsorption”
Inorg. Chem., 52, 3634-3642 (2013)
3. 学会��
(1) 土方 優，榊 茂好「プロトン伝導性配位高分子の電子状態に関する理論的研究」
日本化学会第 93 春季年会 滋賀 2013/3/22-25－ 177 －

fukui2012_02.indb 177

14.1.9 1:46:39 PM

Ⅳ 研究業績 (2012)(2) 土方 優，榊 茂好「配位不飽和サイトにおける静電相互作用に関する理論的研究」
錯体化学会第 62 回討論会 富山 2012/9/21-23(3) 土方 優，榊 茂好「プロトン伝導性配位高分子の電子状態に関する理論的研究」
第 4 回協定講座シンポジウム「計算生物学と材料化学の融合」 兵庫

2012/12/19－ 178 －

fukui2012_02.indb 178

14.1.9 1:46:39 PM

Ⅳ 研究業績 (2012)

�� ��
特推研究フェロー
�� 今年度の研究の要�
本年度は遷移金属錯体に対する周期的結晶効果や溶媒和効果を中心に研究を行った。
【序論】

理論化学における重要な課題の１つに、溶媒や結晶といった周囲の環境からの影響を考慮して注目する分子の構造や電子状態を検討する事が挙げられる。特に近年、分子デバイスの開発に対する要請を背景に、結晶およびアモルファスなど固体中での電子励起や発光、スピン状態などの分子的性質が実験と理論の双方で研究対象として多くの興味を持たれている。特に、様々な分子性結晶の構造が X 線や中性子散乱実験によって明らかにされているものの気相中での孤立系計算による理論予測とは異なる事も多く、注目する分子に対する周囲の分子集団からの影響の考慮は必要不可欠である。
固体中に含まれる無数の分子を独立に扱い計算をする事は事実上不可能であるが、分子集団の周期的構造性を仮定する事による自由度の削減により計算可能なものとする。周期的分子性結晶を扱う際に有用な手法として、主に次の２つの理論的手法が挙げられる。１つは周期的密度汎関数理論であり、もう１つは QM/MM 法である。前者においては、注目する分子に周期的並進操作を施す事で無限サイズの結晶を直接計算する事ができ、特に注
目する分子とその周囲からの集団的な影響を等価な計算レベルで記述できる点が長所に挙げられる。しかしながら密度汎関数理論に基づくため、多参照性が求められる電子励起状
態などの記述において原理的に限界がある。一方、後者は周囲の分子集団を古典的モデル
によって記述する点において、注目する分子に掛る結晶効果の記述精度に限界があるが、注目する分子の励起状態に対して高精度な電子状態計算を適用する事が原理的に可能である点が長所として挙げられる。
本研究では周期的分子性結晶中での励起状態の理論化学研究を目標として、今回まずQM/MM 法の枠組みにおいて、結晶中における基本単位格子同士が全て等しい状態にある場合における結晶分子の構造および格子ベクトルの最適化法を開発した 1。この周期的分子性結晶の最適化方法を、水分子が O サイト向きで Pt 金属に配位した典型的な O 配向構造を持つ Pt(CN)4・2H2O 2 と、水分子が H サイト向きで Pt 金属へと水素結合した珍しい H
配向構造を持つ trans- PtCl2(NH3)(N-glycine)・H2O 3 という２つの水素結合性結晶系へ適－ 179 －

fukui2012_02.indb 179

14.1.9 1:46:39 PM

Ⅳ 研究業績 (2012)

用し（図１）、また孤立系計算で得られる最適化構造と比較する事で周囲の分子集団からの影響による分子構造と電子状態の違いについて検討した。

図１基本単位格子内の分子構造(a) Pt(CN)4・2H2O (C2 対称性)(b) trans-PtCl2(NH3)(N-glycine)・H2O (Ci 対称性)

【計算方法】 本研究における QM/MM 法は周期的分子性結晶の基本単位格子を QM 領域、あるいは基本単位格子内に対称性がある場合は対称操作を行う事で基本単位格子を再現できるような最小構成ユニットを QM 領域に選ぶ事とした。これは注目する QM 領域に対して並進および対称操作を行う事で周期的分子性結晶全体を再現できるからである。また
QM 領域以外の結晶部分を MM 領域と見做し、QM エネルギーEQM と QM/MM 相互作用
エネルギーEQM/MM の 1/2 の和（式(1)）を変分原理によって最小化するように、注目するQM 領域の電子波動関数ΦQM を決定する。

E crystal  E QM 11
E QM/MM   QM Hˆ gas  QM  E ES  E LJ 
2
2

式(1)

本研究は式(1)において QM/MM 相互作用を静電項と Lennard-Jones 項の和で表現し、特に静電項に含まれる MM 分子電荷に関しては QM 分子における電荷解析値と並進操作

Ttrans および対称操作 Tsym を介して等価になるように定めた（式(2)、(3)）。
 * (r )  (r )Z i 
qi
1  w(ra )  式(2)E ES   q a   P  dr  
w(ra )  ra  r aMMiQM ra  ri
iQM ra  ri  
q a  q a  qi     Qˆ i   Z i  n : Ttrans (a )  afor    : Tsym (i )  a 

式(3)ここで   (r ) は原子軌道関数、 P は一電子密度行列、 q a と qi は MM 分子サイト i およびQM 分子サイト a の有効電荷、 Q̂i は QM 分子サイト i における電荷演算子、 w(r ) は
Switching 関数。これにより変分原理を用いて式(1)を最小化する事で Fock 行列を導出した（式(4)）。

－ 180 －

fukui2012_02.indb 180

14.1.9 1:46:40 PM

Ⅳ 研究業績 (2012)

Fcrystal  Fgas Qi , * (r )  (r ) 1
1  w(ra ) qdrw(ra )  a  
2 aMM ra  r  iQM ra  ri




 * (r )  (r )Z i qi
1
1  w(ra )    Qa ,    P  dr w(ra )  
2 aMMra  r iQM ra  ri
iQM ra  ri  


式(4)

式(4)は第一項の孤立系での Fock 行列と残る周囲の分子集団からの一電子補正項により構成されるが、一電子補正項には無限周期からの長距離効果が含まれており、今回 Ewald
和により評価するようプログラム化した。更に解析的な gradient を導出する事で、MM 分子の経験的な分子内ポテンシャルを定める事なく分子構造と格子ベクトルおよび対称操作に関する最適化を行った 1。（Scheme）

Scheme : 周期的分子性結晶における電荷 Q、分子座標 r、格子と対称操作 t の決定
この基底状態下の結晶分子および格子の構造最適化法を B3PW91 汎関数による DFT レ
ベルで上記の Pt 錯体へ適用した。Pt は 60 個の内殻電子を Hay-Wadt ECP に置き換えて（11111/11111/111/1）基底を、その他の原子には 6-31++G**基底を用いた。Lennard-Jones
変数には AMBER および SPC モデルの値を用いた。

【結果】

テトラシアノ錯体、グリシン錯体での基本単位格子は４分子により構成されているものの、対称性を持つため独立な分子は、図１に示した 1、2 の２分子である。またテ
トラシアノ錯体の 1、2 間には水配位子の H サイトと CN 配位子の N サイトを介した水素結合が２つ、1、2’ 間には１つ存在し（図２）、グリシン錯体の分子間では水分子の H サイ
トとグリシンの COOH 基の O サイトおよび水分子の O サイトとグリシンの COOH 基の
H サイトを介した水素結合が存在する（図３）。孤立したテトラシアノ錯体の単量体では最適化構造は結晶構造中と一致するが、二量体、四量体では Ow(1A)-Hw 距離（図２）が伸び、プロトン移動性が現れる。一方、結晶を考慮した QM/MM 計算ではプロトン移動性は－ 181 －

fukui2012_02.indb 181

14.1.9 1:46:41 PM

Ⅳ 研究業績 (2012)

現れない。この点は周囲分子から掛かる静電ポテンシャルが水分子の Ow サイトから CN
配位子の N サイトへ向かうにつれ増大している点により、正電荷に誘起された Hw サイト
が受ける力が N→O 向きである事が理由であると分かった。また、孤立したグリシン錯体の単量体では水分子が Cl 配位子と NH3 配位子の間で水素結合を作り、結晶構造中と大きく異なる。二量体、四量体となるに従って結晶構造に近付くが、水分子の相対位置やPt(1)-Pt(1’) 距離は依然として結晶構造中とは異なる。
周囲の結晶分子を考慮した QM/MM 計算によって得られた最適化構造はこれら２つの錯体共に実験結果を再現し、構造最適化の定量性に関して Lennard-Jones 変数の大きさや
RESP 変数の使用に関する QM/MM 相互作用の評価方法に更なる議論と改善が必要なものの、QM/MM 法に基づき今回構築した計算方法は周期的分子結晶中での基底状態など、基本単位格子同士が全て等しい状態にある結晶環境についてのモデル化に有用であると考えられる。

図２：テトラシアノ錯体 (a) 基本セル内 (b) 基本セル間水素結合

図３：グリシン錯体 (a) 水分子の相対位置 (b) 分子間水素結合[1] : S. Aono, S. Sakaki, Chem. Phys. Lett. 2012, 544, 77[2] : C. Mühle, J. Nuss, M. Jansen, Z. Kristallogr. New Cryst, Struct. 2009, 224, 9.
[3] : S. Rizzato, J. Berges, S. A. Mason, A. Albinati, J Kozelka, Angew. Chem. 2010, 49, 7443.

－ 182 －

fukui2012_02.indb 182

14.1.9 1:46:41 PM

Ⅳ 研究業績 (2012)

2. 論�(1) Shinji Aono, Takashi Hosoya, and Shigeyoshi Sakaki, “A 3D-RISM-SCF methodwith dual solvent boxes for a highly polarized system: application to
1,6-anhydrosugar formation reaction of phenyl alpha- and beta-D-glucosides
under basic conditions” Phys. Chem. Chem. Phys. 17 6368 (2013)(2) Shinji Aono and Shigeyoshi Sakaki, “Evaluation Procedure of Electrostatic
Potential in 3D-RISM-SCF Method and Its Application to Hydrolyses of Cis- andTransplatin Complexes” J. Phys. Chem. B 116 13045 (2012)(3) Shinji Aono and Shigeyoshi Sakaki, “Proposal of new QM/MM approach forgeometry optimization of periodic molecular crystal: Self-consistent point
charge representation for crystalline effect on target QM molecule” Chem.
Phys. Lett. 544 77 (2012).
3. 学会発�(1) 青野信治、榊茂好「周期的分子性結晶に対するQM/MM法の開発：SCF点電荷による結晶効果のモデル化」
分子科学討論会2012 東京 2012/9/19 2E04
4. �の�
(1) 青野信治、細谷隆史、榊茂好「塩基性条件下におけるグルコシドからのレボグルコサン生成機構：α体とβ体の反応性の相違に関する 3D-RISM-SCF法による理論的研究」
京都大学福井謙一記念研究センターシンポジウム2012 京都 2012/11/30 P53－ 183 －

fukui2012_02.indb 183

14.1.9 1:46:41 PM

Ⅳ 研究業績 (2012)

�本��

特推研究フェロー
�� �年�の研究の��五配位 Ni(II)錯体の結晶中でのスピンクロスオーバー現象の理論的考�【������】遷移金属錯体の結晶中でのスピンクロスオーバー現象は、工業的な応用が期 待 さ れ る 。 近 年 、 五 配 位 Ni(II) ス ピ ン ク ロ ス オ ー バ ー (SCO) 錯 体
TpPh,MeNi(S2CNMe2)[TpPh,Me=hydrotris(3-phenyl-5methyl-1-pyrazolyl)borate]が、結晶中で二つの独立な構造 Ni1, Ni2 を持ち (Scheme1, Fig1)、磁気的性質が異なることが、X 線構造と磁化率の測定によって明らかにされた 1。Ni1 の構造は 123K と 293K で大きな違いがないが、Ni2 では 123K と 293K で構造が大きく異なる。このことは SCO が Ni1 で起こ
らず、Ni2 で起きていることを示している。
本研究では、単量体の構造と電子状態、及び結晶化の影響を考慮した場合の違いを電子状態計算から議論し、分子性結晶中のスピンクロスオーバー現象の理由を説明した。

Ni2

Ni1

Ni2

Ni1

Fig.1 X-ray structure of TpPh,MeNi(S2CNMe2) in 123K

Scheme 1 TpPh,MeNi(S2CNMe2)【計算方�】単量体の構造最適化を行い X 線構造と比較した。Ph, Me を H 原子に置換したモデル錯体で電子状態と一重項、三重項の相対安定性を議論した。結晶の効果を取り入れるため、周囲の置換基の一部を考慮したモデルで、置換基の位置を X 線構造で固定した構造最適化 Embedded model と QM/MM 計算を行った。ここで MM の電荷は QM と MMの電荷が等しくなるように決定し、QM/MM 間の相互作用はレナードジョーンズポテンシ
ャルで記述した。基底関数は BSI (Ni: SDD ECP plus 2f polarization functions, C, H, N, B,
S: 6-31G(d)), BSII (Ni: C, H, N, B, S: cc-pVDZ) を用い、構造最適化は B3PW91/BSI, 相対エネルギーは B3LYP*/BSII で計算した。結晶の a,b,c 軸方向の影響は X 線構造から構築したクラスターモデルで評価した。結晶の a,b,c 軸方向の分子間力は金属の電子状態を S=0に固定し、B97XD で評価した。
[結果と考�] 単量体の最適化構造から Ni1 は 123K, 293K ともに triplet 構造、Ni2 は123K で singlet, 293K で triplet 構造に対応している(Table 1)。このことから SCO は Ni1
で起こらず、Ni2 で起きていることを示している。しかし、Ni2 の 123K の実験構造と単量体の最適化構造の一致は悪い。Embedded model と QM/MM を導入すると Ni2 の最適化構造が改善され(0.25 から 0.05, 0,04)、結晶の影響が Ni2 で大きい。一方で Ni1 は単量体、embedded model, QM/MM で標準誤差に大きな違いがなく且つ値も小さいので、結晶化の影響が小さい。

－ 184 －

fukui2012_02.indb 184

14.1.9 1:46:42 PM

Ⅳ 研究業績 (2012)

Table 1. TpPh,MeNi(S2CNMe2)の最安定化構造
Ni1

embedded

T (K)

QM/MM

expl.

embedded

123K

QM/MM

expl.

isolated

293K

multiplicity

tripletHStripletHSsinglettripletNi-N1 (Å)

2.027

2.095

2.038

2.035

2.111

2.048

2.927

2.069

Ni-N3 (Å)

2.123

2.160

2.111

2.119

2.151

2.111

1.929

2.128

Ni-N5 (Å)

2.074

2.003

2.048

2.071

2.005

2.058

1.913

2.063

Ni-S2 (Å)

2.379

2.366

2.342

2.381

2.374

2.344

2.219

2.379

Ni-S1 (Å)

2.448

2.419

2.401

2.447

2.421

2.393

2.227

2.436

RMS

0.03

0.04

0.03

0.04

Ni2

embedded

QM/MM

embedded

QM/MM

expl.

isolated

multiplicity

singletLS

tripletHS

Ni-N1 (Å)

2.478

2.386

2.401

2.050

2.170

Ni-N3 (Å)

1.934

2.025

1.972

2.138

Ni-N5 (Å)

1.945

1.953

2.003

Ni-S2 (Å)

2.249

2.302

Ni-S1 (Å)

2.234

2.292

RMS

0.05

0.04

expl.

singlettriplet

2.149

2.927

2.069

2.031

2.046

1.929

2.128

2.055

2.090

2.083

1.913

2.063

2.272

2.387

2.425

2.361

2.219

2.379

2.257

2.451

2.367

2.323

2.227

2.436

0.07

0.04

0.25

0.03

Table 2. HS-LS 相対安定性E(HS-LS)の a,b,c 軸方向依存
Packing direction

123K

293K

Ni1-Ni2

15.9

-4.1

c

20.6

-3.0

a two blocks

15.3

-5.4

a three blocks

15.1

-5.8

b

15.9

-4.6

次に a, b, c 方向の影響を調べるため X 線構造から構築したモデルクラスターで HS-LS 相
対安定性と分子間相互作用を調べた。結晶構造から一つの単位格子の中に Ni1-Ni2 二量体が存在するので、この二量体を最小単位として a,b,c 方向に伸長したモデルで評価した。
123K では Ni1-Ni2 二量体は LS が安定で、293K では HS が安定と計算され、実験の傾向を再現した、c 方向では 123K でE(HS-LS)の値に変化が見られたが、a,b 方向では
E(HS-LS) の 値 に 変 化 が ほ と ん ど な い (Table 2) 。 こ の こ と か ら c 方 向 の 影 響 がE(HS-LS)の値に大きな影響を与えることが分かった。分子間力の a, b, c 方向の影響を調
べると、a,b 方向依存性より Ni1-Ni2 二量化と c 方向依存性が大きい (Table 3)。以上の結果から、Ni1-Ni2 の c 方向の二量化が Ni2 の相対安定性に影響を与えることが示唆された。

－ 185 －

fukui2012_02.indb 185

14.1.9 1:46:43 PM

Ⅳ 研究業績 (2012)

Table 3.分子間力の a,b,c 軸方向依存
Packing direction

123K

293K

E(real)

LS

HS

LS

HS

a







b







c







Ni1-Ni2







ここで、錯体の Ph, Me 基を H 原子に置き換えたモデル錯体で singlet と triplet の電子状態と構造を調べた。Singlet の HOMO は Ni dz2-Nax lone pair の反結合性軌道で LUMO
は Ni dxy –Neq lone pair の反結合性軌道である (Fig.2)。一方、triplet ではこれらの軌道が SOMO である。最適化構造を比較すると、Singlet の最適化構造は triplet 構造より
Ni-S, Ni-Neq 距離が短く、Ni-Nax 距離が長い (Fig.2)。singlet と triplet の構造の違いは電子状態を反映している。singlet の Ni-Nax 距離が長い理由は二重占有の dz2-Nax lonepair anti-bonding orbital に由来し、triplet では dz2-Nax lone pair と dxy –Neq lone pairが SOMO になることで、Ni-Nax 距離が短く Ni-S, Ni-Neq 距離が長い。
zyxdz2(HOMO)
dxy(LUMO)
spin density of triplet
Fig.2 singlet の HOMO と LUMO. Triplet の�����

SinglettripletFig.3 モデル錯体の最適化構造
モデル錯体及びリアル錯体でE(HS-LS)を評価すると、triplet が singlet より安定である
ため、結晶化により Ni2 は 123K で singlet が安定になっていると言える。実際、123K ではE(HS-LS)は singlet が安定、LS 構造では分子間力が大きい(Table 2, 3)。この理由はsinglet と triplet の分子構造の違いと結晶中での分子の配向に由来している。123K と 293Kの単位格子を比較すると結晶群は共に P 1 で、293K の単位格子は 123K の単位格子より
a,b,c 方向にそれぞれ 0.14, 0.13, 0.38Å 長い。c 方向の単位格子の伸長が大きいことと(Table2)、c 方向のE(HS-LS)と分子間力が大きいことから(Table3)、c 方向に影響する分子に着目すると、Ni1 と Ni2 の二量体が c 軸方向に整列していることが見て取れる (Fig.1)。

－ 186 －

fukui2012_02.indb 186

14.1.9 1:46:43 PM

Ⅳ 研究業績 (2012)

Ni1 の Ni-S 分子面は a 軸方向、Ni2 の分子面は c 軸方向を向いている。モデル錯体で見た通り、singlet は Ni-Neq, Ni-S 距離が短く、triplet は逆に長い。そのため 123K では Ni2
が singlet 構造を取る方が c 軸方向の Ni1-Ni2 二量体が空間的に小さく立体反発を避けることが出来るため二量化エネルギーが大きい(Table 3)。結晶化による構造変化も 123K での Ni2 の相対安定性に重要である。最適化構造を用いるとE(HS-LS) は8.3 kcal/mol でtriplet が安定であるが、X 線構造を用いるとE(HS-LS)は 5.7 kcal/mol で singlet が安定であり、実験結果を支持する。以上の結果から、Ni2 が 123K で singlet を取る理由は、1.
Ni-Neq, Ni-S 距離が短く c 軸方向の Ni1-Ni2 二量化エネルギーが大きくなるため 2. 結晶化による構造変化により singlet が有利になるため、と結論付けられる。123K  293K でNi2 が singlettriplet へ SCO を起こす理由は、振動エントロピーで説明出来る。Tripletの振動エントロピーは singlet より大きいため、ギブスの自由エネルギーを考慮すると、高温で triplet の自由エネルギーが安定になる。
䛆ᩥ⊩䛇㻌 㻝㻕 Huaibo M. et al. JACS, 2011, 133, 5644.

2. 論�(1) “A theoretical study of luminescent vapochromic compounds including an AuCu2(NHC)2core” S. Tsukamoto and S. Sakaki, Dalton Trans. 2013, 42, 4809.
3. 学会発�(1) 塚本 晋也、榊 茂好「Au(I)-Cu(I)相互作用を含む多核金属錯体の発光メカニズ
ムと金属間相互作用」第15回理論化学討論会 仙台福祉プラザ
2012/5/24(木)-26(土）ポスター 1P07
(2) Shinya Tsukamoto、Shigeyoshi Sakaki「A Theoretical Study for Solid-state Spincrossoverr of Ni(II) in N3S2 ligand field」14th ICQC Interactional Congressof Quantum Chemistry, Boulder, Colorado, USA, June 25-30, Poster IV.48(3) 塚本 晋也、榊 茂好「五配位 Ni(II)-N3S2 錯体の理論研究:スピン状態と結晶構造の関連」第 6 回分子科学討論会 東京 2012/9/18(火)-21(金) ポスター 2P-095(4) 塚本 晋也、榊 茂好 「五配位 Ni(II)錯体の結晶中でのスピンクロスオーバー現象の理論的考察: A Theoretical study of Spin Cross Over (SCO) in solid stateof five coordinated Ni(II) Complex - the reason of SCO in solid state」錯
体化学会第 62 回討論会 富山大学 五福キャンパス 2012/9/21(金)-23 日(日) 口
頭 2Ba-05
4. その�
(1) 「五配位 d8 Ni(II) 錯体 の構造と電子状態及び結晶中でのスピンクロスオーバ
ーについての理論的考察: A Theoretical study of geometry and electronic－ 187 －

fukui2012_02.indb 187

14.1.9 1:46:44 PM

Ⅳ 研究業績 (2012)

structure of Spin Cross Over (SCO) in solid state of five coordinated Ni(II)Complex」福井謙一京都大学第9回京都大学福井謙一記念研究センターシンポジウム
京都 2012/3/16－ 188 －

fukui2012_02.indb 188

14.1.9 1:46:44 PM

Ⅳ 研究業績 (2012)

Milind Madhusudan DESHMUKHSPR Fellow, Fukui Kenichi Memorial Research Group 2
1. Summary of the research carried out during April 2012 to March 2013.
A) Absorption of Gas Molecules into the Porous Coordination Polymer:
Understanding of the Determining Factors for Absorption position and Energy
We recently proposed a two step evaluation method for evaluation of binding energy(BE) of van der Waals complex/cluster through reasonable approximations (Deshmukh
M. M. and Sakaki S. J. Comput. Chem.2012, 33, 617). This approximation was shown to
be useful for number of systems. This developed strategy was extremely useful in of ourstudy of absorption/adsorption of CO2 and CS2 into porous coordination polymers (PCPs).
PCPs recently attract much attention to the potential application to gas storage, gas
separation, and catalysis and these desired properties were well investigated in past.
Recently, optical and magnetic properties and their responses to inclusion of a guest
molecule have started to draw new attention in the chemistry of PCP. Recently thechemo-responsive switching of spin-state was recently shown to occur by gas absorption
in the Hofmann-type three-dimensional PCP {FeII(Pz)[PtII(CN)4]}n (Pz=pyrazine). For
instance, the absorption of such bulky molecules as benzene, pyrazine, water, methanoletc. stabilizes the high spin state; note that though water and methanol are not bulky, they
forms bulky cluster in PCP. Of particular interest is the absorption of CS2 molecule;despite of its small size, CS2 absorption induces the spin transition from the high-spin to
the low-spin state. This is the reverse to the spin transition by bulky molecules. On theother hand, the absorption of similar CO2 does not induce any spin transition.
In this work, we theoretically investigated the interactions of CS2 and CO2 moleculeswith a realistic model (RM) consisting of a unit cell of the Hofmann-type PCP{Fe(Pz)[Pt(CN)4]}n as shown in Figure 1.

Figure 1: Realistic model (RM) of CS2-absorbed PCP; Fe (green), Pt (pink), N (blue), C(gray), and S (yellow).
The purposes of the present work are to find the binding sites of these gases in the
Hofmann-type PCP, to evaluate their BE, and to clarify the determining factors forabsorption site and absorption energies of these gases with the PCP. We believe that theknowledge of such determining factors is indispensible to understanding the gas
1－ 189 －

fukui2012_02.indb 189

14.1.9 1:46:45 PM

Ⅳ 研究業績 (2012)absorption with PCP and finding a gas molecule which induces the spin transition
between high and low spin states.
The BE of gas molecule with was evaluated with ONIOM scheme, as shown in Eq. 1.
High
High
Low
Low
(1)
BE ONIOM BE Low
RM
RM  BESM1  BESM1  BESM 2  BESM 2



 



where superscripts “High” and “Low” represents the high quality calculation and low
quality calculation, respectively and subscripts, “RM”, “SM1”, and “SM2” represents
realistic model, small model 1 and small model 2 (cf. Figure 2).

Figure 2: Small models (a) SM1 and (b) SM2 representing the Pz and Pt interaction
sites respectively. These models were used in ONIOM calculations.
The first term on the right hand side of Eq. 1 is BE of gas molecule with realistic
model, RM. This is a “real low” component of the ONIOM equation. The second term
represents, BE of gas molecule with small model SM1 and the third term represent BEwith small model SM2. The M06-2X level of theory was employed with cc-pVTZ basis
sets for low quality calculation and scaled MP2 methods21 were used with aug-cc-pVTZ
basis sets for high quality calculation. The calculated potential energy surfaces (PES) forCS2 and CO2 absorption in Hofmann-type PCP, are shown in Figure 3(a) CS2 absorption(b) CO2 absorption

Figure 3: Potential energy surface for absorption of (a) CS2 and (b) CO2 into PCP.
As seen in Figure 3, BE of CS2 and CO2 are evaluated to be -17.3 kcal mol-1 and -4.0 kcal
mol-1, respectively at the ONIOM(MP2.5:M06-2X) level, indicating that CS2 strongly
absorbs in PCP but CO2 weakly. The absorption positions of these molecules arecompletely different between CO2 and CS2; CO2 molecule exists between two Pt sites. To
the contrary, one S atom of CS2 exists between two Pz ligands and the other S atom is
between two Pt sites. The optimized position of CS2 agrees with experimentally reported
2－ 190 －

fukui2012_02.indb 190

14.1.9 1:46:45 PM

Ⅳ 研究業績 (2012)

X-ray structure. Based on energy decomposition analysis and electrostatic potential of the
PCP framework, it is concluded that both of the large binding energy and absorption
position of CS2 arise from large dispersion interaction between CS2 and Pz. The different
absorption position of CO2 arises from large electrostatic interactions between CO2 and Pt
site, and small binding energy of CO2 comes from weak dispersion interaction with bothPz and Pt site.
B) Theoretical study of Molecular Hydrogen and Carbon Dioxide Functionalization
with Zinc Hydride: Insights into Interesting Catalytic Cycle
The discovery of catalytic methods is important for (i) the rapid generation of H2 asuse a fuel source and (ii) utilization of CO2 as an effective C-source. Transition metal
complexes are shown by number of studies that they can act as effective catalyst forvariety of conversion of chemical entities into desired products. Recent experimental
study reported that [tris(2-pyridylthio)methyl] zinc hydride 1 is an effective catalyst forH2 generation from methanol or water and for CO2 utilization (J. Am. Chem. Soc. 2011,
133, 9708). However, no detailed mechanistic insights have been presented.
In this work, we theoretically investigated the reaction mechanism and proposed acomplete catalytic cycle for CO2 functionalization and also for the H2 generation process.
The CO2 functionalization occurs via CO2 insertion into the Zn-H bond of 1 (cf. Figure 4)
followed by a metathesis of Zn-OCOH compound with hydrosilane to generate silyl
formate (cf. Figure 5.)

1 + CO2
TS1
2(G= -8.33 kcal mol-1)
0.00(Ga=12.5 kcal mol-1)
Figure 4: Detailed mechanism for the reaction of CO2 with catalyst 1.

2 + HSi(OEt)3TS2
1(G= +0.71 kcal mol-1)
0.0(G=14.07 kcal mol-1)
Figure 5: The reaction mechanism for the regeneration of catalyst 1 from 2 and HSi(OEt)3

In CO2 insertion, the second step (TS2) is rate determining step, wherein silicon moiety
takes hypervalent structure. The formation of hypervalent silicon is seems to be important
for the formation of silyl formate.

3－ 191 －

fukui2012_02.indb 191

14.1.9 1:46:46 PM

Ⅳ 研究業績 (2012)

The reaction of 1 with methanol occurs through a metathesis between the Zn-H andthe O-H bond of methanol to obtain molecular hydrogen and the Zn-OMe compound.
The next step is the metathesis between the Zn-OMe bond and hydrosilane to regenerate
1 and silylether (cf. Figure 6). Here, on going from TS4 to TS5 via Int 1, the silicon
center gradually changes its structure from tetrahedral to trigonal bipyramidal.

Figure 6: Catalytic cycle for H2 generation using [K3-Tptm]ZnH catalyst, 1.
The small activation barrier and large exothermicity for the H2 generation and CO2
insertion reaction indeed suggest that 1 is effective catalyst and produces product P4 andP1, respectively. The analysis of electronic structures suggests a strong charge transfer(CT) from the valence s- and p-orbital of Zn to the CO2 moiety which stabilizes TS1 forCO2 insertion. Also, the rapid generation molecular hydrogen is facilitated by a strong
CT from metal center to hydride hydrogen of 1 and also to the hydrogen of methanol
through oxygen moiety.
For the regeneration of catalyst 1 and formation of silyl formate or silyl ether, theformation of respective hypervalent silicon structures are found to be important. For
instance, the small activation barrier and exothermicity of these reactions is shown to
nicely correlate with the stability of hypervalent structure.
Table 1: The reaction energy (G) and the activation barrier (Ga) for regeneration of 1 using

P1 or P4 and along with the stabilization energy of hypervalent silicon species.
aSilaneHSi(OEt)3
PhSiH3

G (kcal/mol)
4.23
16.59

HSi(OEt)3
PhSiH3

+0.37
+6.84

Reaction of P1 and SilaneG (kcal/mol)EStabilization (kcal/mol)
0.71-17.87
20.97-16.61
Reaction of P4 and Silane-14.13-51.22-7.11-44.11

4－ 192 －

fukui2012_02.indb 192

14.1.9 1:46:46 PM

Ⅳ 研究業績 (2012)

Based on Table 1, the higher reactivity of HSi(OE)3 than PhSiH3 and also the higher
reactivity of P4 than P1 is explained.
It is concluded that catalytic cycle for CO2 functionalization and H2 generation
reactions indeed occurs rapidly and (i) the above discussed strong CT interaction and (ii)the stability of hypervalent silicon in the transition states are the two important factors forthese rapid catalytic cycles.
2. Original Papers(1) Deshmukh Milind M. and Sakaki Shigeyoshi"Two-step Evaluation of Potential Energy Surface and Binding Energy of van der
Waals Complexes"
J. Comput. Chem., 33, 617 (2012).
(2) Deshmukh Milind M.; Ohba Masaaki, Kitagawa Susumu, and Sakaki Shigeyoshi,"Absorption of CO2 and CS2 into the Hofmann-Type Porous Coordination Polymer:
Electrostatic versus Dispersion Interactions.”
J. Am. Chem. Soc. 135, 4840 (2013).
(3) Deshmukh Milind M. and Sakaki Shigeyoshi"Rapid Generation of Molecular Hydrogen and Carbon Dioxide Functionalization
with Zinc Hydride: Theoretical Insights into Interesting Catalytic Cycle"
To be submitted (2013).
3. Presentations at academic conferences(1) Deshmukh Milind M. and Sakaki Shigeyoshi,“Absorption of CO2 and CS2 into the Hofmann-type Porous Coordination Polymer:
ONIOM(MP2.5:DFT) Study of Absorption Position and Energy”
Challenges in Organic Materials & supramolecular Chemistry (ISACS 10), Kyoto
University, Japan, June 18-21, 2013.
(2) Deshmukh Milind M. and Sakaki Shigeyoshi,“Reaction between CO2 and Zinc Hydride: Interesting Theoretical Insights”
The 7th Annual Meeting of Japan Society for Molecular Science, Kyoto University,
Kyoto Terrsa, Japan, September 24-27, 2013.
4. Others(1) Deshmukh Milind M. and Sakaki Shigeyoshi“Comparative Theoretical Study of Reactivities of Pd(II), Pd(III), and Pd(IV)Complexes towards the C-C Bond Reductive Elimination Reaction”
The 6th Annual Meeting of Japan Society for Molecular Science, University ofTokyo, Japan, September 18-21, 2012.
(2) Deshmukh Milind M. and Sakaki Shigeyoshi“Absorption of I2 in Hofmann-type Porous Coordination Polymer: Unusual
Absorption Position and Determining Factors”
The 10th symposium of Fukui Institute for Fundamental Chemistry, Kyoto University,
Kyoto, November. 30, 2012.

5－ 193 －

fukui2012_02.indb 193

14.1.9 1:46:47 PM

Ⅳ 研究業績 (2012)

Guixiang ZENGSPR Fellow, Fukui Kenichi Memorial Research Group 2
1. Summary of the research of the year
Unexpected Electronic Process of H2 Activation by a New Nickel Borane Complex:
Comparison with the Usual Homolytic and Heterolytic Activations. [1]H-H σ-bond activation promoted by transition-metal catalysts is of great importance not only infundamental chemistry [2] but also in the hydrogen storage technology [3]. Usually, the H−H
σ-bond is either homolytically or heterolytically cleaved by transition-metal complexes, as
displayed in Scheme 1.[4]Scheme 1. H−H σ-Bond Activation.

The former cleavage occurs through the oxidative addition of the H−H σ-bond to a metal center toform a dihydride complex (type A in Scheme 1), where the oxidation state of the metal center
increases by 2. This kind of reaction is possible for electron-rich late transition metals. The latter
reaction generally occurs under the cooperative functions of an electron-deficient transition-metal
center and an electron-rich Lewis base (LB) ligand, where the metal center and the ligand accept ahydride and a proton, respectively (type B in Scheme 1). In this type of reaction, the oxidation stateof the metal center does not change at all. However, the H−H σ-bond cleaved by the cooperation ofan electron-rich transition-metal center and an electron-deficient Lewis acid (Z) ligand is rarely
reported (type C in Scheme 1).
To elucidate the electronic process of the
Scheme 2. H−H σ-Bond Activation by 1Mes.
type C reaction in Scheme 1, we investigatedthe H2 activation by a nickel-borane complex
1Mes, as shown in Scheme 2. [5] First, one H2
molecule coordinates with the nickel center toform a dihydrogen complex, 2, which induces
an increase in the nickel 3d and 4p orbital
populations and thus a decrease in the nickel
1－ 194 －

fukui2012_02.indb 194

14.1.9 1:46:47 PM

Ⅳ 研究業績 (2012)

oxidation state, as shown in Figure 1. Then, theH−H σ-bond is cleaved under the cooperationof the electron-rich nickel center and theelectron-deficient borane ligand in a polarizedmanner, leading to an unprecedented
trans-nickel(II) hydridoborohydrido complex, 3.
In the transition state, charge transfer (CT)occurring from the H2 moiety to the 1Mes
moiety (0.683 e) is much larger than the reverse
CT (0.284 e); see Scheme 3. As a result,cleavage of the H−H σ-bond affords two
positively charged hydrogen atoms. In thisprocess, the boron atomic population and thenickel 4p orbital population increase, but thenickel 3d orbital population decreases. After the
H−H σ-bond cleavage, CT from the nickel 4p
orbital to these positively charged hydrogenatoms occurs to afford 3, where the oxidation
state of the nickel center increases to +2.

Figure 1. Changes in bond distance (in Å) andelectron populations (in e) along the intrinsic
reaction coordinate (IRC) of the H−H σ-bondactivation by the nickel-borane unit. .

Scheme 3. The geometry of the TS1/2 for the HH σbond activation and the charge transfer (CT)between the H2 and nickel-borane moieties in TS1/2.

Original papers[1] Guixiang ZENG and Shigeyoshi SAKAKI
2－ 195 －

fukui2012_02.indb 195

14.1.9 1:46:48 PM

Ⅳ 研究業績 (2012)“Unexpected Electronic Process of H2 Activation by a New Nickel Borane Complex:
Comparison with the Usual Homolytic and Heterolytic Activations”
Inorg. Chem. 52, 2844-2853 (2013).
[2] Sean E. Clapham, Alen Hadzovic, and Robert H. Morris“Mechanisms of the H2-Hydrogenation and Transfer Hydrogenation of Polar Bonds
Catalyzed by Ruthenium Hydride Complexes” Coord. Chem. Rev. 248, 2201-2237, (2004).
[3] Charles W. Hamilton, R. Tom Baker, Anne Staubitz and Ian Manners, “B-N
Compound for Chemical Hydrogen Storage.” Chem. Soc. Rev. 38, 279-293 (2009).
[4] Jesse W. Tye, Marcetta Y. Darensbourg and Michael B. Hall “In Activation of Small
Molecules: Organometallic and Bioinorganic Perspectives” Tolman, W. B., Ed.;
Wiley-VCH: Weinheim, Germany, 2006; p 121.
[5] Harman, W. H.; Peters, J. C. “Reversible H2 Addition across a Nickel–Borane Unit as a
Promising Strategy for Catalysis ” J. Am. Chem. Soc. 134, 5080-5082 (2012).
Iridium-catalyzed Acceptorless Alcohol Dehydrogenation: Interplay Between Theoretical andExperimental Studies for Understanding Reaction Mechanism and Finding New Efficient Catalysts
Promoterless AAD reactions are desirable for the requirement of green chemistry, which has
attracted extensive interests in the past decade.

Since 2008, Yamaguchi, Fujita, and their coworkers

have successfully applied a series of efficient iridium complexes (Cat 4 to Cat 6) to the AAD reaction; see
Scheme 1.

These iridium catalysts work efficiently under relatively mild conditions (<100ºC).

Scheme 1. Iridium Complexes Efficient for AAD Reaction.

Recently,

they

synthesizedanewpentamethylcyclopentadienyl); see Scheme 1.

iridium

complexCp*Ir(bipyridonate)

Cat

7

(Cp*=

Cat 7 is much more active than Cat 4 to Cat 6 and works

well not only in the AAD of aromatic alcohols but also in the AAD of the aliphatic alcohol under mild
conditions.

This is interesting because the acceptorless AAD of aliphatic alcohol has been limited,

compared with that for the aromatic alcohols. The sole difference between Cat 7 and Cat 4 to Cat 6 is thefunctional bipyridonate ligand (bpyO). Furthermore, if the bpyO is substituted for a phenanthroline-based
functional ligand (phenO), the reactivity of the catalyst (Cat 8) decreases very much; see Scheme 2 for the3－ 196 －

fukui2012_02.indb 196

14.1.9 1:46:48 PM

Ⅳ 研究業績 (2012)

phenO ligand.

These results suggest that the reactivity of the Cp*Ir catalyst is sensitive to the ligand, andthe bpyO ligand is the best ligand now. But, the reason is not clear. Also, it is unclear whether the mechanismis the same as that of the previous catalysts such as Cat 4 or not.
First, we explored the reaction mechanism, where two possible pathways are investigated, as shown in
Scheme 2. Our computational results demonstrated that that concerted pathway is much more favorable than
the stepwise pathway. This is different from the AAD mechanism mediated by Cat 4, where these tworeaction pathways are comparable.
Next, the electronic process of the AAD reaction was examined. In this process, we found that the Cp*
ligand receives electrons from the iridium center in the dehydrogenation step, but it donates electrons to theiridium center in the dihydrogen complex formation step. Because the dihydrogen complex formation step isthe rate-determining step, therefore, the electron donating ligand is more favorable for the AAD reaction.

Scheme 2. Proposed reaction pathways of the AAD reaction mediated by Cat 7.

Then, a new efficient AAD catalyst (Ben)Ru(bpyO) 1RuB with a cheaper and abundant 4d
ruthenium element was predicted both theoretically and experimentally. The construction procedureis shown in Scheme 3. 1-RuB exhibits good reactivity in the AAD reaction according to our
computational results, which is verified by the experimental work. Experimental results also
demonstrated that when the benzene ligand is substituted for a hexyl methyl benzene ligand, thereactivity of the catalyst is enhanced. This is consistent with our computational result that theelectron donating ligand is more favorable the AAD reaction.
Scheme 3. Prediction of a New Catalyst.

4－ 197 －

04-3 gyoseki_kenkyuin2.indd 197

14.1.9 2:10:09 PM

Ⅳ 研究業績 (2012)

Original paper
Guixiang Zeng, Kenichi Fujita, Ryohei Yamaguchi, and Shigeyoshi Sakaki “Iridium-catalyzed
Acceptorless Alcohol Dehydrogenation: Interplay Between Theoretical and Experimental Studies
for Understanding Reaction Mechanism and Finding New Efficient Catalysts” in preparation.
2. Presentation at academic conferences
Guixinag Zeng, Shigeyoshi Sakaki“Unexpected Electronic Process of the H2 Activation by a New Nickel(0)−Borane
Complex: Comparison with the Usual Homolytic and Heterolytic Activations”
The 60th Symposium of Organometallic Chemistry, Osaka, September 14, 2012
3. Others
Guixinag Zeng, Shigeyoshi Sakaki“Unexpected Electronic Process of the H2 Activation by a New Nickel(0)−Borane
Complex: Comparison with the Usual Homolytic and Heterolytic Activations” The 9th
symposium of Fukui Institute for Fundamental Chemistry, Kyoto, Nov. 30, 2012.

5－ 198 －

fukui2012_02.indb 198

14.1.9 1:46:49 PM

Ⅳ 研究業績 (2012)

Nozomi TAKAGISPR Fellow, Fukui Kenichi Memorial Research Group 2
1. Summary of the research of the year
A Theoretical Study of Unusual Y-Shaped Three-coordinate Pt Complex: Pt(0) σ-Disilane
Complex or Pt(II) Disilyl Complex?
The unusual Y-shaped structure of therecently reported three-coordinate Pt complex
Pt[NHC(Dip)2](SiMe2Ph)2N-heterocycliccarbene;2,6-diisopropylphenyl)

was

(NHC

=

Dip

=

considered

a

N

N
C

139.8°

2.126Å

Pt

snapshot of the reductive elimination ofSi

disilane (Figure 1). A density functional theory

80.3°

2.345Å
Si

3.025Å

study indicates that this structure arises from

Si-Pt-C-N = 27.3°

the strong trans-influence of the extremely

Figure 1. Optimized structure of Pt[NHC(Dip)2](SiMe3)2
at the B3PW91 level.

σ-donating carbene and silyl ligands. Though

this complex can be understood to be a Pt(II) disilyl complex bearing a distorted geometry due to
the Jahn-Teller effect, its 195Pt NMR chemical shift is considerably different from those of Pt(II)complexes but close to those of typical Pt(0) complexes. Its Si···Si bonding interaction is 50% of
the usual energy of a Si-Si single bond. The interaction between the Pt center and the (SiMe2Ph)2
moiety can be understood in terms of donation and back-donation interactions of the Si-Si
σ-bonding and σ*-antibonding molecular orbitals with the Pt center (Scheme 1). Thus, we conclude
that this is likely a Pt(0) σ-disilane
5dz2

complex and thus a snapshot after aconsiderable amount of the charge transfer

Pt[NHC(Dip)2]

from the two silyl groups to the Pt centerhas occurred. Phenyl anion (Ph ) and

5dyz

+

donation(0.607e)-[R-Ar]- [R-Ar = 2,6-(2,6-iPr2C6H3)2C6H3]

6pz

back-donation(0.307e)disilane

as well as the divalent carbon(0) ligand

-bonding MO

-antibonding MO

Scheme 1－ 199 －

fukui2012_02.indb 199

14.1.9 1:46:51 PM

Ⅳ 研究業績 (2012)

N

138.4°
Si

2.112Å

2.133Å

Pt

2.308Å
83.3°

139.6°
139.2°
81.2°

2.318Å

Si

Si-Pt-C-C = 89.9°

3.017Å(A) [Pt(Ph)(SiMe3)2]-N

2.086Å
141.4°

148.6°

2.436Å
2.436Å
76.9°
Ge

Ge-Pt-C-N = 19.8°

3.031Å

Si-Pt-C-N = 19.9°(D) Pt[NHC(Dip)2](GeMe3)2

3.144ÅSi(C) Pt[C(NHC)2](SiMe3)2

N

N

N

C

C

Pt

153.5° Pt 135.7°

2.024Å
62.7°

2.082Å

2.381Å

B
B B-Pt-C-N = 0.0°
O O2.107ÅO O

Ge

Pt 2.323Å
85.2°

Si-Pt-C-C = 83.3°

2.064Å

Pt

N

Si-Pt-C-C = 73.3°

C

141.6°Si(B) [Pt(R-Ar)(SiMe3)2]-NCC

2.319Å

Si

Si-Pt-C-C = 72.4°

3.067Å

C

137.4° 2.119Å

Pt

Si

N

N

C

C

N

70.8° B

Si 2.550Å

Si-Pt-C-N = 21.4°(E) Pt[NHC(Dip)2](BO2C2H2)2

1.988ÅO

B-Pt-C-N = 16.0°(F) Pt[NHC(Dip)2](SiMe3)(BO2C2H2)

Figure 2. Various snapshots for reductive elimination of Si-Si, Ge-Ge, B-B, and B-Si bonds calculated at theB3PW91 level.

C(NHC)2 also provide similar unusual Y-shaped structures. Three-coordinate digermyl, diboryl, andsilyl-boryl complexes of Pt and a disilyl complex of Pd are theoretically predicted to have similar
unusual Y-shaped structures when a strongly donating ligand coordinates to the metal center. In a
trigonal-bipyramidal Ir disilyl complex Ir(SiR3)2(NHC)(PH3)2, the equatorial plane has a similar
unusual Y-shaped structure. These results suggest that various snapshots can be shown for the
reductive eliminations of the Ge-Ge, B-B, and B-Si σ-bonds (Figure 2).

Theoretical

Study

of

ReactivityofGe(II)-hydrideCompound:Comparison

withRh(I)-hydride Complex and Prediction of Full Catalytic Cycle by Ge(II)-hydride
The reaction of a Ge(II) hydride compound HC{CMeArN}2GeH (Ar = 2,6-iPr2C6H3) 1 with
2,2,2-trifluoroacetophenone (CF3PhCO) is theoretically investigated with DFT and SCS-MP2
methods. This reaction easily occurs with moderate activation barrier and considerably large
exothermicity, to afford a Ge(II) alkoxide 2 through a four-membered metathesis-like transition
state (Figure 3). In the transition state, the charge-transfer (CT) from the Ge-H σ-bonding
molecular orbital (MO) to the C=O π*-antibonding MO of CF3PhCO plays an important role.
Acetone ((CH3)2CO) and benzophenone (Ph2CO) are not reactive for 1, because their
π*-antibonding MOs exist at higher energy than that of CF3PhCO. Though 2 is easily formed, the－ 200 －

fukui2012_02.indb 200

14.1.9 1:46:53 PM

Ⅳ 研究業績 (2012)

catalytic hydrogenation of CF3PhCO by 1
is difficult because the reaction of 2 with adihydrogenmolecule

needs

a

large

activation energy (Figure 4). On the other
hand, our calculations clearly show thatthe catalytic hydrogenation of ketone by
cis-RhH(PPh3)24

easilyoccurs,as

expected. The comparison of catalytic
cycle between 1 and 4 suggests that thestrong Ge-O bond of 2 is the reason of thevery large activation energy for thehydrogenation by 1. To overcome thisdefect, we investigated various reagentsand found that the catalytic cycle can becompleted with the use of SiF3H. The

Figure 3. Geometry changes in hydrogenation andhydrosilylation of CF3PhCO by the Ge(II) hydride 1 calculated
at the B3PW91 level.

product is silylether CF3PhCHOSiF3,
which is equivalent to alcohol because it
easily undergoes hydrolysis to afford
CF3PhCHOH. The similar catalytic cycles
are

also

theoretically

predictedforhydrosilylations of CO2 and imine. This is
the first theoretical prediction of the full
catalytic cycle with a heavier main-groupelement compound.

Figure 4. Potential (∆E) and Gibbs (∆G0) energy changes (inkcal/mol) in (a) the hydrogenation and hydrosilylation of
CF3PhCO by the Ge(II) hydride 1 and (b) the hydrogenation of
CF3PhCO by the Rh(I) hydride 4 at the SCS-MP2//B3PW91
level, where ∆E and ∆G0 are shown before and after the slash,respectively.

－ 201 －

fukui2012_02.indb 201

14.1.9 1:46:54 PM

Ⅳ 研究業績 (2012)

2. Original papers(1) "A Theoretical Study of Unusual Y-Shaped Three-coordinate Pt Complex: Pt(0) σ-Disilane
Complex or Pt(II) Disilyl Complex?"
N. Takagi, and S. Sakaki, J. Am. Chem. Soc., 2012, 134, 11749-11759.
(2) "Theoretical Study of Reactivity of Ge(II)-hydride Compound: Comparison withRh(I)-hydride Complex and Prediction of Full Catalytic Cycle by Ge(II)-hydride"N. Takagi, and S. Sakaki, J. Am. Chem. Soc., in press.
3. Presentation at academic conferences(1) "Theoretical Study of Ketone Insertion into Ge(II)-H Bond: Comparison with that into
Rh(I)-H Bond"
N. Takagi, and S. Sakaki, Annual Meeting of Japan Society for Molecular Science, Tokyo,
September, 18 – 21, 2012.
(2) "A Theoretical Study of Unusual Y-Shaped Three-coordinate Pt Complex: Pt(0) σ-Disilane
Complex or Pt(II) Disilyl Complex?"
N. Takagi, and S. Sakaki, The 62nd Japan Society of Coordination Chemistry Symposium,
Toyama, September, 21 – 23, 2012.
(3) "A Theoretical Study of Activation of Ketone by Ge(II) Hydride: Reaction Mechanism,
Comparison with Rh(I) Hydride, and Prediction as a Main-group-based Catalyst"
N. Takagi, and S. Sakaki, The 10th Fukui Institute for Fundamental Chemistry Symposium,
Kyoto, November 30, 2012.
(4) "A theoretical study of ketone activation by a Ge(II) hydride compound and prediction of afull cycle."
N. Takagi, and S. Sakaki, The 93rd Annual Meeting of the Chemical Society of Japan,
Shiga, March 22-25, 2013.

－ 202 －

fukui2012_02.indb 202

14.1.9 1:46:55 PM

Ⅳ 研究業績 (2012)

Masayuki NAKAGAKISPR Fellow, Fukui Kenichi Memorial Research Group 2
1. Summary of the research of the year
Spin state of inverted sandwich type complexes of hetero transition metals
bridged by N2
β-diketiminate ligands make low-valent and low-coordinate transition metal complexes and form theinversed sandwich type complexes (ISTCs). Especially, ISTCs bridged by dinitrogen molecule areinteresting for its spin states and coordination mode of N2. The (μ-N2)[Fe(DDP)]2 (DDPH =2-{(2,6-diisopropyl-phenyl)imino}pent-2-ene, which is refer to “nacnac” in several works) takes septet spinstate. On the other hand, (μ-N2)[Cr(DDP)]2 takes singlet spin state. Furthermore, the coordination modes of
N2 in Cr and Fe complexes are different; the Fe complex takes η1-end-on mode, though the Cr complex takes
η2-side-on mode. Previously, we could explain these differences of spin state and coordination mode by thedifference of bonding interaction between metal atoms and N2.
In this study, we investigated the electronic structure of the dinitrogen bridged ISTCs of hetero transition

metals; the combination of chromium(I), manganese(I), and iron(I) atoms, to expect the unique character.
Scheme 1 (μ-N2)[M1(AIP)][M2(AIP)]2 ([M1,M2]=[Mn,Fe], [Cr,Mn], [Cr,Fe]; DDP: R=Me,
R’=2,6-iPr2C6H3; AIP: R=H, R’=H)

We replaced the DDP ligands with AIP (AIPH = 1-amino-3-imino-prop-1-ene; Scheme 1) for brevity.
Geometry optimizations were carried out for each spin states by the complete active space self-consistent
field (CASSCF) method. The active space consists of the d-orbitals of two metals and two π* orbitals ofdinitrogen molecule. The second-order perturbation theory with a CASSCF reference function (CASPT2)
calculations were carried out at CASSCF optimized structures. CASCI calculations with the orbitals werecarried out to obtain the occupation number and spin density of each localized orbitals
The

relativeenergiesof1

variousspin

statesof(μ-N2)[Mn(AIP)][Fe(AIP)]

and2(μ-N2)[Cr(AIP)][Mn(AIP)] with η -end-on and η -side-on structures calculated by CASPT2 methods arelisted in Table 1. In the (μ-N2)[Mn(AIP)][Fe(AIP)], the A2 state with η1-end-on structure corresponds to the－ 203 －

fukui2012_02.indb 203

14.1.9 1:46:55 PM

Ⅳ 研究業績 (2012)

B2 state with η2-side-on structure. In these states, the octet state is the most stable spin state but the quartet
and the sextet states are also relatively stable than the singlet state. The 8A2 state with η1-end-on is 1.7
kcal/mol more stable than the 8B2 state with η2-side-on, which is the medium value between that of(μ-N2)[Mn(AIP)]2 and (μ-N2) [Fe(AIP)]2. The A1 state with η2-side-on structure is similar to the grand stateof Cr complex, in which the doublet state is the most stable spin state but the energy differences among the
doublet state to the dectet state are very small, though the B1 sate is energetically quite higher than the B2state.
In the (μ-N2)[Cr(AIP)][Mn(AIP)], the B1 state with η2-side-on structure is the electronic grand state,
which corresponds to the B1 state with η1-end-on structure. In these states, the dectet state is the most stablespin state but the energy differences among the doublet to the dectet are very small. The A 2 state with
η2-side-on structure corresponds to the B2 state with η1-end-on structure. In these states, among the doublet
to the octet states are close each other. In η2-side-on structure, doublet state is the most stable spin state. On
the other hand, the octet state is the most stable spin state in the η1-end-on structure. Different from the B1state, the relative energies between the η2-side-on and the η1-end-on structures are close. The 2A2 state with
η2-side-on is 3.2 kcal/mol more stable than the 8B2 state with η2-side-on but 4.4kcal/mol less stable than the10

B1 state with η2-side-on. The result of the (μ-N2)[Cr(AIP)][Fe(AIP)], is similar to that of the(μ-N2)[Cr(AIP)][Mn(AIP)]. Due to the doubly occupied dx2 orbital in Fe, the most stable spin state of B1 andA2 states are nonet and triplet, respectively. And the energy difference of these states is only 1.4 kcal/mol.
Table 1 Relative energies of various spin states of (μ-N2)[M1(AIP)][M2(AIP)] calculated by CASPT2
methods (in kcal/mol).
(μ-N2)[Mn(AIP)][Fe(AIP)](μ-N2)[Cr(AIP)][Mn(AIP)]

η1-endη1-endη2-sideη2-sidemultiplicity A2 state B2 state A1 state B2 state B1 state A2 state B1 state
10tet

26.5

12.1

30.7

13.5

14.1

18.3

0.0

8tet

0.0

1.7

29.8

7.6

15.5

6.2

1.4

6tet

5.7

6.4

28.3

8.2

16.0

5.7

2.3

4tet

9.6

9.7

27.1

9.5

16.2

5.5

2.8

2let

20.2

16.8

26.3

11.4

16.1

4.4

3.0

Molecular orbital (MO) interaction diagram of (μ-η1:η1-N2)[Mn(AIP)][Fe(AIP)]2 is shown in Scheme
2. The Mn(AIP) moiety has six d-electrons and the dx2 orbital is doubly occupied in the ground state ofisolated Mn(AIP); see the right hand of Scheme 2. The Fe(AIP) moiety has seven d-electrons and the dx2-y2
and dz2 orbitals are doubly occupied and other three d-orbitals are singly occupied in the grand state; see theleft hand of Scheme 2. In the η1-end-on structure, the dxz and dyz orbitals overlap with N2 π*x and π*y MOs tofrom bonding ψ1 and ψ2 MOs and anti-bonding ψ10 and ψ11 MOs, as shown in Scheme 2. The
CASSCF(11,11) natural orbitals of (μ-η1:η1-N2)[Mn(AIP)][Fe(AIP)]2 are shown in Figure 1. Numbers in－ 204 －

fukui2012_02.indb 204

14.1.9 1:47:00 PM

Ⅳ 研究業績 (2012)

parentheses represent occupation numbers in the octet state. In this complex, the dx2 orbital of Fe was
excluded from the active space to avoid the convergence problem. In these orbitals, the ψ1 and ψ2 are doubly
occupied in the main electron configuration, which mainly consist of dxz-π*x and dyz -π*y bonding interaction,
respectively. However, their occupation numbers are much smaller than 2.00. On the other hand, theoccupation numbers of their anti-bonding counterparts are considerably large. These results indicate that theone- and two- electron from φ1 and φ2 to φ10 and φ11 considerably contribute to the wavefunction. Two dz2-y2,
dxy orbitals, dx2 orbital of Mn and non-bonding dxz, dyz orbitals are singly occupied. Because these MOs areeither purely non-bonding or nearly non-bonding, the highest spin multiplicity of octet is the grand state.
Scheme 2 MO diagram of (μ-η1:η1-N2)[Mn(AIP)][Fe(AIP)]

φ7,a2(1.00)

φ8,a1(1.00 )φ9,b1(1.00) φ10,b2(0.55) φ11,b1(0.51)

φ1,b1(1.49)

φ2,b2(1.45)

φ3,a1(1.00)

φ4,a2(1.00 )8

φ5,a1(1.00)
1

φ6,b2(1.00)

1Figure 1. CASSCF(11,11) optimized orbitals of A2 state of (μ-η :η -N2)[Mn(AIP)] [Fe(AIP)]. Upper side isMn(AIP) and lower side is Fe(AIP).

The MO diagrams of (μ-η2:η2-N2)[Cr(AIP)][Mn(AIP)] are shown in Scheme 3. In isolated Cr(AIP)
moiety, five d orbitals are singly occupied; see the right hand of Scheme 3. In the 10B1 state, the dyz orbitalsof Cr and Mn overlap with N2 π*z orbital to form bonding MO φ1, anti-bonding MO φ11 and SOMO φ6; see
Scheme 3(a). The φ2 to the φ5 MOs are non-bonding d orbital of Mn, and the φ7 to the φ10 MOs are that of Cr.

－ 205 －

fukui2012_02.indb 205

14.1.9 1:47:04 PM

Ⅳ 研究業績 (2012)

The N2 π*x orbital is week interact to Cr dxy orbital. As the results, the anti-bonding MO φ12 is formed,
though it seems 4d-type orbital of Cr. The CASSCF(10,11) optimized orbitals and occupation numbers in B1
state are shown in Figure 2(a). The φ1 is very stable and almost doubly occupied. The φ6 is bonding
interaction between Cr and N2 but anti-bonding interaction between Mn and N2. The other 9 d-orbitals, φ2 to
φ10 including φ6, are essentially singly occupied and the φ11 and φ12 MOs are unoccupied in Hartree-Fockconfiguration.
Scheme 3 MO diagram of (μ-η2:η2-N2)[Cr(AIP)][Mn(AIP)]
(a)

(b)

(a) B1 state(b) A2 state

φ9,a1(1.00) φ10,b2(1.00) φ11,b1(0.04) φ12,a2(0.01) φ9,b2(0.96) φ10,a2(0.76) φ11,b1(0.50) φ12,b2(0.00)

φ5,a1(1.00) φ6,b1(1.00) φ7,a2(0.99) φ8,a1(1.00)

φ5,a1(1.00) φ6,a1(1.00) φ7,a2(1.00) φ8,a1(1.00)

φ1,b1(1.96) φ2,a1(1.00) φ3,a2(1.00) φ4,b2(1.00)

φ1,b1(1.50) φ2,a2(1.24) φ3,a1(1.00) φ4,b2(1.04)

Figure 2 CASSCF(11,12) optimized orbitals of (a)B1 and (b)A2 states of(μ-η2:η2-N2)[Cr(AIP)][M(AIP)] (M=Mn, Fe). Upper side is Cr(AIP) and lower side is Mn(AIP).

－ 206 －

fukui2012_02.indb 206

14.1.9 1:47:17 PM

Ⅳ 研究業績 (2012)

In the 2A2 state, the dyz orbitals of Cr and Mn overlap N2 π*z orbital to form bonding MO φ1,
anti-bonding MO φ11 and φ12. The Mn dxy orbital overlaps with π*x orbital to form bonding MO φ2 andanti-bonding MO φ10. On the other hand, Cr dxy orbital seems to be non-bonding MO φ7. The Cr(AIP) moiety
has four non-bonding d orbitals and the Mn(AIP) moiety has three non-bonding d orbitals. The electron spinsin these orbitals are opposite each other; see Scheme 3(b). The CASSCF(10,11) optimized orbitals andoccupation numbers in A2 state are shown in Figure 2(b).
Table 2 shows the spin density of N2 and two M(AIP) moieties calculated by CASCI method withlocalized molecular orbitals. In the (μ-N2)[Mn(AIP)][Fe(AIP)], large negative spin density is obtained on N2.
The single occupation of non-bonding orbitals causes the spin polarization of bonding orbitals, α-electron
localizes to metal side moieties and β-electron localizes to N2 side, and the high-spin state is favorable. This
electronic structure is similar to that of the (μ-N2)[Mn(AIP)]2 and the (μ-N2)[Fe(AIP)]2. In the(μ-N2)[Cr(AIP)][Mn(AIP)], the spin polarization does not occur in B1 state. However, in A2 state, N2 and Cr
have same spin density but Mn has opposite spin density. In the10

B1 state, the main configuration has
doubly occupied N2 π*z orbital and singly occupied Mn dyz orbital. In the second reading terms, asingle electron moves from N2 π*z orbital to Cr dyz orbital compared to the main configuration. It
suggests that the dπ-π* bonding interaction between Cr and N2 is stronger than that between Mn
and N2. On the other hand, in the A2 state, the dπ-π* bonding interaction between Mn and N2 isstronger, though the highest b1 orbital was excluded from active space because the Cr dyz and N2 π*yorbitals could not be separated.
Table 2 Spin densities calculated by LMO-CASCI method(Mn,Fe)(Cr,Mn)η1-8A2

η2-10B1 η2-2A2

M1(AIP)

4.80

4.01

1.99

M2(AIP)

3.49

4.98

−1.45

N2

−1.28

0.02

0.47

Total

7.00

9.00

1.00

Summary
In the (μ-N2)[Mn(AIP)][Fe(AIP)], the spin states of two metal atoms take strong high-spin coupling, theoctet states is the most stable spin state. They form two bond between N2 and two M(AIP) moieties;
π(dyz)-bond and δ(dxy)-bond in η2-side-on and π(dyz)-bond and π(dxz)-bond in η1-end-on. There is large
negative spin density on N2 and the high-spin state is favorable, which is similar to that of the(μ-N2)[Mn(AIP)]2 and the (μ-N2)[Fe(AIP)]2.
In the (μ-N2)[Cr(AIP)][Mn(AIP)], we found two electronic states which has different electronic structurefrom the (μ-N2)[Cr(AIP)]2 and the (μ-N2)[Mn(AIP)]2. The B1 state takes dectet spin state whichhasπ(dyz)-bond. On the other hand, the A2 state takes doublet state. Though the A2 state has π(dyz)-bond andδ(dxy)-bond, the 2A2 state is 4.4 kcal/mol higher than the 10A1 state.

－ 207 －

fukui2012_02.indb 207

14.1.9 1:47:23 PM

Ⅳ 研究業績 (2012)

2. Presentation at academic conferences(1) 中垣 雅之，黒川 悠索，榊 茂好「窒素分子を挟んだ逆サンドイッチ型二核金属錯体の特異的なスピン状態に関する理論的研究」
第１５回理論化学討論会 2012 仙台 仙台 2012/5/24-26 1B5b 口頭(2) Masayuki Nakagaki, Yusaku I. Kurokawa, Shigeyoshi Sakaki“CAS-PT2 and LMO-CAS Study of Spin States and Coordination Modes of N2 bridged
Inverted Sandwich Type Complexes”
14th ICQC Interactional Congress of Quantum Chemistry (Boulder, Colorado, USA)
2012/6/25-30 I15 poster(3) 中垣 雅之、黒川 悠索、榊 茂好「異種金属原子による窒素分子を挟んだ逆サンドイッチ型錯体の電子構造に関する理論的研究」
第６回分子科学討論会 2012 東京 東京 2012/9/18-21 3P130 ポスター
(4) 中垣 雅之，黒川 悠索，榊 茂好「窒素分子を挟んだ逆サンドイッチ型二核金属錯体の特異的なスピン状態に関する理論的研究」
錯体化学会第６２回討論会 富山 2012/9/21-23 2Ba-06 口頭
3. Others(1) 中垣 雅之、榊 茂好「異種金属原子による窒素分子を挟んだ逆サンドイッチ型錯体の電子構造に関する理論的研究」
第10回京都大学福井謙一記念研究センターシンポジウム 京都 2012/11/30－ 208 －

fukui2012_02.indb 208

14.1.9 1:47:24 PM

Ⅳ 研究業績 (2012)

Terutaka YOSHIZAWASPR Fellow, Fukui Kenichi Memorial Research Group 2(To 30 Sep. 2012)
1. Summary of the research of the year
NMR shielding constants of CuX, AgX, and AuX (X = F, Cl, Br, and I) investigated by density
functional theory based on the Douglas–Kroll–Hess Hamiltonian
Introduction
NMR shielding constants of heavy metal elements are of considerable interest in molecularscience and theoretical chemistry, because those shielding constants reflect characteristic electronic
structure, in particular, relativistic effects in the system including heavy elements. Actually, David andRestrepo recently reported that the paramagnetic term of the Au nuclear magnetic resonance (NMR)
shielding constant of AuF molecule is more than three times as large as those of AuCl, AuBr, and AuI.
They discussed that this result arises from spin-orbit (SO) effect enhanced by the highelectronegativity of F atom. Since their report, the relation between the SO effect and theelectronegativity attracts a lot of interests, because the SO effect does not seem to directly relate toelectronegativity. However, the mechanism of the relation has not been elucidated yet.
In the present study, we combined the DFT method with the second-order DKH (DKH2)
one-electron Hamiltonian and applied it to the calculation of the NMR shielding constant. Then, weapplied this method to the NMR shielding constant of the metal in CuX, AgX, and AuX (X = F, Cl, Br,
and I), investigated relativistic effects on the NMR shielding constant, and discussed the reasons why
the electronegativity of halogen influences the NMR shielding constant.
Results and discussion
Second-order magnetically relativistic (MR2) effect on metal shielding constant in MX
The MR2 effects on the Cu, Ag, and Au shielding constants are summarized in Table 1 andSupporting Information Table S5 [1], where they were defined as the difference between the DKH2
magnetic operators and the Breit-Pauli magnetic operators. As shown in Table 1, the MR2 effectconsiderably decreases the DKH2(SR+SO) value. Interestingly, the MR2 effect in CuF is considerablylarger than those for other halides. This result is consistent with the understanding that the MR2 effectis not always large only for the heavier system. The largest MR2 effect for CuF is attributed to theoverestimation of the SD+FC term (= 2783 ppm) by the Breit-Pauli magnetic operators, while theMR2 effect is moderate in the paramagnetic and diamagnetic terms.
1－ 209 －

fukui2012_02.indb 209

14.1.9 1:47:24 PM

Ⅳ 研究業績 (2012)

The MR2 effect in AgX is not large; see Table 1 and Supporting Information Table S5 [1]. The
moderate MR2 effect in AgF to AgBr arises from the cancellation of the MR2 effects between the
diamagnetic term and the sum of the paramagnetic and SD+FC terms. In AuX, the MR2 effect isremarkably large because of the extremely large overestimation of the SD+FC term and the somewhat
large overestimation of the paramagnetic term by the Breit-Pauli magnetic operators, as shown in
Table 1. This result indicates that the Breit-Pauli magnetic operators cannot be applied to the NMR
study of Au compounds.
Table 1. Second-order magnetically relativistic (MR2) effects on Cu, Ag, and Au shielding
constants estimated by the full DKH2-BP86 method containing the scalar relativistic (SR), SO,
and MR2 effects and the DKH2-BP86 method containing only the SR and SO effects.
DKH2

DKH2

(SR+SO)(SR+SO+MR2)

Dia

2510

Para

Trend[a]

MR2%

2285

Down

–8.9

–2548

–2512

Down

–1.4

SD+FC

2783

1525

Down

–45.2

Total

2745

1298

Down

–52.7

Dia

2539

2314

Down

–8.9

Para

–1413

–1381

Down

–2.2

SD+FC

813

647

Down

–20.4

Total

1939

1580

Down

–18.6

Dia

5000

4373

Down

–12.5

Para

–816

–690

Down

–15.5

SD+FC

1202

1314

Up

9.3

Total

5386

4997

Down

–7.2

Dia

5027

4409

Down

–12.3

Para

–778

–646

Down

–17.0

SD+FC

153

1046

Up

584.3

Total

4402

4809

Up

9.3

Dia

11093

9647

Down

–13.0

Para

–6076

–5176

Down

–14.8

SD+FC

173376

19276

Down

–88.9

Total

178393

23747

Down

–86.7

Dia

11123

9766

Down

–12.2

Para

–3203

–2482

Down

–22.5

SD+FC

15771

6912

Down

–56.2

Molecule

σ

CuF

CuCl

AgF

AgCl

AuF

AuCl

2
－ 210 －

fukui2012_02.indb 210

14.1.9 1:47:25 PM

Ⅳ 研究業績 (2012)

Total

23691

14196

Down

–40.1

[a] ”Down” means that absolute value decreases by the MR2 effects.
Conclusions
We developed the two-component relativistic method for NMR shielding constant based on the DKH2
one-electron Hamiltonian. Important results are summarized, as follows:(1) The shielding constant considerably depends on the basis set in the DKH2 method like the 4c
relativistic theory only with the restricted kinetic balance, viz., without an explicit diamagnetism.
(2) The DKH2-DFT method presents the shielding constant of heavy atom (up to Xe) comparable tothe 4c-DFT-calculated value and reproduces well the experimental I shielding constant of CuI and AgI
and the experimental Xe shielding constant of XeF2.
(3) The DKH2-DFT-calculated increasing order of the Ag shielding constant AgF < AgBr < AgI agrees
with the experimental result, but the DKH2-HF-calculated order does not.
(4) AuF exhibits extremely large Au shielding constant, which is the largest in AuX, but CuF and AgF
do not exhibit very large Cu and Ag shielding constants.
(5) The FC term in the sdσ+pσ → sdσ–pσ transition is responsible for the large SD+FC term of AuF.
One important reason is the small orbital energy separation between the sdσ+pσ and sdσ–pσ MOs in
AuF.
(6) The large paramagnetic term of AuF arises from the large metal d-orbital components in the dπ–pπ
and sdσ–pσ MOs. This large paramagnetic term compensates the positive SD+FC term in AuF to someextent.
(7) For all these compounds, the MR2 effect decreases the diamagnetic term, the absolute value of theparamagnetic term, and the SD+FC term which is overestimated by the Breit-Pauli magnetic operators
except for the SD+FC terms of AgF and AgCl.
(8) The MR2 effect is important even for CuF. The relatively small MR2 effect in AgF to AgBr is
attributed to the cancellation of the MR2 effect for the diamagnetic term by that for the paramagnetic
and SD+FC term.
Considering all these results, we believe that the DFT method based on the DKH2 Hamiltonian isuseful for calculating NMR shielding constant of heavy metal element.
Reference[1] T. Yoshizawa, S. Sakaki, J. Comput. Chem. 34, 1013, (2013).

3－ 211 －

fukui2012_02.indb 211

14.1.9 1:47:25 PM

Ⅳ 研究業績 (2012)

2. Original papers(1) T. Yoshizawa and T. Nakajima “A new computational scheme for the spin–orbit part of zero-field
splitting tensor” Chem. Phys. Lett. 549, 108–112, (2012)(2) T. Yoshizawa and S. Sakaki “NMR shielding constants of CuX, AgX, and AuX (X = F, Cl, Br, andI) investigated by density functional theory based on the Douglas–Kroll–Hess Hamiltonian” J. Comput.
Chem. 34, 1013–1023, (2013)
3. Presentation at academic conferences
T. Yoshizawa and S. Sakaki “NMR shielding constants of CuX, AgX, and AuX (X = F, Cl, Br, and I)
investigated by density functional theory based on the Douglas–Kroll–Hess Hamiltonian” Annual
Meeting of Japan Society for Molecular Science, 3P099, September 18-21, 2012, the University ofTokyo, Tokyo (Japan).

4－ 212 －

fukui2012_02.indb 212

14.1.9 1:47:25 PM

Ⅳ 研究業績 (2012)

Wei GUANSPR Fellow, Fukui Kenichi Memorial Research Group 2
1. Summary of the research of the year
Interest in new heterodinuclear transition-metal/main-group-metal complexes: DFT study ofelectronic structure and mechanism of fluoride sensing function
Fluoride anion plays a crucial role in biological process and daily life. However, excessive intake will leadto dental and skeletal fluorosis and even osteosarcoma. Taking into account these adverse effects of fluoride
anion, the recognition and sensing of fluoride anions
are necessary. For a potential fluoride chemosensor,

Scheme 1such factors as large ion affinity, high selectivity,
visible photophysical response, and hydrolytic
stability must be satisfied.
In this work, the colorimetric fluoride sensing
propertyoftransition-metaltheheterodinuclear

complexes

main-group/[(o-(Ph2P)C6H4)3M1-M2Cl]+ (M1 = As, Sb, or Bi; M2 = Pd or Pt) was
systematically investigated with the DFT method(Scheme 1).
(1) Not only the larger F − capturing ability of the Lewis acidic M1 center but also the allostericcoordination of the third phosphine with the M2 center is indispensable for the colorimetric sensing of thefluoride anion. The stabilization energy by the fluoride adduct formation is −15.5 and −16.2 kcal mol−1 for 3(M1 = Sb; M2 = Pd) and 6 (M1 = Sb; M2 = Pt), respectively. The formation of the hypervalent M1–F bondinduces the allosteric coordination of the P3 with the M 2 center. Accordingly, the coordination geometry of
the M2 center changes from a four-coordinate planar structure in 3–8 to a five-coordinate trigonal-bipyramidin fluoride adducts (3F–8F).
(2) The calculated absorption spectra agree with the experimental ones (Figure 1). For instance, the twoabsorption bands at 383
and 315 nm (2) disappear
but a new strong peak
appears at 332 nm (2F),
when 2 converts to 2F.
These

absorptions

aremainlyassignedto

LFT/LMCT. The additionof fluoride anion to 3

Figure 1. Comparisons of experimental and calculated absorption spectrab ofquenches the absorption

2, 2F, 3, and 3F. a PCM(CH2Cl2)/TD-PBE0/BS-II level.

－ 213 －

fukui2012_02.indb 213

14.1.9 1:47:26 PM

Ⅳ 研究業績 (2012)

band around 400 nm but newly produces two absorption peaks (475 and 451 nm) in the long wavelength
region in 3F. They are assigned to the Pd-based LFT, d�� → �� � and �� � ��� → �� � including LMCT

character. The allosteric coordination of the P3 with the Pd center plays a crucial role in decreasing the d-dorbital energy separation and hence the resultant spectrum appears in the visible region in the fluoride
adduct.

(3) This kind of heterodinuclear complex 3 exhibits high selectivity for fluoride anion. In theanion-capturing process of 3 for such other anions as chloride, bromide and thiocyanide anions, the Pd center
does not change to a trigonal-bipyramidal structure and their binding energies with those anions are only 6.0,
4.3, and 3.1 kcal mol−1, respectively. The binding energy for cyanide adduct (9.9 kcal mol−1) is moderately
smaller than that for the fluoride adduct, but it is enough to bind the cyanide anion. The allostericcoordination is not stable in the cyanide adduct of the Sb-Pd combination, however, in the cyanide adduct of
the Sb-Pt the allosteric coordination form is more stable than the other structure without the allostericcoordination. Actually, the cyanide adduct 6CN provides a large absorption in visible region. Thus, the Sb-Pt
combination is suggested to be useful for detecting cyanide anion.
(4) In the absence of fluoride anion, the strain energy of the bridging (o-(Ph2P)C6H4)3Sb moiety of 3' ismuch larger than the stabilization induced by the coordination of the third phosphine. In the fluoride adduct,on the contrary, the moderate strain energy is overcome by the Pd-P3 coordinate bond. Hence, the chelating
structure of (o-(Ph2P)C6H4)3Sb is the origin of the absence of the P3 allosteric coordination in 3 but thepresence of the P3 coordination in 3F; in other words, this ligand plays a crucial role in the allostericcoordination.
The Bi-Pd (5) and Bi-Pt (8) combinations provide a moderately smaller binding energies (‒10.5 and ‒10.9
kcal mol‒1) than that of 3, and the Sb-Pt combination (6) presents a bit larger binding energy (‒16.2 kcal mol‒1

) than 3. Also, 5, 6, and 8 exhibit similar spectral changes to those of the 3 → 3F conversion because of theallosteric coordination on the Pd/Pt center in the fluoride adduct. The Bi-Pd combination is recommended for
fluoride sensing material without interference from cyanide anion.
Mechanism Investigation of Nickel-Catalyzed Decarboxylative [4 + 2] Cycloaddition of Isatoic
Anhydrides with Alkynes
Heterocyclic compounds play a vital role in life processes due to their biological activities in agrochemicaland pharmaceutical applications. As the demand for these chemicals increases, it is very essential fordeveloping novel and efficient synthetic methods to prepare heterocyclic compounds. Among a variety ofsynthetic transformations, intermolecular cycloadditions catalyzed by transition-metal complexes are
powerful methodologies for constructing structurally diverse heterocyclic compounds in modern syntheticorganic chemistry.
Here, Ni-catalyzed decarboxylative [4Scheme 2+ 2] cycloaddition of isatoic anhydrides
withalkynestoquinolones

wastheoretically investigated with the DFT
method (Scheme 2).

－ 214 －

fukui2012_02.indb 214

14.1.9 1:47:26 PM

Ⅳ 研究業績 (2012)(1) The overall catalytic cycle is found to consist of four basic processes: oxidative addition,
decarboxylation, cycloaddition, and reductive elimination (Scheme 3). The interesting selectivity between
the C−O, C−C, and C−N bond activations of the isatoic anhydride R1 is examined first. Calculations suggestthat the anhydride C(=O)−O bond is preferentially activated in either the bis-ligand (phosphine and alkyne)
pathway or the alternative monophosphine pathway. Comparatively, although there is competition between
the two mechanisms through equilibrium reaction, the bis-ligand (phosphine and alkyne) pathway is morefavorable (ΔG°⧧ = 14.31 kcal/mol) (Figure 2). It means that the alkyne participates into the reaction in theinitial catalytic stage. FMO analyses of TS1aAL1 indicate that the CT from the 3dπ-Ni MO to the antibonding

LUMO of isatoic anhydrides contributes to a weakening of the anhydride C(=O)−O bond in the oxidative
addition process. The replacement of strong electron-donating ligand enhances the degree of CT, accordingly
promote the anhydride C(=O)−O bond cleavage.

Scheme 3(2) The exothermic decarboxylation proceeds through two steps, the formation of Ni−N bond and CO2
elimination, with a ΔG°⧧ value of 12.92 and 9.71 kcal/mol, respectively. Wherein, the donation from－ 215 －

fukui2012_02.indb 215

14.1.9 1:47:27 PM

Ⅳ 研究業績 (2012)

p-electrons of N to empty acceptor Ni orbital contributes the Ni‒N bond formation, which essentiallypromotes the following CO2 elimination. In view of this point, other heteroatom (O and S) and C atom effecton the decarboxylation process was examined. The substitution of N by C signficantly increases the ΔG°⧧
value of decarboxylation to 41.91 kcal/mol, even though the oxidative addition becomes easier with ΔG°⧧

value of 11.05 kcal/mol. The substitutions of N by O and S with more valence electron pairs facilitate theoxidative addtion and decarboxylation processes, especially the later step. The O and S substitutions
signficantly decrease the ΔG°⧧ value of decarboxylation to 2.17 and ‒9.17 kcal/mol, respectively.

Figure 2. Energy Profile (ΔGº353.15) for the Full Catalytic Cycle in Scheme 3.
(3) Cycloaddition process also undergoes two steps: the ligands (AL1 and PMe3) rotation and thebut-2-yne (AL1) insertion. The former step requires a ΔG°⧧ value of 7.40 kcal/mol. Then, AL1 more readily

inserts into the acyl-nickel (Ni−CO) bond instead of the Ni−N bond after CO2 elimination with a ΔG°⧧ valueof 12.26 kcal/mol. In the ligands rotation step, the gradually bending AL1 ligand decreases its unoccupied π*orbital energy, which favors the accumulation of electrons on the AL1 by πNi back donation, and then makes
C10 become an active nucleophilic site to interact with electrophilic C2 center in the following the AL1
insertion step. Additionally, regioselectivity of the alkynes insertion was investigated when the polarizedalkynes, 1-(silyl)propyne (AL3) and 1-(trimethylsilyl)propyne (AL4), are utilized. It is found that bothelectronic effect and steric effect influence the regioselectivity, but the latter play a major role.
(4) The last and facile reductive elimination is found to be promoted by the addition of a second
electron-donating AL1 ligand with a very facile step a ΔG°⧧ value of 4.65 kcal/mol.

The present mechanism investigations on this efficient and complicated Ni-catalyzed intermoleculardecarboxylative cycloaddition reaction should be not only improve our understanding of the observed
experimental facts but also shed important light on how to further expand their scope and utility.

－ 216 －

fukui2012_02.indb 216

14.1.9 1:47:27 PM

Ⅳ 研究業績 (2012)

2. Original papers(1) Wei Guan, Shinichi Yamabe, Shigeyoshi Sakaki“Interest in new heterodinuclear transition-metal/main-group-metal complexes: DFT studyof electronic structure and mechanism of fluoride sensing function”
Dalton Trans. 42, 8717–8728(2013).
(2) Shinichi Yamabe, Wei Guan, Shigeyoshi Sakaki“Three Competitive Transition States at the Glycosidic Bond of Sucrose in Its
Acid-Catalyzed Hydrolysis”
J. Org. Chem. 78, 2527−2533(2013).
(3) Shinichi Yamabe, Wei Guan, Shigeyoshi Sakaki“Presence or absence of a novel charge-transfer complex in the base-catalyzed hydrolysisof N-ethylbenzamide or ethyl benzoate”
Beilstein J. Org. Chem. 9, 185–196(2013).
(4) Shinichi Yamabe, Gui-Xiang Zeng, Wei Guan, Shigeyoshi Sakaki“An aniline dication-like transition state in the Bamberger rearrangement”
Beilstein J. Org. Chem. 9, 1073–1082(2013).
(5) Shinichi Yamabe, Wei Guan, Shigeyoshi Sakaki“How is the anionic tetrahedral intermediate involved in the isomerization of aspartyl
peptides to iso-aspartyl ones? A DFT study on the tetra-peptide”
Org. Biomol. Chem. 10, 8007−8015(2012).
(6) Zhong-Ling Lang, Wei Guan, Li-Kai Yan, Shi-Zheng Wen, Zhong-Min Su, Li-Zhu Hao“The self-assembly mechanism of the Lindqvist anion [W6O19]2− in aqueous solution: adensity functional theory study”
Dalton Trans. 41, 11361–11368(2012).
(7) Wei Guan, Zhi-Jian Wu, Zhong-Min Su“DFT study of ionic peapod structures from single-walled carbon nanotubes and Lindqvist
tungstates”
Dalton Trans. 41, 2798–2803(2012).
3. Presentation at academic conferences(1) Wei Guan, Shinichi Yamabe, Shigeyoshi Sakaki“DFT study of colorimetric fluoride ion sensing by the heterodinuclear
main-group/transition-metal complexes through allosteric coordination”
The 6th Annual Meeting of Japan Society for Molecular Science (2P-126) Tokyo, Sep. 19,
2012.

－ 217 －

fukui2012_02.indb 217

14.1.9 1:47:28 PM

Ⅳ 研究業績 (2012)

Yue CHENSPR Fellow, Fukui kenichi Memorial Research Group 2(From 16 Jul. 2012)
1. Summary of the research of the year
Theoretical Study of Mononuclear Nickel(I), Nickel(0), Copper(I), and Cobalt(I) Dioxygen Complexes:
New Insight into Differences and Similarities in Geometry and Bonding Nature
Activation of dioxygen by such first row transition metals as Mn, Fe, Co, Ni, and Cu plays
crucial roles in biological oxidation. However, the nickel-dioxygen interaction and the role ofthe nickel center in the relevant dioxygen complexes have been much less investigated thanthose of copper-dioxygen complexes despite the importance of the nickel-dioxygen species insuperoxide dismutase. It is of considerable importance to know how much and why theelectronic structure and bonding interaction of the nickel dioxygen complex are different from
and/or similar to those of the copper dioxygen complex.
In the present work, we theoretically investigated (N^N)Ni(O2), its cobalt(I) and copper(I)analogues,

and(Ph3P)2Ni(O2)

by

DFT

and

multi-state

restrictedactivespace

multi-configurational second-order perturbation (MS-RASPT2) method with large active space;see Scheme 1. We selected these complexes in expectation that we can clarify the differences
and/or similarities among cobalt(I), nickel(I),and copper(I) and between nickel(I) andnickel(0). Our purposes here are (1) toelucidate the electronic structures of thesecomplexes, in particular, to elucidate which
understanding of peroxo and superoxo iscorrect in these complexes, (2) to disclosethe metal and ligand effects on the M-O2
interaction, and (3) to find the determining

Scheme 1. The real and model complexes offactors for the M-O and the O-O bond(N^N)Ni(O2) and (N^N)Cu(O2)lengths and their bonding natures. During
this work, we found that pseudo-Jahn-Teller

distortion occurs only in (N^N)Ni(O2) but does not in other three complexes. We wish toemphasize that this new finding deeply relates to the electronic structures of these dioxygen
complexes interestingly.
Both DFT and MS-RASPT2 calculations clearly show that (N^N)Ni(O2) is not C2V but CS
symmetrical with different Ni-O bond lengths. On the other hand, (N^N)mCu(O2),(N^N)mCo(O2), and (Me3P)2Ni(O2) all have a C2V symmetrical structure in the ground state.

－ 218 －

fukui2012_02.indb 218

14.1.9 1:47:31 PM

Ⅳ 研究業績 (2012)

In (N^N)mNi(O2) with a C2V symmetry, the main configuration of the ground state is; see Table 1. The first excited state exists near the
ground state, where the energy difference is only 1.8 kcal·mol-1. On the other hand, the energy

Table 1. The relative energies of the ground and low lying excited states of model complexes.
WeightRelative Energy(%)(kcal·mol-1)

61.4

0.0

62.9

1.8

Ground state ( A”)

44.1

-1.0

First excited state (2A”)

45.2

3.3

54.1

0.0

54.6

14.4

66.6

0.0

30.9

4.0

Ground state ( A’)

64.5

0.0

First excited state (1A”)

55.9

19.1

State (symmetry)

Configurations(N^N)mNi(O2) (C2V)

Ground state (2A”)
2First excited state ( A”)(N^N)mNi(O2) (CS)
2

(N^N)mCu(O2)1

Ground state ( A’)1First excited state ( A”)(N^N)mCo(O2)Ground state (3A’)
3First excited state ( A”)(Me3P)2Ni(O2)1

gap in (N^N)mCu(O2), (N^N)mCo(O2), and (Me3P)2Ni(O2) are 14.4, 4.0, and 19.1 kcal·mol-1,
respectively, which are larger than in (N^N)mNi(O2). More important is the symmetry of theelectronic state; in (N^N)mNi(O2), both of the ground and the first excited states belong to A”
irreducible representation under CS symmetry, while they belong to different irreducible
representation in other complexes (Table 1).
The

forms a bonding orbital

orbital; see Scheme 2. Though theand an anti-bonding orbitalwith the O2

is singly occupied in (N^N)mNi, thebecomessingly occupied in (N^N)mNi(O2). The reason is easily understood by Scheme 2. Because theoverlaps well with the O2

orbital, its bonding MO becomes more stable in energy than theand its anti-bonding MO becomes more unstable than the

becomes singly occupied. The presence of one singly occupied. Hence, theprovides the low-lying

first excited state in (N^N)mNi(O2), which is responsible for the symmetry lowering. This is one－ 219 －

fukui2012_02.indb 219

14.1.9 1:47:34 PM

Ⅳ 研究業績 (2012)of the interesting features of (N^N)Ni(O2).
The O2 moiety strongly interacts with the metal moiety in the, as seen in Scheme

2. In the other natural orbitals, the d orbitals of the metal moiety and the �* orbitals of the O2
moiety are well localized. It is noted that theorbital of the O2 moiety is doubly occupied in

all these complexes. Thus, the character of the O2 moiety is mainly determined by the
Because theparticipates in the anti-bonding counterpart

population of the.

, we evaluated theconsidering all the natural orbitals. Also, we calculated the electron
population (moiety. The) of theorbital of the O2

is found between 0.96 and1.14. The total d orbital population is about
7 in (N^N)mCo(O2), 8 in the Ni analogue, 9in the Cu analogue, and 9 in (Me3P)2Ni(O2).
One of the important factors todetermine which is correct understanding,peroxo or superoxo, is the O-O �-bondorder; the �-bond order should be zero forperoxo and 0.5 for superoxo. The � bondorder

is defined by eq. (1);(1)

Scheme 2. The interactions between metal orbitals(

and) and O2

orbitals (

and

) in

where

is the occupation number ofthe�

orbital. The � bond order of the O2

moiety is evaluated to be 0.38 to 0.50.
Based on these results, it is likely concluded
that these complexes exhibit a considerable
superoxo nature rather than a peroxo
nature from the viewpoint of electron

distribution.
Here, all four complexes exhibit considerable superoxo nature in the O2 moiety, but the
M-O bond and O-O distance are considerably different among them. The M-O bond length
becomes shorter in the order (N^N)mCu(O2) > (N^N)mNi(O2) > (Me3P)2Ni(O2) > (N^N)mCo(O2).
In these dioxygen complexes, the charge transfer mainly occurs from theto theorbital of the O2 moiety via the π-type interaction (Scheme 2). One can expect that the M-O2
bonding interaction becomes stronger and the RM-O becomes shorter, as the CT from the metal－ 220 －

fukui2012_02.indb 220

14.1.9 1:47:38 PM

Ⅳ 研究業績 (2012)

d orbital to the O2

increases. The CT strength is determined by theorbital energy ()

in the valence state. We employed another parameter to take the difference in ionic radius into
account, as shown in eq (2).
(2)
where

is the M-O bond length in the complex andradius offrom that of Ni2+, as defined by eq (3).

is the difference of ionic(3)
where “n+” is the oxidation state. We found a good linear relationship between thetheas shown in Figure 1A. Also, we examined the relationship between theand the binding energy (increases as therelation between thewith theand). As expected, the calculated

value linearly

increases; see the red line in Figure 1B. The parabolic-likeand the(black line in Figure 1B) can be understoodorbital energy in the valence state and the promotion energy of the metal

moiety to the valence state.

－ 221 －

fukui2012_02.indb 221

14.1.9 1:47:41 PM

Ⅳ 研究業績 (2012)(A)
Figure 1. The correlations of (A)

(B)
vs.

and (B)

and

vs.

.

),

One can expect that the O-O distance depends on the electron population of the O2 moiety (because the O-O distance becomes longer as the electron population increases in theandorbitals. However, this relationship is not successful, as shown in Figure 2A. Because of thepresence of various CTs, the electron population of the O2 moiety is not a good index for the O-O
bond distance. For instance, the CT from the metal

to the O2

increases both theand the O-O distance, as expected. However, the O2 moiety has avalence state. This means that the CT can occur from the O2
doubly occupied. This CT decreases theto the M

conifiguration in thewhen thevalue and decreases the O-O distance. When the

(A)

value

is notis(B)

Figure 2. The correlations of the O-O bond length vs. (A) Mulliken charge of O2, and (B) O-O bondorder BOO-O.
－ 222 －

fukui2012_02.indb 222

14.1.9 1:47:42 PM

Ⅳ 研究業績 (2012)

unoccupied or singly occupied, the CT occurs from the O2

to the. Such CT decreases thebut increases the O-O distance, because the electron population decreases in the bonding MO.
Finally, we employed the O-O � bond order (relationship is presented between the), which is defined above. Apparently, a good

and the O-O bond distance, as shown in Figure 2B.

2. Original papers(1) Yue Chen, Shigeyoshi Sakaki“Theoretical Study of Mononuclear Nickel(I), Nickel(0), Copper(I), and Cobalt(I) Dioxygen
Complexes: New Insight into Differences and Similarities in Geometry and Bonding Nature”(submitted).
3. Presentation at academic conferences(1) Yue Chen, Shigeyoshi Sakaki“Electronic State and Bonding Nature of Nickel(I)- and Copper(I)- Dioxygen complexes:
MS-RASPT2 Study”
10th FIFC Symposium, Fukui Institute for Fundamental Chemistry, Kyoto Unviersity, Nov.
30, 2012－ 223 －

fukui2012_02.indb 223

14.1.9 1:47:42 PM

Ⅳ 研究業績 (2012)

Sayyed Fareed BHASHASPR Fellow, Fukui Kenichi Memorial Research Group 2(From 1 Feb. 2013)

Theoretical study of CO2 Insertion into Ni(I)-Alkyl and Ni(II)-Alkyl Bonds
The conversion of carbon dioxide (CO2) to useful chemicals is one of the most escalating areas of research.
Aryl halide is one of the best substrates for the synthesis of carboxylic acid from CO2. However, a direct CO2
insertion into aryl halide bond is not easy. In this context, the recently reported Ni-catalyzed direct carboxylationof PhCH2Cl with CO2 is considered efficient CO2 transformation reaction, where Ni(PCp3)2 (Cp = cyclopentyl) is
employed as a catalyst. Experimental results suggest that the Ni(I) species participates in the CO2 insertion, as
shown in Eq. (1), but the evidence has not been provided.
We theoretically investigated this reaction to unravel the reason why Ni(I) species is crucial for this reaction
and why Ni(II) is not suitable for the CO2 insertion; see Eq. (2).
(Cp3P)2NiI(CH2Ph) + CO2 →(Cp3P)2NiII(CH2Ph)Cl(Cp3P)2NiI(OOCCH2Ph)+ CO2 →

(Cp3P)2NiII(OCOCH2Ph)Cl

(1)
(2)

All geometries were optimized with the dispersion corrected B3LYP-D functional with BS-I basis set
system. In BS-I, Lanl2Tz(f) basis set for Ni, 6-31G(d) for H, C, O, P, and 6-31+G(d) for Cl were employed. The
solvent effect of N,N-dimethylformamide (DMF) was estimated by conductor-like polarizable continuum model(CPCM). A better basis system (BS-II) was used for evaluation of solvent effect. In BS-II, we employedLanl2Tz(f) basis set for Ni, cc-pVDZ for H, C, O, P, and aug-cc-pVDZ for Cl. The reliability of the B3LYP-D
functional is verified here with the oxidative addition to a model complex Ni(PH3)2; Ni(PH3)2 + PhCH2Cl →Ni(PhCH2)(Cl)(PH3)2. The calculated activation energy agrees well with that of CCSD(T).

Geometry and energy changes for the CO2 insertion into the Ni(I)-CH2Ph bond of (Cp3P)2NiI(CH2Ph) are
shown in Figure 1. First, CO2 coordinates to the Ni(I) centre to form 2-coordinated CO2 complex 2, from which
CO2 insertion occurs to afford a carboxylate complex 3 through a four-member transition state TS2-3 with anactivation barrier of 6.6 kcal/mol. Complex 3 isomerises to the most stable 2-coordinated carboxylate complex(Cp3P)2NiI(2-O2CCH2Ph) 4. The CO2 insertion into the Ni(II)-CH2Ph of (Cp3P)2NiII(CH2Ph)Cl 5 occurs througha four-member transition state without the formation of a Ni(II)-CO2 complex, as shown in Figure 2. The－ 224 －

fukui2012_02.indb 224

14.1.9 1:47:43 PM

Ⅳ 研究業績 (2012)activation barrier is 38.8 kcal/mol, which is substantially larger than that into the Ni(I)-CH2Ph bond. These results
indicate that the Ni(II)-CH2Ph is not reactive for CO2 insertion but the Ni(I)-CH2Ph is reactive.
We investigated the reasons from the bond energy and the interaction in the transition state. By the CO2
insertion reaction, the Ni-C bond is broken and the Ni-OCOR bond (R=CH2Ph)

Figure 1. Geometry and energy changes in the CO2 insertion of Ni(I)-CH2Ph bond of (Cp3P)2NiI(CH2Ph). Gibss
free energies are provided in parenthesis. All the bond lengths are in angstroms and angles are in degrees.
is formed. The Ni(I)-CH2Ph bond is calculated to be stronger (42.5 kcal/mol) than the Ni(II)-CH2Ph bond (32.1
kcal/mol) but the Ni(I)-OCOR bond (103.3 kcal/mol) is much stronger than the Ni(II)-OCOR bond (79.7
kcal/mol). NBO population analysis of TS2-3 and TS5-6 suggest that charge transfer (CT) from the Ni(I)-benzyl
moiety to CO2 much more strongly occurs than that from the Ni(II)-benzyl. The is because the benzyl group is
more negatively charged in the Ni(I)-benzyl complex than in the Ni(II)-benzyl group.

Figure 2. Geometry and energy changes in the CO2 insertion of Ni(II)-CH2Ph bond of (Cp3P)2NiII(CH2Ph)(Cl).
Gibss free energies are provided in parenthesis. All the bond lengths are in angstroms and angles are in degrees.

Thus, it is concluded that the CO2 insertion into Ni(I)-alkyl bond is thermodynamically andkinetically favourable.

－ 225 －

fukui2012_02.indb 225

14.1.9 1:47:44 PM

Ⅳ 研究業績 (2012)��

�

日本学術振興会 特別研究員(大阪大学) 訪問研究員 (2012 年 12 月 31 日まで)1� 今年度の研究の要�
今年度は酸化還元電位の算出に関する計算スキームの開発を行った。
1. 1 標準水素電極ポテンシャルと酸化還元電位の算出【序】物質の酸化還元反応は分子内の電子のやり取りによって生じる。この反応の起こりやすさは分子に固有な酸化還元電位によって定量化され、物質のみならず生体内においても非常に重要な役割を担うことが多い。しかし、酸化還元電位は絶対値の測定が不可能であるため、基準となる電極(標準水素電極(SHE)ポテンシャル)を用いた相対値で測定されている。量子化学計算を用いて酸化還元電位を算出するには、後で示すように酸化状態と還元状態のギブスエネルギーを計算して SHE
ポテンシャルを引くこととなる。だが、これまでの計算ではプロトンのギブスエネルギーに関する情報がなく、実験値として報告されている 4.44 V を計算手法に関わらず採用していたため、酸化還元電位の計算において大きな誤差が生じていた。本発表では、新しく SHE ポテンシャルを計算手法に依存する形で求める方法を提案し、生体内での電子移動に用いられる小分子(ビタミン c 等)から NADH, ユビキノン, 核酸塩基まで様々な大きさの分子における酸化還元電位の計算へ応用することを目的とする。
【方法】SHE ポテンシャル(ESHE)は、気相中の水素分子のギブスエネルギーとプロトンのギブスエ
ネルギーの 2 つにより計算できる。ここで、F はファラデー定数である。
ESHE={G(H+, aq)-1/2G(H2, gas)}/F.

(1)(1)式により SHE ポテンシャルが求まると、酸化還元電位(Eredox)は反応に寄与する電子数 n とギブスエネルギーΔGredox を用いて次式により導出できる。
Eredox= ΔGredox/nF - ESHE.

(2)

ただ、量子化学計算により水中でのプロトンのギブスエネルギーを導出することはできない。それに対して本研究においては、数種類のアルコールの pKa 値(実験値)と各分子における脱プロトン化に必要なギブスエネルギー(計算値)をプロットして線形近似を用いて、近似した直線の切片から水中でのプロトンのギブスエネルギーを導出する方法[1]を採用した。本研究では溶媒モデル(C-PCM)
を用いて、量子化学で頻繁に用いられる B3LYP 法を中心として計算を行った。また、比較のために高精度に自由エネルギーを算出する Gaussian-3 B3LYP (G3B3)法や HF, MP2 での基底関数極限を外挿的に求め、CCSD(T)などの高精度な計算手法によって補正する手法を採用した。
【結果】pKa 値(実験値)と計算の脱プロトンエネルギーの相関を図 1 に示す。図にあるように、アルコール分子においては線形関係にあることが分かった。Gaussian-3(G3)法で-265.5 kcal/mol と文献値(-265.9 kcal/mol)に極めて近い結果が得られた。

－ 226 －

fukui2012_02.indb 226

14.1.9 1:47:44 PM

Ⅳ 研究業績 (2012)

SHE ポテンシャルは、計算手法によって大きく変化するが、高精度な計算では実験値として採用されている 4.44 V に極めて近い値を算出している。一方で、HF では 3.83 Vと実験値よりも 0.6 V 程度低い値を出しているが、これは G(H2)が電子相関の欠如のために低く見積もられているためである。
MP2 においても TZ から QZ に増やしたが、若干 ESHE が大きく評価されたために、補外された CBS-limit では少し過大評価されてしまう。CCSD(FE, T)/aDZ の計算を行った所、frozen

図 1: HF, post HF 法による脱プロトン化エネルギ
ーの計算値と実験による pKa 値の相関 +SHE
G(H ,aq)core での結果とそこまで大きな変化はなかった。そのため、今回は Frozen core と Full electron で大きな差はないと思われる。一方で、CCSD(T,full)/aTZ の計算を実行すると ESHE が 4.48 V となって改善され global standard な SHE potential に近づく。その時の G(H+, aq)が-265.41 kcal/mol となり、それから得られるプロトンの水に対する溶媒和エネルギーが-259.13 kcal/mol と得られた。
これを利用して、小分子における 8 種類の酸化還元反応電位の実験値との平均誤差は表 1 のようになった。SHE ポテンシャルを調整しなければ、
B3LYP や HF においては大きな誤差が生じている。一方で、CCSD(T)や G3B3 などでは平均誤差

表 1: 小分子における酸化還元電位の平均絶対誤差(V)の SHE ポテンシャル調整前後での変化

調整前

調整後

B3LYP/6-31++G(d,p)

0.26

0.08

HF/CBS-Limit

0.48

0.17

CCSD(T)/aug-cc-pVDZ

0.10

0.08

G3B3

0.09

0.06

が 0.1V 程度とこの時点でも正確な値が出ている。
ここで、得られた SHE ポテンシャルを適用すると B3LYP で の 平 均 誤 差 は 0.08 V と な り 、
CCSD(T)などの高精度な計算と同程度の誤差に収まることが分かった。また、HF においても誤差は大幅に減っていることから、HF や DFT を用いて酸化還元電位を算出する場合、SHE ポテ

ンシャルの補正が不可欠となることがこの結果からも明らかとなった。
現在は、この SHE ポテンシャルを調整した計算スキームを用いて、ビタミン類・核酸塩基の酸化還元電位の算出を行っている。

1. 2 溶媒和モデルでの電�補正を��た金属錯体の酸化還元電位計算
遷移金属イオンを含む電子伝達タンパク質は構造や周りの環境に応じて電子伝達の性質、すなわ
ち酸化還元電位を変化させることができる。そのような効果を検証する一つの手法として、量子化
学計算に基づいた正確な電位の計算手法の確立が求められている。しかしながら、密度汎関数法を用いた金属錯体の電位計算においては(1)電位の零点となる標準水素電極(SHE)ポテンシャルの扱い(2)溶媒和モデルによる大きい価数を持つ錯体の溶媒和エネルギーの算出が難しい－ 227 －

fukui2012_02.indb 227

14.1.9 1:47:45 PM

Ⅳ 研究業績 (2012)などの困難を伴うことから、これまでに正確な計算は多く報告されてこなかった。そこで本研究では、特に(2)の問題に対してカウンターイオンを擬似的に置き、その溶媒和エネルギーを補正する手法を提案し、実際にヘム系に適用することを目的とする。本研究においては、Generalized-Born の式を基にして(3)式のような近似を提案する。
Eredox=1/F(Eox-Ered)- A (1-1/εr){ q|q| erf(µrq) -B(q-1)|q-1| erf(µr(q-1))}/r-ESHE(3)

ここで、Eox, Eredは酸化状態、還元状態の最適化構造でのエネルギーを、Fはファラデー定数、qは酸化状態の錯体の電荷、εr は測定に用いられた溶媒の誘電率を表す。r は溶媒和モデルにおいて、最初に生成する空洞を球とみなしたときの半径である。また、Aは擬似的に置いたカウン
ターイオンの半径に対応し、ESHE は先程と同様SHEポテンシャルである。本研究ではこれらのパラメータをテスト分子によりフィッティングして求めることとする。一連の計算はGaussian09 を用い、溶媒和モデルはC-PCM 法、密度汎関数はB3LYP を採用した。
フィッティングの結果、B3LYP/6-31++G(d,p)レベルの計算においては、テストの39 種類の錯体における平均誤差は0.14 V となった。特に酸化状態において+3 価, -3 価と大きな電荷を持つ10 種の錯体においては、一定のSHE ポテンシャルを用いた場合では平均誤差は0.78 V となるのに対して、(3)式を用いた場合は0.16 V まで大幅に減少する。また、この系は一度パラメータを決めた場合、どの金属錯体にも適用が可能となる。M1(bpy)3 (M1=Fe, Ru, Os)やM2(mnt)2 (M2=Ni, Pd,Pt)などの重金属を含む錯体の酸化還元電位も実験値と0.2 V 以下の誤差で算出することに成功した。最後に、
ヘムc のモデル錯体で誘電率依存性を算出したところ、1/εr と酸化還元電位に線形関係があり、タンパク質の環境とされるεr =4-20 の間で符号の変化が生じることが分かった。
【参考文献】[1] Matsui, T.; Baba, T.; Kamiya, K.; Shigeta, Y. Phys. Chem. Chem. Phys. 2012, 14, 4181. [2]Matsui, T.; Kitagawa, Y.; Okumura, M.; Shigeta, Y.; Sakaki, S. J. Comput. Chem.2013, 34, 21. [3] Matsui, T.;
Kitagawa, Y.; Shigeta, Y.; Okumura, M. J. Chem. Theory Comput. in press.

2. 論文(1) Y. Kitagawa, N. Yasuda, H. Hatake, T. Saito, Y. Kataoka, T. Matsui, T. Kawakami, S. Yamanaka,
M. Okumura and K. Yamaguchi, “Combination of approximate spin-projection and spin-restrictedcalculations based on ONIOM method for geometry optimization of large biradical systems”,
International Journal of Quantum Chemistry, 113, p.290-295 (2013).

(2) T. Matsui, Y. Kitagawa, M. Okumura, Y. Shigeta and S. Sakaki, "Consistent Scheme for
Computing Standard Hydrogen Electrode and Redox Potentials", Journal of Computational
Chemistry, 34, p. 21-26 (2013).

3. 学会�表(1) 松井 亨，馬場 剛史，安田 奈都美，神谷 克政, 北河 康隆，重田 育照，奥村 光隆「タンパク質内アミノ酸側鎖の酸解離定数の新規算出法と応用」
第15回 理論化学討論会 仙台 2012/5/25(2) Toru Matsui, Takeshi Baba, Katsumasa Kamiya, Mitsutaka Okumura, and Yasuteru Shigeta“Density functional theory based estimation of pKa value of polar residues: from amino acids to－ 228 －

fukui2012_02.indb 228

14.1.9 1:47:46 PM

Ⅳ 研究業績 (2012)minimal proteins”
14th International Congress of Quantum Chemistry, Colorado University, 2012/6/26(3) 松井 亨，北河 康隆，重田 育照，奥村 光隆, 榊茂好「標準水素電極ポテンシャルと酸化還元電位の算出法」
第6回 分子科学討論会 東京 2012/9/19(4) 松井 亨，北河 康隆，重田 育照，奥村 光隆, 榊茂好「標準水素電極ポテンシャルと酸化還元電位の新規算出法」
第23回基礎有機化学討論会 京都 2012/9/19(5) 松井 亨，北河 康隆，重田 育照，奥村 光隆「溶媒和モデルを利用した金属錯体の酸化還元電位の算出法と応用」
第93回 日本化学会春季年会、草津 2013/3/25－ 229 －

fukui2012_02.indb 229

14.1.9 1:47:46 PM

Ⅳ 研究業績 (2012)��

励

分子��研究所 ��研究�(���グループ所�)(2012 年 6 月 30 日まで)
1. 今年�の研究の��ブリッジ経由三重項励起エネルギー移動[1]【���】�
光合成系では、直接反応に寄与しない副産物として三重項励起状態が生成されることがあり、この三重項状態を励起エネルギー移動によって輸送し処理する過程の存在が確認されている。また、
有機 LED ではその原理上、発行に寄与しない大量の三重項励起状態が生成される。このような三重項励起状態の輸送は三重項ゆえに禁制遷移であり、中間状態をはさんだ二次以上の相互作用によって行われる。本研究では、そのような中間状態として、ブリッジを含む様々な電荷分離状態や励起状態を導入し、それぞれの状態の寄与を調べることで、三重項励起エネルギー移動のしくみを明ら
かにした。
【�法】
以前一重項励起エネルギー移動について計算した GFPc-ブリッジ-CFPcのモデルシステム[2](図１)の X=Tyrの構造を用いて、さらに、以前開発したプログラムを三重項励起エネルギー状態に拡張して同様の計算を行った。計算には以前と同様に CIS/D95 を用いており、計算手順も同様に、参照
図 1. GFPc-X-CFPc モデル。

分子として GFPc (両端に CH3 を含む)、
CFPc (両端に CH3 を含む)および、X (側鎖及びα炭素を含む)の３つを用いた MOD 法[3]により、それぞれのフラグメントに局在化した分子軌道を作り、残りのペプチド部分を Pipek-Mezey 法で局在化するというハイブリッド局在化法[4]を行いてモデル全域における局在化分子軌道を得ている。分子軌道は GFPc-pep1-X-pep2-CFPc の 5
か 所 の フ ラ グ メ ン ト に 局 在 化 し て お り 、 こ れ ら の 局 在 分 子 軌 道 か ら 今 回 は 三 重 項 Slater
determinant を基底として、EET トンネル経路を計算した。電子トンネル経路の計算にはグリーン関数法、トンネルエネルギーは CFPc と GFPc のそれぞれの最低三重項状態と基底状態のエネルギー
差の平均値を用いた(0.0724au)。
【��】
以前計算した一重項励起エネルギー移動では、フェルスター機構に基づく双極子共鳴相互作用の直接項が主体であり、ブリッジ経由の項についても、同様の双極子共鳴による局在励起状態経由の－ 230 －

fukui2012_02.indb 230

14.1.9 1:47:47 PM

Ⅳ 研究業績 (2012)

トンネル経路が主体となる(図 2 上段)。
このような相互作用は長距離力であり、トンネル経路は少ないステップで構成されていた。一方で今回計算した三重項励
起エネルギー移動では、上記の双極子相互作用は禁制であり、結果として、より弱く短距離でしか効かない電子移動、ホール移動型の相互作用が主体となった。
その結果、ドナー、アクセプター状態間の直接項の寄与は小さいものになり、ブリッジ経由項は図 2 下段に示したような
複数ステップの電位移動とそれとカップル

図 2. 一重項および三重項ブリッジ経由励起エネ

したホール移動の組み合わせによる多段階

ルギー移動トンネル経路模式図

ステップのトンネル経路を持つことがわかった。
[1] T. Kawatsu, J. Hasegawa, J. Phys. Chem. C 116 23252-23256(2012).
[2] T. Kawatsu, J. Hasegawa, Int. J. Quantum Chem. 113, 563-568(2013).
[3] K. Toyota, M. Ehara, H. Nakatsuji, Chem. Phys. Lett. 356, 1-6(2002).
[4] J. Hasegawa, T. Kawatsu, K. Toyota, K. Matsuda, Chem. Phys. Lett. 508, 171-176(2011).

2. 論�(1) Tsutomu Kawatsu, “Review: Pathway analysis for peptide-mediated electronic
coupling in the super-exchange mechanism of ET and EET,” Pep. Sci. 100,
100-113(2013).
(2) Tsutomu Kawatsu, and Jun-ya Hasegawa, “Sequentially Coupled Hole–ElectronTransfer Pathways for Bridge-Mediated Triplet Excitation Energy Transfer,”
J. Phys. Chem. C 116, 23252–23256(2012).
(3) Tsutomu Kawatsu, Jun-ya Hasegawa, and Kenji Matsuda, “Singlet Excitation
Energy Transfer Mediated by Local Exciton Bridges,” J. Phys. Chem. C 116,
13865-13876(2012).
3. 学会��
(1) 河津励、長谷川淳也「三重項励起エネルギー移動のトンネル経路」
第 15 回理論化学討論会 仙台 2012/5/25 2P14(2) 長谷川淳也、河津励「凝集系における分子の励起状態：局在化軌道を用いた分子間相互作用の解析」
第 15 回理論化学討論会 仙台 2012/5/24 1P30

－ 231 －

fukui2012_02.indb 231

14.1.9 1:47:47 PM

fukui2012_02.indb 232

14.1.9 1:47:48 PM

Ⅴ 資料 (2012)Ⅴ資料

１．外国人共同研究者受入れ状況（平成 24 年度）

氏名

受入れ身分

受入れ期間

所属機関・職

Vayssilov Georgi

外国人

平成24年7月21日〜

University of Soﬁa

共同研究者

平成24年8月18日（ブルガリア）・教授

Petkov Petko

外国人

平成24年7月23日〜

University of Soﬁa

共同研究者

平成24年8月2日（ブルガリア）・助手

Rangelov Miroslav

外国人

平成24年7月23日〜

Bulgarian Academy of

共同研究者

平成24年8月2日

Sciences

受入れ教員

諸熊奎治

諸熊奎治

諸熊奎治

（ブルガリア）・助手

研究内容

複雑分子系のシミュレーション

複雑分子系のシミュレーション

複雑分子系のシミュレーション

Oak Ridge National
Predrag Krstic

外国人

平成25年2月17日〜

Laboratory

共同研究者

平成25年3月2日（アメリカ）Senior

諸熊奎治

複雑分子系のシミュレーション

Research Staff Member－ 233 －

fukui2012_02.indb 233

14.1.9 1:47:48 PM

Ⅴ 資料 (2012)

２．海外渡航一覧（平成 24 年度）

職

名

氏

名

期間（自）

期間（至）

研究員（学術研究奨励）諸熊奎治

2012.5.21

2012.7.1

アメリカ合衆国

准教授

長谷川

淳也

2012.5.29

2012.6.3

カナダ

2012.6.24

2012.7.2

アメリカ合衆国研究員（学術研究奨励）

KIM CHUNGHAN

目

的

地

准教授

長谷川

淳也

2012.6.25

2012.7.2

アメリカ合衆国

特任准教授

石田

俊正

2012.6.24

2012.7.2

アメリカ合衆国

特定研究員

畑中

美穂

2012.6.24

2012.7.2

アメリカ合衆国

2012.6.24

2012.7.2

アメリカ合衆国

JSPS 外国人特別研究員

PETROVA, Galina

研究員（学術研究奨励）榊茂好2012.6.25

2012.7.2

アメリカ合衆国

研究員（科学研究）中垣雅之

2012.6.25

2012.7.2

アメリカ合衆国

研究員（科学研究）塚本晋也

2012.6.24

2012.6.30

アメリカ合衆国

特定研究員

岡本

隆一

2012.6.23

2012.6.30

アメリカ合衆国

助教

池野

豪一

2012.7.22

2012.7.28

中国

特定研究員

岩城

貴史

2012.7.27

2012.8.7

ロシア

研究員（学術研究奨励）諸熊奎治

2012.8.4

2012.8.15

中国

研究員（学術研究奨励）榊茂好2012.8.9

2012.8.12

中国

研究員（学術研究奨励）諸熊奎治

2012.8.17

2012.8.25

アメリカ合衆国

教授

田中

一義

2012.9.4

2012.9.8

アメリカ合衆国研究員（学術研究奨励）

Li, Haibei

2012.9.17

2012.10.1

ドイツ

研究員（学術研究奨励）諸熊奎治

2012.9.14

2012.9.22

ロシア

センター長

田中

一義

2012.10.10

2012.10.15

ドイツ連邦共和国研究員（学術研究奨励）榊茂好2012.10.2

2012.10.6

フランス

研究員（学術研究奨励）諸熊奎治

2012.10.12

2012.10.18

アルジェリア

センター長

田中

一義

2012.11.22

2012.11.26

イギリス

研究員（学術研究奨励）諸熊奎治

2013.2.6

2013.2.19

アメリカ合衆国研究員（学術研究奨励）諸熊奎治

2013.3.3

2013.3.11

ベルギー、フランス

特定研究員

畑中

美穂

2013.3.5

2013.3.10

フランス

助教

池野

豪一

2013.2.17

2013.2.24

オランダ

特任准教授

石田

俊正

2013.2.24

2013.2.28

台湾

研究員（学術研究奨励）

Bai Fu-Quan

2013.3.1

2013.3.4

中国－ 234 －

fukui2012_02.indb 234

14.1.9 1:47:49 PM

Ⅴ 資料 (2012)

３．研究業績一覧（平成 24 年度）№

Authors

長谷川

Title

JournalVolume (Number),first page tolast page

year

淳也

1

J. Hasegawa

Fragment-Based Configuration
Interaction Wave Function to Calculate
Environmental Effect on Excited States inProteins and Solutions

2

S. Nishizawa, J. Hasegawa,
K. Matsuda

Theoretical Investigation of the β Value ofthe Phenylene and Phenylene Ethynylene
Units by Evaluating Exchange Interaction
between Organic Radicals

Chem. Phys.
Lett.

555, 187–190

2013

3

T. Kawatsu and J. Hasegawa

Excitation Energy Transfer in GFP-XCFP Model Peptides (X=amino acids):
direct vs. through-bridge energy transfers

Intern. J.
Quantum. Chem.

113(4), 563-568

2013

4

T. Kawatsu and J. Hasegawa

Sequentially Coupled Hole-ElectronTransfer Pathways for Bridge-MediatedTriplet Excitation Energy Transfer

J. Phys. Chem.
C

116(44), 23252–
23256

2012

5

J. Hasegawa, K. J. Fujimoto,and T. Kawatsu

A Configuration Interaction Picture for a
Molecular Environment Using Localized
Molecular Orbitals: The Excited States ofRetinal Proteins

J. Chem. Theo.
Comp.

8(11), 44524461

2012

6

T. Kawatsu, K. Matsuda, and
J. Hasegawa

Singlet Excitation Energy Transfer
Mediated by Local Exciton Bridges

J. Phys. Chem. C

116(26), 1386513876

2012

7

J. Hasegawa, K. Fujimoto,and H. Nakatsuji

Color tuning in human cone visual
pigments: the role of the protein
environment

Progress in
Theoretical
Chemistry andPhysics

26, 89-502

2012

8

T. Sakano, J. Hasegawa,K. Higashiguchi, and K.
MatsudaChronological Change from FaceOn to Edge-On Ordering of Zinc
Tetraphenylporphyrin at PhenyloctaneHOPG Interface

Chem. Asian J.

7(2), 394-399

2012

9

Y. Yamamoto, J. Hasegawa,and Y. Ito

Kinetic investigation on carbamate
formation from the reaction of carbon
dioxide with amino acids in homogeneous
aqueous solution

J. Phys. Org.
Chem.

25(3), 239-247

2012

10

S. Akatsu, Y. Kanematsu,
T. Kurihara, S. Sueyoshi,
Y. Arikawa, M. Onishi,
S. Ishizaka, N Kitamura,
Y. Nakao, S. Sakaki, K.
Umakoshi

Syntheses and Luminescent Propertiesof 3,5-Diphenylpyrazolato-Bridged
Heteropolynuclear Platinum Complexes.
The Influence of Chloride Ligands on
the Emission Energy Revealed by the
Systematic Replacement of Chloride
Ligands by 3,5-Dimethylpyrazolate

Inorg. Chem.

51, 7977-7992

2012

11

Y. Nakajima, S. Sakaki, Y.
Nakao, H. Suzuki

Theoretical Study of Dihydrogen
Activation by a Trinuclear Ruthenium μ3Imido Complex

Organometallics

31, 5342–5348

2012

12

Y. Hayashi, Y. Matano, K.
Suda, Y. Kimura, Y. Nakao,
H. Imahori

Effects of Carbon–Metal–Carbon
Linkages on the Optical, Photophysical,
and Electrochemical Properties of
Phosphametallacycle-Linked Coplanar
Porphyrin Dimers

Chem. Eur. J.

18, 1597215983

2012

中尾

Chem. Phys.
Lett.

571, 77–81

2013

嘉秀

－ 235 －

fukui2012_02.indb 235

14.1.9 1:47:49 PM

Ⅴ 資料 (2012)

Title

JournalVolume (Number),first page tolast page

year

13

Wilfredo Credo Chung,
Shinkoh Nanbu, andToshimasa Ishida

A QM/MM Trajectory Surface Hopping
Approach to Photoisomerization of
Rhodopsin and Isorhodopsin. The Origin
of Faster and More Efficient Isomerization
for Rhodopsin

J. Phys. Chem. B

116, 8009−8023

2012

14

Tatsuhiro Murakami,
Manabu Nakazono, Alexey
Kondorskiy, Toshimasa
Ishida and Shinkoh Nanbu

Photochemical dynamics ofindolylmaleimide derivatives

Phys. Chem.
Chem. Phys.

14, 11546–
11555

2012

15

Toshimasa Ishida andShigetoshi Aono

A model theoretical study on ligand
exchange reactions of CooA

Phys. Chem.
Chem. Phys.

15, 6139-6148

2013

16

Jun-ichi Aihara, Masakazu
Makino, Toshimasa Ishida,
and Jerry R. Dias

Analytical Study of Superaromaticity
in Cycloarenes and Related Coronoid
Hydrocarbons

J. Phys. Chem. A

in press

2013

17

Thomas Höche, and Hidekazu
Ikeno, Marisa Mäder, Grant
S. Henderson, and Robert I.R.
Blyth, Brian C. Sales, andIsao Tanaka

Vanadium L2,3 XANES experiments andfirst-principles multielectron calculations:
Impact of second-nearest neighboring
cations on vanadium-bearing fresnoites

Am. Mineral.

98, 665-670

2013

18

Hidekazu Ikeno, MichaelKrause, Thomas Hoöhe,
Christian Patzig, Yongfeng
Hu, Antje Gawronski, Isao
Tanaka and Christian Rüssel

Variation of Zr-L2,3 XANES in tetravalentzirconium oxides

J. Phys.:Condens. Matter

25, art. no.
165505

2013

№

石田

池野

永瀬

Authors

俊正

豪一

茂

19

H. Zheng, X. Zhao, W. -W.
Wang, T. Yang, and S. Nagase

Sc2@C70 Rather Than Sc2C2@C68: Density
Functional Theory Characterization ofMetallofullerene Sc2C70

J. Chem. Phys.

137, 014308(5 pages)

2012

20

S. Sato, S. Seki, G. Luo, M.
Suzuki, J. Lu, S. Nagase, andT. Akasaka

Tunable Charge-Transport Properties
of Ih-C80 Endohedral Metallofullerenes:
Investigation of La2@C80, Sc3N@C80, andSc3C2@C80

J. Am. Chem.
Soc.

134,1168111686

2012

21

L. Feng, M. Rudolf, S.
Wolfrum, A. Troeger, Z.
Slanina, T. Akasaka, S.
Nagase, N. Martin, T. Ameri,
C. J. Brabec, and D. M. Guldi

A Paradigmatic Change: Linking
Fullerenes to Electron Acceptors

J. Am. Chem.
Soc.

134, 1219012197

2012

22

W. -W. Wang, J. -S. Dang,
J. -J. Zheng, X. Zhao, E.
Osawa, and S. Nagase

Metal-Promoted Restoration of Defective
Graphene

J. Mater. Chem.

22, 1637016375

2012

23

J. -S. Dang, W. -W. Wang,
J. -J. Zheng, X. Zhao, E.
Osawa, and S. Nagase,

Fullerene Genetic Code: Inheritable
Stability and Regioselective C2 Assembly

J. Phys. Chem. C

116, 1623316239

2012

24

K. Sato, M. Kako, M. Suzuki,
N. Mizorogi, T. Tsuchiya, M.
M. Olmstead, A. L. Balch, T.
Akasaka, and S. Nagase

Synthesis of Silylene-Bridged Endohedral
Metallofullerene Lu3N@Ih-C80

J. Am. Chem.
Soc.

134,1603316039

2012

25

Y. Takano, S. Obuchi, N.
Mizorogi, R. Carcia, M.
A. Herranz, M. Rudolf, S.
Wolfrum, D. M. Guldi, N.
Martin, S. Nagase, and T.
Akasaka

Stabilizing Ion and Radical Ion Pairs
States in a Paramagnetic Endohedral
Metallofullerene/π-Extended
Tetrathiafulvalene Conjugate

J. Am. Chem.
Soc.

134, 1610316106

2012－ 236 －

fukui2012_02.indb 236

14.1.9 1:47:50 PM

Ⅴ 資料 (2012)№

Authors

Title

JournalVolume (Number),first page tolast page

year

26

T. Yang, X. Zhao, and S.
NagaseStructural Determination on Yb@C78
Reveals an Unexpected Relationship of
Yb@C2n (2n = 74-78)

J. Phys. Chem. C

116, 2164021645

2012

27

T. Yang, X. Zhao, S. -T. Li,
and S. Nagase

Is the Isolated Pentagon Rule Always
Satisfied for Metallic Carbide Endohedral
Fullerenes?

Inorg. Chem.

51, 1122311225

2012

28

Z. Slanina, F. Uhlik, S.
-L. Lee, L. Adamowicz, T.
Akasaka, and S. Nagase

Stability Computations for Isomers of
La@Cn (n = 72, 74, 76)

Molecules

17, 13146-13156

2012

29

M. Suzuki, Z. Slanina, N.
Mizorogi, X. Lu, S. Nagase,
M. M. Olmstead, A. L. Balch,and T. Akasaka,

Single-Crystal X-ray Diffraction Study ofThree Yb@C82 Isomers Cocrystallizedwith NiII (octaethylporphyrin)

J. Am. Chem.
Soc.

134, 187721877

2012

30

Y. Takano, S. Obuchi, N.
Mizorogi, R. Garcia, M. A.
Herranz, M. Rudolf, D. M.
Guldi, N. Martin, S. Nagase,and T. Akasaka

An Endohedral Metallofullerene as a Pure
Electron Donor: Intramolecular ElectronTransfer in Donor-Acceptor Conjugates of
La2@C80 and 11,11,12,12-Tetracyano-9,10anthra-p-quinodimethane (TCAQ)

J. Am. Chem.
Soc.

134, 1940119408

2012

31

T. Tanikawa, M. Saito, J.
-D. Guo, S. Nagase, and
M. MinouraSynthesis,
Structures, andOptical Properties ofHeterasumanenes Containing
Group 14 Elements and Their
Related Compounds

Synthesis, Structures, and Optical
Properties of Heterasumanenes
Containing Group 14 Elements and Their
Related Compounds

Eur. J. Org.
Chem.

7135-7142

2012

32

K. Sato, M. Kako, N.
Mizorogi, T. Tsuchiya, T.
Akasaka, and S. Nagase

Bis-Silylation of Lu3N@Ih-C80:
Considerable Variation in the Electronic
Structures

Org. Lett.

14, 5908-5911

2012

33

X. Lu, L. Feng, T. Akasaka,
and S. Nagase

Current Statues and Future Developmentsof Endohedral Metallofullerenes

Chem. Soc. Rev.

41, 7723-7760

2012

34

N. Kano, N. Yoshinari, Y.
Shibata, M. Miyachi, T.
Kawashima, M. Enomoto, A.
Okazawa, N. Kojima, J. -D.
Guo, and S. Nagase

Anionic Iron Complexes with a Bondbetween an Ate-Type PentacoordinatedGermanium and an Iron Atom

Organometalic

21, 8059-8062

2012

35

T. Tsuchiya, M. Rudolf,
S. Wolfrum, S. G.
Radhakrishnan, R. Aoyama,
Y. Yokosawa, A. Oshima, T.
Akasaka, S. Nagase, and D.
M. Guldi,

Coordinative Interactions between
Porphyrins and C60, La@C82, and La2@
C80

Chem. -Eur.

19, 558-565

2013

36

L. Feng, M. Suzuki, N.
Mizorogi, X. Lu, M. Yamada,
T. Akasaka, and S. Nagase

Mapping the Metal Positions inside
Spherical C80 Cages: Crystallographic andTheoretical Studies of Ce2@D5h-C80 and
Ce2@Ih-C80

Chem. -Eur. J

19, 988-993

2013

37

W. -W. Wang, J. -S. Dang, J.
-J. Zheng, X. Zhao, and S.
NagaseSelective Growth of Fullerenes from C60
to C70: Inherent Geometrical Connectivity
Hidden in Discrete Experimental
Evidence

J. Phys. Chem. C

117, 2349-2357

2013

38

T. Yang, X. Zhao, and S.
NagaseQuantum Chemical Insight of theDimetallic Sulfide Endohedral
Fullerene Sc2S@C70: Does It Possess theConventional D5h Cage?

Chem. Eur.

19, 2649-2654

2013

39

M. Yamada, Z. Slanina, N.
Mizorogi, A. Muranaka,
Y. Maeda, S. Nagase, T.
Akasaka, and N. Kobayashi

Application of MCD Spectroscopy and
TD-DFT to Endohedral Metallofullerenes
for Characterization of their Electronic
Transitions

Phys. Chem.
Chem. Phys.

15, 3593-3601

2013－ 237 －

fukui2012_02.indb 237

14.1.9 1:47:50 PM

Ⅴ 資料 (2012)

JournalVolume (Number),first page tolast pageyear

Toward a Silicon Version of Metathesis:
From Schrock-Type Titanium Silylidenes
to Silatitanacyclobutenes

J. Am. Chem.
Soc.

135, 2987-2990

2013

41

Y. Morinaka, S. Sato, A.
Wakamiya, H. Nikawa, N.
Mizorogi, F. Tanabe, M.
Murata, K. Komatsu, K.
Furukawa, T. Kato, S. Nagase

X-Ray Observation of a Helium Atom andPlacing a Nitrogen Atom inside He@C60
and He@C70

Nat. Commun.

4, 1554(5 pages)

2013

42

T. Kuwabara, M. Saito, J. –D.
Guo, and S. Nagase

Unexpected Formation of Ru 2Sn 2 Bicyclic
Four-Membered Ring Complexes
with Butterfly and Inverse-Sandwich
Structures

Inorg. Chem.

52, 3585-3587

2013

43

S. Sato, Y. Maeda, J. –D.
Guo, M. Yamada, N.
Mizorogi, S. Nagase, and T.
Akasaka

Mechanistic Study of the Diels-Alder
Reaction of Paramagnetic Endohedral
Metallofullerene: Reaction of La@C82 with
1,2,3,4,5-Pentamethylcyclopentadiene

J. Am. Chem.
Soc.

135, 5582-5587

2013

44

Y. –P. Xie, X. Lu, T.
Akasaka, and S. Nagase

New Features in Coordination Chemistry:
Valuable Hints from X-Ray Analyses ofEndohedral Metallofullerenes

Polyhedron52, 3-9

2013

45

S. Nagase

Multiple Bonds between Lead Atoms andShort Bonds between Transition Metals

Pure Appl. Chem.

85, 649-659

2013

諸熊

奎治

46

P. S. Krstic, J. P. Allain, C. N.
Taylor, J. Dadras, S. Maeda,
K. Morokuma, J. Jakowski,
A. Allouche, and C. H.
Skinner

Deuterium Uptake in Magnetic Fusion
Devices with Lithium Conditioned
Carbon Walls

Phys. Rev. Lett.

110, 105001/1-5

2013

47

B. Fu, J. M. Bowman, H.
Xiao, S. Maeda, and K.
Morokuma

Quassiclassical Trajectory Studies of the
Photodissociation Dynamics of NO3 fromthe D0 and D1 Potential Energy Surfaces

J. Chem. Theo.
Comp.

9, 893–900

2013

48

K. R. S. Chandrakumar,
A. J. Page, S. Irle and K.
Morokuma

Carbon Coating Precedes SWCNT
Nucleation on Silicon Nanoparticles:
Insights from QM/MD Simulations

J. Phys. Chem. C

117, 4238–4244

2013

49

S. Maeda, K. Ohno and K,
Morokuma

Systematic Exploration of the Mechanismof Chemical Reactions: the Global
Reaction Route Mapping (GRRM)
Strategy by the ADDF and AFIR Methods

Phys. Chem.
Chem. Phys.

15, 3683-3701

201
3

50

A. J. Page, C.-P. Chou, B. Q.
Pham, H. Witek, S. Irle and K.
Morokuma

Quantum Chemical Investigation of
Epoxide and Ether Groups in Graphene
Oxide and Their Vibrational Spectra

Phys. Chem.
Chem. Phys.

15, 3725-3735

2013

51

L. Ding, L. W. Chung, K.
Morokuma

Reaction Mechanism of Photo-induced
Decarboxylation of the Photoactivatable
Green Fluorescent Protein: An
ONIOM(QM:MM) Study.

J. Phys. Chem. B

117, 1075-84

2013

52

K. R. S. Chandrakum ar, A.
Puretzky, C. Rouleau, J. D.
Readle, D. B. Geohegan,
K. More, V. Krishnan, G.
Duscher, B. Sumpter, S. Irle,
and K. Morokuma

High-Temperature Transformation of FeDecorated Single-Wall Carbon Nanohorns
to Nanooysters: A Combined Experimental
and Theoretical Study,

Nanoscale5, 1849–1857

2013

53

S. Maeda, E. Abe, M.
Hatanaka, T. Taketsugu, and
K. Morokuma

Exploring Potential Energy Surfacesof Large Systems with Artificial Force
Induced Reaction in Combination with
ONIOM and Microiteration

J. Chem. Theo.
Comp.

5, 5058–5063

2012

№

Authors

Title

40

V. Y. Lee, S. Aoki, T.
Yokoyama, S. Horiguchi, A.
Sekiguchi, H. Gornitzka, J.
–D. Guo, and S. Nagase－ 238 －

fukui2012_02.indb 238

14.1.9 1:47:50 PM

Ⅴ 資料 (2012)№

Authors

Title

JournalVolume (Number),first page tolast page

year

54

A. J. Page, T. Isomoto,
J. Knaup, S. Irle, and K.
Morokuma

Effects of Molecular Dynamics
Thermostats on Descriptions of Chemical
Non-Equilibrium

J. Chem. Theo.
Comp.

8, 4019–4028

2012

55

A. Y. Timoshkin, and K.
MorokumaNovel group 13 Lewis superacids and 1315 donor-acceptor cryptands for hydrogen
activation: a theoretical study

Phys. Chem.
Chem. Phys.

14, 1491114916

2012

56

H.-B. Li, A. J. Page, S. Irle,
and K. Morokuma

SWCNT Growth from Chiral Carbon
Nanorings: Prediction of Chirality andDiameter Influence on Growth Rates

J. Am. Chem.
Soc.

134, 15887–
15896

2012

57

P. S. Krstic, J. P. Allai, A.
Allouched, J, Jakowski, J.
Dadras, C. N. Taylor, Z. Yang,
K. Morokuma, and S. Maeda

Dynamics of deuterium retention andsputtering of Li–C–O surfaces

Fusion Eng,
Design87, 1732-1736

2012

58

Z. Ke, S. Abe, T. Ueno, and K.
Morokuma

Catalytic Mechanism in Artificial
Metalloenzyme: QM/MM Study of
Phenylacetylene Polymerization by
Rhodium Complex Encapsulated in apoFerritin

J. Am. Chem.
Soc.

134, 15418–
15429

2012

59

H. Xiao, S. Maeda and K.
Morokuma

Global Ab Initio Potential Energy Surfaces
for Low-lying Doublet States of NO3

J. Chem. Theo.
Comp.

8, 2600–2605

2012

60

S. Sekharan, K. Katayama, H.
Kandori and K. Morokuma

The “OH-Site” Rule for Seeing Red andGreen

J. Am. Chem.
Soc.

134, 10706–
10712

2012

61

W. Treesuwan, H. Hirao,
K. Morokuma, and S.
Hannongbua

Characteristic vibration patterns andprotein binding of odor compounds frombread baking volatiles: Density functional,
ONIOM study and principal component
analysis (PCA)

J. Mol. Model.

18, 2227–2240

2012

62

Y. Wang, H.-J. Qian, K.
Morokuma, and S. Irle

Coupled Cluster and Density Functional
Theory Calculations of Atomic Hydrogen
Chemisorption on Pyrene and Coronene
as Model Systems for Graphene
Hydrogenation

J. Phys. Chem. A

116, 7154–7160

2012

63

K. P. O’Halloran, C. Zhao,
N. S. Ando, A. J. Schultz,
T. F. Koetzle, P. M. B.
Piccoli, B.Hedman, K. O.
Hodgson, E. Bobyr, M. L.
Kirk, S. Knottenbelt, E. C.
Depperman, B. Stein, T.
M. Anderson, R. Cao, Y. V.
Geletii, K. I. Hardcastle, D.
G. Musaev, W. A. Neiwert, X.
Fang, K. Morokuma, S. Wu, P.
Kögerler and C. L. Hill

Revisiting the Polyoxometalate-Based
Late-Transition-Metal-Oxo Complexes:
The “Oxo Wall” Stands

Inorg. Chem.

51, 7025–7031

2012

64

S. Maeda, T. Taketsugu and K.
Morokuma

Automated Exploration of Photolytic
Channels of HCOOH: Conformational
Memory via Excited State Roaming

J. Phys. Chem.
Lett.

3, 1900-1907

2012

65

H.-B. Li, A. J. Page, Y. Wang,
S. Irle, and K. Morokuma

Sub-Surface Nucleation of Graphene
Precursers near a Ni(111) Step Edge

Chem. Comm.

48, 7937-7939

2012

66

J. Kim, A. J. Page, S. Irle, and
K. Morokuma

The Dynamics of Local Chirality during
SWCNT Growth: Armchair versus Zigzag
Nanotubes

J. Am. Chem.
Soc.

134, 9311–9319

2012

67

Jakowski, S. Irle,. B. Sumpter,and K. Morokuma

Modeling charge transfer in fullerene
collisions via real time electron dynamics
simulations

J. Phys. Chem.
Lett.

3, 1536–1542

2012

68

M. A. Addicoat, A. J. Page,
Z. E. Brain, L. Flack, K.
Morokuma and S. Irle

Optimization of a Genetic Algorithm for
the Functionalization of Fullerenes

J. Chem. Theo.
Comp.

8, 1841−1851

2012－ 239 －

fukui2012_02.indb 239

14.1.9 1:47:51 PM

Ⅴ 資料 (2012)№

Authors

Title

JournalVolume (Number),first page tolast page

year

69

J. Jakowski. S. Irle and K.
MorokumaTime–dependent quantum dynamical
simulations of C2 condensation under
extreme conditions,Phys. Chem.
Chem. Phys.

14, 6266-6272

2012

70

V. P. Ananikov, N. V. Orlov,.S.
S. Zalesskiy, I. P. Beletskaya,.
V. N. Khrustalev, K.
Morokuma and D. G. Musaev

Catalytic Adaptive Recognition of Thiol(SH) and Selenol (SeH) Groups Towards
Synthesis of Functionalized Vinyl
Monomers

J. Am. Chem.
Soc.

134, 6637-3349

2012

71

H.-B. Li, A. J. Page, S. Irle,
and K. Morokuma

Theoretical Insights into ChiralityControlled SWCNT Growth from a
Cycloparaphenylene Template

ChemPhysChem

13, 1479-1485

2012

72

M. N. Ryanzantsev A. Altun
and K. Morokuma

Color Tuning in Rhodopsins: The
Origin of the Spectral Shift between the
Chloride-bound and Anion-free Forms ofHalorhodopsin

J. Am. Chem.
Soc.

134, 5520-5523

2012

榊

茂好

73

Hisako Hashimoto, Fukuda
Tetsuya, Hitomi Tobita,
Mausumi Ray, andShigeyoshi Sakaki

Formation of a Germylyne
Complex: Dehydrogenation of aHydrido(hydrogermylene)tungsten Complex with Mesityl
Isocyanate

Angew. Chem.,
Int. Ed.

51 (12), 29302933

2011

74

Kentaro Kido, Hirofumi Sato,
Shigeyoshi Sakaki

Systematic Assessment on Aqueous pK(a)and pK(b) of an Amino Acid Base on
RISM-SCF-SEDD Method: Toward First
Principles Calculations

Int. J. Quant.
Chem.

112(1), 103-112

2011

75

Milind Deshmukh,
Shigeyoshi Sakaki,

Two-step evaluation of binding energy
and potential energy surface of van der
Waals
complexes

J. Compt. Chem..

33(6), 617-628

2011

76

Yusaku I. Kurokawa,
Shigeysohi Sakaki

Theoretical Study of Inverted SandwichType Complexes of 4d Transition Metal
Elements: Interesting Similarities to andDifferences from 3d Transition Metal
Complexes

J. Phys. Chem. A

116(9), 22922299

2011

77

Guixiang Zeng, S. Sakaki

Theoretical Study on the Transition-Metal
Oxoboryl Complex: M-BO Bonding
Nature, Mechanism of the Formation
Reaction, and Prediction of a New
Oxoboryl Complex

Inorg. Chem.

51(8), 45974605

2011

78

Ken Saito, Yoshinori Eishiro,
Yoshihide Nakao, Hirofumi
Sato, Shigeyoshi Sakaki

Oscillator Strength of SymmetryForbidden d-d Absorption of Octahedral
Transition Metal Complex: Theoretical
Evaluation

Inorg. Chem.

51(5), 27852792

2011

79

N. Takagi, S. Sakaki

A Theoretical Study of an Unusual
Y-Shaped Three-Coordinate Pt Complex:
Pt(0) sigma-Disilane Complex or Pt(II)Disilyl Complex?

J. Am. Chem.
Soc.

134(28), 1174911759

2011

80

Seiji Akatsu, Yasunori
Kanematsu, Taka-aki
Kurihara, Shota Sueyoshi,
Yasuhiro Arikawa,
Masayoshi Onishi, Shoji
Ishizaka, Noboru Kitamura,
Yoshihide Nakao, Shigeyoshi
Sakaki, Keisuke Umakoshi

Syntheses and Luminescent Properties of
3,5-Diphenylpyrazolato-Bridged
Heteropolynuclear Platinum Complexes.
The Influence of Chloride Ligands on
the Emission Energy Revealed by the
Systematic Replacement of Chloride
Ligands by 3,5-Dimethylpyrazolate

Inorg. Chem.

51(15), 79777992

2011

81

Yumiko Nakajima,
Shigeyoshi Sakaki, Yoshihide
Nakao, Hiroharu Suzuki

Theoretical Study of Dihydrogen
Activation by a Trinuclear Ruthenium
mu(3)-Imido Complex

Organometallics

31(15), 53425348

2011－ 240 －

fukui2012_02.indb 240

14.1.9 1:47:51 PM

Ⅴ 資料 (2012)№

Authors

Title

JournalVolume (Number),first page tolast page

year

82

S. Aono, S. Sakaki

Proposal of new QM/MM approachfor geometry optimization of periodic
molecular crystal: Self-consistent point
charge representation for crystalline
effect on target QM molecule

83

S. Aono, S. Sakaki

Evaluation Procedure of Electrostatic
Potential in 3D-RISM-SCF Method and
Its Application to Hydrolyses of Cis- andTransplatin Complexes

J. Phys. Chem. B

116(43), 1304513062

2011

84

Atsushi Ishikawa, Yudai
Tamura, Yoshihide Nakao,
Hirofumi Sato, Shigeyoshi
SakakiComplicated Electronic Process of C-C
sigma-Bond Activation of Cyclopropene
by Ruthenium and Iridium Complexes:
Theoretical Study

Organometallics

31 (23), 81898199

2011

85

Shinichi Yamabe, Wei Guan,
Shigeyoshi Sakaki

How is the anionic tetrahedral
intermediate involved in the isomerizationof aspartyl peptides to iso-aspartyl ones?
A DFT study on the tetra-peptide

Org. Biomol.
Chem.

10(39), 80078015

2011

Probability of double-strand breaks ingenome-sized DNA by g-ray decreases
markedly as the DNA concentration
increases

J. Chem. Phys.

Accepted

2013

岩城
86

嶺澤

Chem. Phys.
Lett.

544, 77-82

2011

貴史
Shunsuke F. Shimobayashi,
Takafumi Iwaki, Toshiaki
Mori, and Kenichi Yoshikawa

範行

87

Noriyuki Minezawa andMark S. Gordon

Optimizing Conical Intersections of
Solvated Molecules: The Combined SpinFlip Density Functional Theory/Effective
Fragment Potential Method

J. Chem. Phys.

137(3), 034116[12 pages]

2012

88

Kurt R. Brorsen, Noriyuki
Minezawa, Feng Xu, Theresa
L. Windus, and Mark S.
GordonFragment Molecular Orbital Molecular
Dynamics with the Fully Analytic Energy
Gradient

J. Chem. Theory
Comput.

8, 5008-5012

2012

Phase separation in a binary mixture
confined between symmetric parallel
plates: Capillary condensation transition
near the bulk critical point

Phys. Rev. E

87(3),032405(10 pages)2013

2007

岡本
89

齋藤

隆一
Shunsuke Yabunaka, Ryuichi
Okamoto, and Akira Onuki

拓也

90

Takuya Saito and Takahiro
SakaueProcess time distribution of driven
polymer transport

Phys. Rev. E

85, 061803(7)

2012

91

Takahiro Sakaue, Takuya
Saito and Hirofumi Wada

Dragging a polymer in a viscous fluid:
Steady state and transient

Phys. Rev. E

86, 011804(8)2012

F-Quan Bai
92

Qi Cao, Jing Wang, ZhaoShuo Tian, Zai-Feng Xie andFu-Quan Bai

Theoretical investigation on thephotophysical properties of N-heterocycliccarbene iridium (III) complexes (fpmb)
xIr(bptz)3-x (x=1-2)

J. Comput.
Chem.

33(10), 10381046

2012

93

Juan Jin, Fu-Quan Bai,
Guang-Hua Li, Ming-Jun Jia,
Jin-Jing Zhao, Hong-Li Jia,
Jie-Hui Yu and Ji-Qing Xu

Synthesis, structural characterizationand photoluminescence property of fourdi(mono)acylhydrazidate-coordinatedCd2+ and Zn2+ compounds

CrystEngComm

14(23), 81628172

2012－ 241 －

fukui2012_02.indb 241

14.1.9 1:47:51 PM

Ⅴ 資料 (2012)

Volume (Number),first page tolast pageyear

Dalton Trans.

41(27), 84418446

2012

An efficient fluorescent sensor for redox
active species based on novel poly(arylether) containing electroactive pendant

J. Mater. Chem.

22(7), 30283034

2012

№

Authors

Title

94

Fu-Quan Bai, Jian Wang,
Bao-Hui Xia, Qing-Jiang Pan
and Hong-Xing Zhang

DFT and TD-DFT study on the electronic
structures and phosphorescent propertiesof 6-phenyl-2,2'-bipyridine tridentate
iridium(III) complexes and their isomer95

Danming Chao, Xiaoteng Jia,
Fu-Quan Bai, Hongtao Liu,
Lili Cui, Erik B. Berda andCe Wang

JournalGuo Jingdon
96

Zachary D. Brown, JingDong Guo, Shigeru Nagase,and Philip P. Power

Experimental and Computational Studyof Auxiliary Molecular Effects on the
Mechanism of the Addition of Hydrazines
to a Low-Valent Germanium Complex

Organometallics

31, 3768-3772

2012

97

Satoru Sato, Yutaka Maeda,
Jing-Dong Guo, Michio
Yamada, Naomi Mizorogi,
Shigeru Nagase, and Takeshi
Akasaka

Mechanistic Study of the Diels-Alder
Reaction of Paramagnetic Endohedral
Metallofullerene: Reaction of La@C82
with 1,2,3,4,5-Pentamethylcyclopentadiene

J. Am. Chem.
Soc.

135, 5582-5587

2013

Density functional theory study offullerene–carbene Lewis acid–baseadducts: critical role of dispersion
interactions

RSC Adv.

3(26), 10177–
10180

2013

99

Ke, Zhuofeng, Abe, S., Ueno,
T., & Morokuma, Keiji*

Rh-catalyzed Polymerization of
Phenylacetylene: Theoretical Studies of
the Reaction Mechanism, Regioselectivity
and Stereoregularity

J. Am. Chem.
Soc.

134 (37),
15418–15429

2012

100

R.-R. Ye, ZhuoFeng Ke, C.-P.
Tan, L. He, L.-N. Ji and Z.-W.
Mao.

Histone Deacetylases Targeted
Fluorescent Ruthenium(II) Polypyridyl
Complexes as Potent Anticancer Agents.

Chem. Eur. J.

19, 10160 –
10169

2013

101

Liu Y., Ma L., Chen W.-H.*,
Park H., Ke Zhuofeng*, &Wang B.*

Binding Mechanism and Synergetic
Effects of Xanthone Derivatives as Noncompetitive α-Glucosidase Inhibitors: a
Theoretical and Experimental Study.

J. Phys. Chem.
B.

Just Accepted2013

Dynamics of Local Chirality during
SWCNT Growth: Armchair versus
Zigzag Nanotubes

J. Am. Chem. Soc

134(22), 9311

2012

Jin Peng
98

Peng Jin and Shigeru Nagase

Zhuofeng Ke

Joonghan Kim
102

Alister Page
103

H.-B. Li, A. J. Page, S. Irle, K.
Morokuma

Theoretical Insights into ChiralityControlled SWCNT Growth from a
Cycloparaphenylene Template

ChemPhysChem

13,6. 1479-1485

2012

104

M. A. Addicoat, A. J. Page,
Z. Brain, L. Flack, S. Irle, K.
Morokuma

Optimisation of a Genetic Algorithm for
the Functionalisation of Fullerenes

J. Chem. Theor.
Comp.

8,5. 1841-1851

2012

105

J. Kim, A. J. Page, S. Irle, K.
Morokuma

The Dynamics of Local Chirality during
SWCNT Growth: Armchair versus
Zigzag Nanotubes

J. Am. Chem.
Soc.

134,22. 93119319

2012

106

H.-B. Li, A. J. Page, Y. Wang,
S. Irle, K. Morokuma

Sub-Surface Nucleation of Graphene
Precursors near a Ni(111) Step-Edge

Chem. Comm.

48,64. 79377939

2012－ 242 －

fukui2012_02.indb 242

14.1.9 1:47:52 PM

Ⅴ 資料 (2012)

Volume (Number),first page tolast pageyear

J. Chem. Theor.
Comp.

8,11. 40194028

2012

SWCNT Growth from Chiral Carbon
Nanorings: Prediction of Chirality andDiameter Influence on Growth Rates

J. Am. Chem.
Soc.

134,38. 1588715896

2012

A. J. Page, C.-P. Chou, P.-Q
Buu, H. Witek, S. Irle, K.
Morokuma

Quantum Chemical Investigation of
Epoxide and Ether Groups in Graphene
Oxide and their Vibrational Spectra

Phys. Chem.
Chem. Phys.

15,11. 37253735

2013

K. R. S. Chandrakumar, A. J.
Page, S. Irle, K. Morokuma

Carbon Coating Precedes SWCNT
Nucleation on Silicon Nanoparticles:
Insights from QM/MD Simulations

J. Phys. Chem. C

117,8. 42384244

2013

111

Miho Hatanaka, Satoshi
Maeda, and Keiji Morokuma

Sampling of Transition States for
Predicting Diastereoselectivity Using
Automated Search Method―Aqueous
Lanthanide-Catalyzed Mukaiyama Aldol
Reaction

J. Chem. Theory
Comput.

in press

2013

112

Satoshi Maeda, Erika Abe,
Miho Hatanaka, Tetsuya
Taketsugu, and Keiji
Morokuma

Exploring Potential Energy Surfacesof Large Systems with Artificial Force
Induced Reaction Method in Combination
with ONIOM and Microiteration

J. Chem. Theory
Comput.

8(12), 50585063

2012

№

Authors

Title

Journal107

A. J. Page, T. Isomoto, J.
Knaup, S. Irle, K. Morokuma

Effects of Molecular Dynamics
Thermostats on Non-Equilibrium Systems

108

H.-B. Li, A. J. Page, S. Irle, K.
Morokuma

109

110

畑中

美穂

Hongyan Xiao
113

Hongyan Xiao, Satoshi
Maeda and Keiji Morokuma

Global ab Initio Potential Energy Surfaces
for Low-Lying Doublet States of NO3

J. Chem. Theory
Comput.

8(8),2600-2605

2012

114

Bina Fu, Joel M. Bowman,
Hongyan Xiao, Satoshi
Maeda and Keiji Morokuma

Quasiclassical Trajectory Studies of the
Photodissociation Dynamics of NO3 fromthe D0 and D1 Potential Energy Surfaces

J. Chem. Theory
Comput.

9(2),893-900

2013

115

Hongyan Xiao, Satoshi
Maeda and Keiji Morokuma

CASPT2 Study of Photodissociation
Pathways of Ketene

J. Phys. Chem. A

in press(DOI: 10.1021/
jp312719a)

2013

SWCNT Growth from Chiral Carbon
Nanorings: Prediction of Chirality andDiameter Influence on Growth Rates

J. Am. Chem.
Soc.

134, 1588715896,

2012

Haibei Li
116

Hai-Bei Li, Aister. J. Page,
Sthephan. Irle and K.
Morokuma,

Lung Wa Chung
117

Lung Wa Chung, Hajime
Hirao, Xin Li and Keiji
Morokuma

The ONIOM method: its foundation
and applications to metalloenzymes andphotobiology

WIREs Comput.
Mol. Sci.

2 (2), 327–350

2012

118

Lina Ding, Lung Wa Chungand Keiji Morokuma

Reaction Mechanism of Photoinduced
Decarboxylation of the Photoactivatable
Green Fluorescent Protein: An
ONIOM(QM:MM) Study

J. Phys. Chem. B

117 (4), 10751084

2013

Reverse hydrogen spillover on andhydrogenation of supported metalclusters: Insights from computationalmodel studies

Phys. Chem.
Chem. Phys.

14 (17), 58795890

2012

Galina Petrova
119

G. V. Vayssilov, G. P. Petrova,
E. A. I. Shor, V. A. Nasluzov,
A. M. Shor, P. S. Petkov, N.
Rösch－ 243 －

fukui2012_02.indb 243

14.1.9 1:47:52 PM

Ⅴ 資料 (2012)

Authors

Title

JournalVolume (Number),first page tolast page

year

120

Yamabe, Shinichi; Fukuda,
Takeshi; Yamazaki, Shoko

Proton Transfers Along Hydrogen Bonds
in the Tautomerization of Purine

J. Phys. Chem. A

116 (4), 12891297

2012

121

T. Machiguchi, T. Hasegawa,S. Yamabe, T. Minato, S.
Yamazaki, and T. Nozoe

Experimental and Theoretical Analysesof Azulene Synthesis from Tropones andActive Methylene Compounds: Reactionof 2-Methoxytropone and Malononitrile

J. Org. Chem.

77, 5318-5330

2012

122

Shinichi Yamabe, Wei Guan
and Shigeyoshi Sakaki

How is the anionic tetrahedral
intermediate involved in the isomerizationof aspartyl peptides to iso-aspartyl ones?
A DFT study on the tetra-peptide

Org. Biomol.
Chem.

10, 8007-8015

2012

123

Shinichi Yamabe, Takeshi
Fukuda and Shoko Yamazaki

A new intermediate in the Prins reaction

Beilstein J. Org.
Chem.

9, 476-485

2013

124

Shinichi Yamabe, Wei Guan
and Shigeyoshi Sakaki

Presence or absence of a novel chargetransfer complex in the base-catalyzedhydrolysis of N-ethylbenzamide or ethyl
benzoate

Beilstein J. Org.
Chem.

9, 185-196

2013

125

Shinichi Yamabe, Wei Guan
and Shigeyoshi Sakaki

Three Competitive Transition States at the
Glycosidic Bond of Sucrose in Its AcidCatalyzed Hydrolysis

J. Org. Chem.

78 (6), 25272533

2013

126

Shinichi Yamabe, Guixiang
Zeng, Wei Guan and
Shigeyoshi Sakaki

An aniline dication-like transition state in
the Bamberger rearrangement

Beilstein J. Org.
Chem.

9, 1073-1082

2013

127

Masakazu Higuchi, Kohei
Nakamura, Satoshi Horike,Yuh Hijikata, Nobuhiro
Yanai, Tomohiro Fukushima,
Jungeun Kim, Kenichi Kato,
Masaki Takata, Daisuke
Watanabe, Shinji Ohshima,and Susumu Kitagawa

Design of flexible Lewis acidic sites inporous coordination polymers by using
the viologen moiety

Angew. Chem.
Int. Ed.

51, 8369-8372

2012

128

Maw Lin Foo, Satoshi Horike,
Tomohiro Fukushima, Yuh
Hijikata, Yoshiki Kubota,
Masaki Takata, and Susumu
Kitagawa

Ligand-based solid solution approachto stabilization of sulphonic acidgroups in porous coordination polymer
Zr6O4(OH)4(BDC)6 (UiO-66)

Dalton. Trnas.

41, 13791-13794

2012

129

Munehiro Inukai, Satoshi
Horike, Daiki Umeyama,
Yuh Hijikata, and Susumu
Kitagawa

Investigation of post-grafted groups ofa porous coordination polymer and its
proton conduction behavior

Dalton. Trnas.

41, 13261-13263

2012

130

Shin-ichiro Noro, Yuh
Hijikata, Munehiro Inukai,
Tomohiro Fukushima,
Satoshi Horike, Masakazu
Higuchi, Susumu Kitagawa,Tomoyuki Akutagawa, andTakayoshi Nakamura

Highly selective CO2 adsorption
accompanied with low-energy
regeneration in a two-dimensional
Cu(II) porous coordination polymer withinorganic fluorinated PF6- anions

Inorg. Chem.

52, 280-285

2013

131

Satoshi Horike, Masayuki
Sugimoto, Kanokwan
Kongpatpanich, Yuh Hijikata,
Munehiro Inukai, Daiki
Umeyama, Shinji Kitao,
Makoto Seto, and Susumu
Kitagawa

Fe2+ based layered porous coordination
polymers and soft encapsulation of guests
via redox activity

J. Mater. Chem.
A

1, 3675-3679

2013

№

山邊

土方

信一

優

－ 244 －

fukui2012_02.indb 244

14.1.9 1:47:52 PM

Ⅴ 資料 (2012)

Volume (Number),first page tolast pageyear

Inorg. Chem.

52, 3634-3642

2013

A 3D-RISM-SCF method with dual
solvent boxes for a highly polarized
system: application to 1,6-anhydrosugar
formation reaction of phenyl alpha- andbeta-D-glucosides under basic conditions

Phys. Chem.
Chem. Phys.

17 63682013

134

Shinji Aono and Shigeyoshi
Sakaki

Evaluation Procedure of Electrostatic
Potential in 3D-RISM-SCF Method and
Its Application to Hydrolyses of Cis- andTransplatin Complexes

J. Phys. Chem. B

116 13045

2012

135

Shinji Aono and Shigeyoshi
Sakaki

Proposal of new QM/MM approachfor geometry optimization of periodic
molecular crystal: Self-consistent point
charge representation for crystalline
effect on target QM molecule

Chem. Phys.
Lett.

544 772012

A theoretical study of luminescentvapochromic compounds including an
AuCu 2(NHC)2 core

DaltonTransactions

42, 4809-4821

2013

№

Authors

Title

132

Yuh Hijikata, Satoshi
Horike, Masayuki Sugimoto,
Munehiro Inukai, Tomohiro
Fukushima, and Susumu
Kitagawa

Pore design of two-dimensional
coordination polymers toward selective
adsorption

133

Shinji Aono, Takashi Hosoya,
and Shigeyoshi Sakaki

青野

塚本
136

Journal

信治

晋也
Shinya Tsukamoto andShigeyoshi Sakaki

Milind Deshmukh
137

Deshmukh, Milind. M.;
Sakaki Shigeyoshi

Two-step Evaluation of Potential Energy
Surface and Binding Energy of van der
Waals Complexes

J. Comput.
Chem.

33, 617-628

2012

138

Khedkar, J. K.; Deshmukh,
Milind M.; Gejji, S. P.;
Gadre, S. R."

Intramolecular Hydrogen Bonding andcooperative interactions in Calix[n]arenes(n = 4, 5)

J. Phys. Chem. A

116, 3739-3744.

2012

139

Deshmukh, Milind M.;
Ohba, Massaki.; Kitagawa,Susumu.; Sakaki Shigeyoshi

Absorption of CO2 and CS2 into the
Hofmann-type Porous Coordination
Polymer:Electrostatic versus Dispersion

J. Am. Chem.
Soc.

135, 4840-4849

2013

2012

髙木

望

140

N. Takagi, S. Sakaki

A Theoretical Study of Unusual Y-Shaped
Three-coordinate Pt Complex: Pt(0)σ-Disilane Complex or Pt(II) Disilyl
Complex?

J. Am. Chem.
Soc.

134, 1174911759

141

N. Takagi, S. Sakaki

Theoretical Study of Reactivity of Ge(II)hydride Compound: Comparison withRh(I)-hydride Complex and Prediction of
Full Catalytic Cycle by Ge(II)-hydride

J. Am. Chem.
Soc.

in press

J. Comput.
Chem.

34, 1013–1023

2013

Chem. Phys.
Lett.

549, 108–112

2012

吉澤

輝高

142

T. Yoshizawa, S. Sakaki

NMR shielding constants of CuX,
AgX, and AuX (X = F, Cl, Br, and I)
investigated by density functional theory
based on the Douglas–Kroll–Hess
Hamiltonian143

T. Yoshizawa, T. Nakajima

A new computational scheme for the
spin–orbit part of zero-field splitting
tensor－ 245 －

fukui2012_02.indb 245

14.1.9 1:47:53 PM

Ⅴ 資料 (2012)№

Authors

Title

JournalVolume (Number),first page tolast page

year

Guan Wei
144

Interest in new heterodinuclear transitionmetal/main-group-metal complexes:
DFT study of electronic structure andmechanism of fluoride sensing function

Dalton Trans.

42, 8717–8728

2013

145

Three Competitive Transition States at the
Glycosidic Bond of Sucrose in Its AcidCatalyzed Hydrolysis

J. Org. Chem.

78, 2527−2533

2013

146

Presence or absence of a novel chargetransfer complex in the base-catalyzedhydrolysis of N-ethylbenzamide or ethyl
benzoate

Beilstein J. Org.
Chem.

9, 185–196

2013

147

An aniline dication-like transition state in
the Bamberger rearrangement

Beilstein J. Org.
Chem.

9, 1073–1082

2013

148

How is the anionic tetrahedral
intermediate involved in the isomerizationof aspartyl peptides to iso-aspartyl ones?
A DFT study on the tetra-peptide

Org. Biomol.
Chem.

10, 8007−8015

2012

149

The self-assembly mechanism of the
Lindqvist anion [W6O19]2− in aqueous
solution: a density functional theory study

Dalton Trans.

41, 11361–
11368

2012

150

Building blocks and formation
thermodynamics of a-Keggin-type[PW12O40]3- anion

Comput. Theor.
Chem.

999, 66–73

2012

151

DFT study of ionic peapod structuresfrom single-walled carbon nanotubes and
Lindqvist tungstates

Dalton Trans.

41, 2798-2803

2012

松井

亨

152

Toru Matsui, Yasutaka
Kitagawa, Mitsutaka
Okumura Yasuteru Shigeta
and Shigeyoshi SakakiConsistent Scheme for ComputingStandard Hydrogen Electrode and Redox
Potentials

Journal ofComputational
Chemistry

34, 21-26

2013

153

Y. Kitagawa, N. Yasuda, H.
Hatake, T. Saito, Y. Kataoka,
T. Matsui, T. Kawakami, S.
Yamanaka, M. Okumura andK. Yamaguchi

Combination of approximate spinprojection and spin-restricted calculations
based on ONIOM method for geometry
optimization of large biradical systems

International
Journal of
Quantum
Chemistry

13, 290-295

2013

河津

励

154

Tsutomu Kawatsu

Pathway analysis for peptide-mediatedelectronic coupling in the super-exchangemechanism of ET and EET

Peptide Science

100, 100-113

2013

155

Tsutomu Kawatsu, Jun-ya
Hasegawa

Sequentially Coupled Hole–ElectronTransfer Pathways for Bridge-MediatedTriplet Excitation Energy Transfer

J. Phys. Chem. C

116, 23252–
23256

2012

156

Tsutomu Kawatsu, Jun-ya
Hasegawa, Kenji Matsuda

Singlet Excitation Energy Transfer
Mediated by Local Exciton Bridges

J. Phys. Chem. C

116, 1386513876

2012－ 246 －

fukui2012_02.indb 246

14.1.9 1:47:53 PM

Ⅴ 資料 (2012)

４．福井謙一記念研究センター

シンポジウムポスター・プログラム

第10回
京都大学福井謙一記念研究センター
シンポジウム日 時会

2012年11月30日(金)10時〜

３F大会議室場 京都大学福井謙一記念研究センター
Fukui Institute for Fundamental Chemistry, Kyoto University

プログラム●10:00 -10:05

開会の辞●10:05 -10:15

ご 挨 拶

田中 一義(センター長)
北野 正雄(京大・工学研究科長)●10:15 -11:15

Weston T. Borden(University of North Texas)“Why Does Cyclobutane-1,2,3,4-tetraone
Have a Triplet Ground State?”●11:30 -12:30

赤木 和夫(京大・院工)「不斉液晶反応場での高分子合成：
ヘリカル共役ポリマーのらせん制御と形態保持炭素化」−昼休み−●14:00 -15:00

榊茂好(福井センター)「金属錯体の分子物性と反応：電子状態に基づく微視的理解」●15:15 -17:15

ポスターセッション●17:30 -19:00

懇親会(１Ｆ多目的ルーム)

問い合わせ先京都市左京区高野西開町34-4
Tel : 075-711-7708
京都大学福井謙一記念研究センター

Fax : 075-781-4757

石田 俊正(ishida@fukui.kyoto-u.ac.jp)

http://www.fukui.kyoto-u.ac.jp－ 247 －

fukui2012_02.indb 247

14.1.9 1:47:54 PM

Ⅴ 資料 (2012)

10-

×6;

ÅÁOĪŒĬŔĦŒńħęŇê
ľőġōŇêö|ö ö üúûü÷bp üþøc ûû  ýú |Ĥæĥö ö
Crö ö ãGO¶ ÕÒn²ºđĠĒģö ö
ö

Æ

ê

÷ýă GÖTö ûúĂúúùûÿĂúúøöö• éćÞöö• Ćvuö©ö Çö ÷ãGOö ¶

ÕÒn²ºđĠĒģèøö/åö íö ÷ãGOö aO²º¸èøöööĢĢĢĢĢĢûúĂúúùûúĂúÿö
ĢĢĢĢĢĢûúĂúÿùûúĂûÿö

• Weston T. Borden (University of North Texas)"Why Does Cyclobutane-1,2,3,4-tetraone Have a Triplet Ground State?”
öö
ö
ö
ö
ö
ö
ö
ö
ö
ĢĢĢĢĢĢûúĂûÿùûûĂûÿ• Ýö :Iö ÷ ãGOGOëö aO²º¸ø÷_}g&N2ćĊé8)SŗĿŎĝŏKńŎŅŔĊđāĕLĈJQV¥"øê
êê
ê
ê
ê
ê
ê
ê
ê
ê
ĢĢĢĢĢĢûûĂýúùûüĂýúħ Ĉ ħ• 榊 茂好ö ÷¶ ÕÒn²ºđĠĒģø
÷ÝDÞĊ8 PĈ&Nŗä8Qĉ1ąýM¼¾ø

ĢĢĢĢĢĢ14:00-15:00

ńĨĬŔĪįĦŌŒê
÷ýă GÖTö ûÿĂûÿùûĀĂûÿøö
ö

R½

ê

÷ûă F­¬Ğģěö ûĀĂýúùûāĂúúøö

－ 248 －

fukui2012_02.indb 248

14.1.9 1:47:55 PM

Ⅴ 資料 (2012)ńĨĬŔĪįĦŌŒê îñóîñíîòóîñêëðô 6

Ç?ì

ê

õ	
   (15:15-16:15)   (16:15-17:15)   
õ	
 Please present your poster at the first half (15:15-16:15) when your poster number is odd and do
it at the second half (16:15-17:15) when the number is even.
êê1.

ĘŒĨĬŒĲŒ{ĉĐēĲŒĶŏ¸À£(&M²[1]ąæGëË£[2]ąæGë¥a[3]) Ąö +[1,2]ą[3]2.

Temperature effect in the fluorescence blueshift of [n]cycloparaphenylenes withincreasing molecular size
(Department of Chemistry, Graduate School of Science, Nagoya University) ĄCristopher Camacho
and Stephan Irle

3.

ΔSCF(2): a balanced, economical approach to multireference perturbation theory(Massachusetts Institute of Technology[1] and Nagoya University[2]) Shane Yost[1], ĄTimKowalczyk[1,2] and Troy Van Voorhis[1].

4.

Theoretical Study on Cycloreversion Reaction of Diarylethene Derivatives: Relation
between Optimized Geometry on Excited State and Cycloreversion Quantum YieldĤêGëB³aĥ ĄKå ąä© Ê¤ą] bąU? 2ąå îª

5.

The Diradical Characters and Third-Order Nonlinear Optical Properties of Bucky
Ferrocenes Systems(Department of Materials Engineering Science, Osaka University) ĄShabbir Muhammad, Takuya
Minami, Ryohei Kishi, Yasuteru Shigeta, Masayoshi Nakano

6.

ĖĦŏ"&NĉBĀēĖņķÚ4Ċ lê(êGëB³a[1]ąÀGëx¥[2]ąêGë¥[3]ą!f¯»GOëaO[4]ąĐēĝĐęģĞG[5])ĄòC(5[1]ą´×w[2]ą

7.

[3]ąÓ6[4]ąMauro Boero[5]ąåîª[1]ąä©Ê¤[1]

eá:@Izâ^{ĉ1ąýĳĴŔœĖĠĪľĬ ï ¬[ŀŒīŒĊä8ÕPĈpĊÄêÊĤêGëB³aĥ Ą©Ðą]°oą]bąåîª8.

>á@Izâ^{ĉĐē ï uã¤Ċ;N¢ÜĊÀ£T{Ċ>¹ê(êGëB³a) ĄîªąKå ąòC (5ąÂ©

bą¶© dHáąä© Ê¤ąå

-2－ 249 －fukui2012_02.indb 249

14.1.9 1:47:56 PM

Ⅴ 資料 (2012)9.

uàwÛç«K8¤Ċ©J+'ļŔĠĊħōħĝŏ.8:PĉĄùĆĊ
Äê
ĤêGëB³aĥĄ] °oą] bą1 tąÎ Éą© Ðą¶© dHáąå îª10. ĜŎĤŎŐŒĉúþēĦŒġŐįĲĽėįĦŌŒĊÄêĤêGëB³aĥĄ1tąÎÉąåîª11. àwÛçħĽĚĴŐĵŏħōħĝŏ8Ċä8qÑĈ8+'PĉĄùĆĊÄê(êGëB³a[1]ą¨Å²ĜėČĒĐ[2]ąêGë¥[3]) Ą]ö b[1]ą]ö °o[1]ą1%ö ·[1]ą
©ö Ð[1]ą¶©ö dHá[1]ąç©ö Ü6[1]ąH©ö  [2]ąö N5[3]ąä©ö Ê¤[1]ąåö îª[1]12. ³"5Ø¬$]«Û\!{úĐċeá:@Izâ^{ĉĐēĜŎĤĖĪŒĊÉQĊê
(êGëB³a) ĄÎö Éą1ö tą¶©ö dáą]ö bąåö îª
13. ÕÝDnÞĊàwPĈ

ÊpĉBĀēěĠĖĲŎĖŏØ8ü%čĀ

lĊÄ
(êGëB³a) ĄíGąZ©Gmą¶©dHáą;5ąä©Ê¤ąåîª14. ÛçàwPĔďĄīĲŐŒèĊå©J;PŗĳĴŔŕĖĠĪľĬŔ¬[1 lê(êGëB³a[1]ą¨Å²ĜėČĒĐĊĕĞčģ[2]) Ą1%ö ·[1]ą¶©ö dHá[1]ąÂ©ö
[1]ąÎö É[1]ą]ö b[1]ąç©ö Ü6[2]ąåö îª[1]15. ĿİőnÕÝD¤Ċħōħĝŏ.8Ĉuå©J;bPĊâĉĄùĆĊÄê(êGëB³a[1]ąêGB³a[2]) ĄZ©ö Gm[1]ą
5[2]ąö ä©ö Ê¤[1]ąåö îª[1]16. ČĞĥĪŒ8ĊàwPĈ
ĤêGëB³aĥĄÂ©

ö íG[1]ą¶©ö dHá[1]ąö ÊpĉBĀē¬[1ö;lĊÄêbą¶©dHáą1%·ąåîª17. r~y¥äpńİŒĦŊŏĈÚ"ÖäĊb»£{êĤêGë¥[1]Ģ G¶ ÕÒn²ºđ[2]ĢêGëB³a[3]ĥĄ ì[1]Ħä© Ê¤[3]Ħ榊 ÍL[2][1,2]Ħ/ gì[1]ĦK

18. (VO)7 ÞĉúþēxĊzâ^úĐċ1Hâ^:PêĤêGë¥ĥĄ/gìĢĢQ©JãÆĢ«ġPSĢ`ÚÛĢZ·ĢKì
19. Gæ| DFT {ĉĐēßqÑ¨gĪŐŒĊä´!ĈĹŒĳqÑĊ( Gë¥[1]ą G ESICB[2])öĄ
$[1][2]-3－ 250 －fukui2012_02.indb 250

14.1.9 1:47:57 PM

Ⅴ 資料 (2012)

20. CäPÝDÚ" ĔùĂľōĩŉĵįĠıĹĘĨĊÂÀĈºêĤ Gëaĥö ĄQ3ö ìáąÎ©ö 6ą ö ą©ö -
21. FMO-LCMO {ĔùĂµÈĊä8!§Ë¾k( Gë¥) Ąóð(Ñ[) RąQÎ È6
22. ōħĝŏĝĮĜŒľŔŏ{ĉĐēåBĻĖŎŔŏ")( Gëa) Ą ö ¼hąÔÎö àą7©ö ¡ĊZ)Sê

23. 8!;ĦņŋŐŔĦŌŒĉĐēĖŏĝŎÝDĸōĘĳy}ĊŖuY!ĨŁĠĲŏ

¾kê
(Gë¥)öĄÎö eąö ×ö 7ì

24. G/2 QM/MM {ĉĐē}œÙ¥&NĊ±ěĶŏğŔÀ£Ĥ Gë¥ĥĄß 5ąZ m
25. }ĉúþēĽĚķŔŏÃCĊä8œľőĲŒ!&NĊÄóê åaPĈĲŒ

ĶŎŒġ
(

lê

Gë¥) Ą¹@ąZm

26. QM/MM {ĊĂĎĊ ESP 5Ûp8£8Ċà( Gë¥[1]ąğĎĠēĠG[2]) Ą ö í[1]ąXö Ú[2]ąß 5[1]ąZ m[1]ąöäj[1]27. ( MD Ĉ QM/MM {ĉĐēőĳľĦŒĊ&NáĊÄ( Gë¥) Ą´× B6,  äj
28. MS-CASPT2 {ĔNÿĂļŎħŒĊÊéÐª,ÓĉĄùĆĊÄ( GëĢ¥[1], ĐĒĠĘċģĔG[2]) Ąå-2[1], y[2], äj[1], *Îä[1]29. Enhanced green fluorescent protein Ċ¶QĉâĀēÄ( Gë¥[1]ą&M²[2]) Ą#©ö ÌÐ[1]ąö îG[2]ąö äj[1]30. Ras-GAP Ċ GTP y¾¿7ĉâĀēÄ( Gë¥[1]ą&M²[2])öĄ yö ;¦[1]ąö ö äj[1]ąö ö îG[2]ązÎö °6[2]31. poly(quinoxaline-2,3-diyl)s Ċ·dqÑĈ<=PĉâĀēÄ( Gëa) Ą© õąAqH ąÎ;y32. Ru ¿7ĉĐēyĊ¾&NĉâĀēÄê( Gëa) Ą ö ,ąÎö ;y33. y}ćĊĖĵŎŒĊĘĜŒ"ĉâĀēÄê( Gëa) Ąö µRą ñ©ö  ąÎö ;y-4－ 251 －fukui2012_02.indb 251

14.1.9 1:47:58 PM

Ⅴ 資料 (2012)

34. A molecular level study of selective cation capture by a host-guest mechanism for 25,

26, 27, 28-tetramethoxycalix[4]arene in MClO4 solution (M=Na, K)(Gëa[1]Ħ

G¶

đ[2]) Aqö H[1]ĦĄ¾3ö [1]ĦÎö ;y[1]Ħ榊ö ÍL[2]35. łŔŏÌÍi`ĉúþēYäĈ5 lêĤ Gëa[1]ą G.²[2]ĥ Ąö Ú[1]ą Îö l[1]ą©ö Ç[1]ąö h"[2]ö
36. &NPWrĈÿĆĊYä@IŗĽōŔŐŒČĊNê( Gëa[1]) Ą~©ö ®[1]ąÎö l[1]ą\3ö ®[1]ą©ö Ç[1]37. ä¾}ĉúþēŎĮęŇ3Ĉht78ĊØQĉâĀēÄ¾kê
Ĥ Gëa[1]ą¶ đ[2]ąVEäaĐĖĞs²[3]ĥĄö ¼[1]ąÎö k[1]ą©ö Ç[1,2]ą
q^ö [3]38.

E¡®ĉ*þĂCäPé8ĖĠĮŋěŔĬŔĊÄêĤGëa[1]ą

G¶

đ[2]ĥ Ąö i[1]ą½åö 2[1]ą©ö Ç[1][2]39. CPMD ĔùĂo8 π K8ĊÉQĉâĀēÄ( Gëa[1],G¶ đ[2]) Ąp© °h[1], Î ;y[1], Y <·[2]40. htōħĝŏĔØ8ĈĀē Co(II)ÞĊPĉâĀēÄ( Gëa[1]ą G¶ đ[2]) Ąå4ö Ã[1]ą Îö ;y[1]ąYö <·[2]41. Theoretical studies on reactions in biomolecules: photoisomerization of rhodopsins

and ligand exchange in CooA

( G¶ đ[1]ąDLSU[2]ąG¥a[3]ą&M²[4]) Ą±©[1]ąWilfredo C. Chung[1,2]ą1
âN[3]ąïåä'[4]42. Cr(III)öCo(II)ĊĜĞĥōĲmsÞĊxcPĉâĀēÄ( G¶ đ[1]ą Gëa[2]) ĄYö <·[1]ą å4ö Ã[2]ąÎö ;y[2]43. Three competitive transition states at the glycosidic bond of sucrose in the

acid-catalyzed hydrolysis.

(FIFC) ĄShinichi Yamabe, Wei Guan and Shigeyoshi Sakaki
44. cgĽĚōĘĲĉúþē Mössbauer ĺōňŔĬĊ #À£( G¶ đ[1]Ħ Gëa[2]) Ąå Ø[1]Ħ© )[2]
45. The Mechanism of Lanthanide-Catalyzed Mukaiyama Aldol Reaction in Water

Solution(FIFC[1],Emory univ[2]) ĄMiho Hatanaka[1], Keiji Morokuma[1,2]ö

-5－ 252 －fukui2012_02.indb 252

14.1.9 1:47:59 PM

Ⅴ 資料 (2012)

46. Revisiting the Mechanisms of Spiropyran Photochromic Ring-Opening Reaction: a

CASPT2//CASSCF Study(FIFC) ĄFengyi Liu, Keiji Morokuma
3

3

3

2

47. Mechanistic investigation on the site selectivity on C(sp )-C(sp ) and C(sp )-C(sp )cleavage by Rh-catalyst: A DFT study(FIFC[1], Kyoto University[2]) ĄLina Ding[1], Naoki Ishida[2], Keiji Morokuma[1]48. Subsurface Nucleation of Uniform Graphene Precursors on Ni(111) Surface(FIFC) ĄHai-Bei Li, Alister J. Page, Ying Wang, Stephan Irle, and Morokuma Keiji
49. Strong Correlations in Decomposition and Chemiluminescence of Dioxetanones(FIFC[1], IMS[2]) ĄLung Wa Chung [1], Yuki Kurashige [2], Takeshi Yanai [2] and Keiji Morokuma[1]
50. Theoretical modeling of DNA-based copper catalysts performance in intramolecularFriedel-Crafts reaction ê(FIFC [1], [2]) ĄGalina Petrova [1], Zhuofeng Ke [2], Keiji Morokuma [1]51. ONIOM study of the ferritin ferroxidase reaction(FIFC) ĄTravis V. Harris and Keiji Morokuma
52. ľőĲŒCPØé8Ċä8QĉâĀēÄê( G¶ đ) Ą>{ö ą榊ö ÍLĉúþēġŏģĦĳûđĊŐŃġŏģĥŒStqŗα Ĉ β Ċ&NPĊÔĉâĀē 3D-RISM-SCF {ĉĐēÄ

53. 31Pj
(

G¶

đ[1]ą

G iCeMS[2])öĄïå [1]ąÄ× ì5[2]ą榊 ÍL[1]854. Øê d Ni(II) Þ ĊqÑĈä8Q%ċ¨gćĊĨļŒĠőĨĜŔĹŔĉĄùĆ

ĊÄ­Aê
(55.

G¶đ) ĄD ą榊ö ÍL

Absorption of Gas Molecules in Metal Organic Framework: A Theoretical Study(FIFC[1], Grad. School. of Sci. Kyushu Univ.[2]) ĄMilind Deshmukh[1], Masaaki Ohba[2],Shigeyoshi Sakaki[1]56. Unexpected Electronic Process of the H2 Activation by a New Nickel(0)−Borane

Complex: Comparison with the Usual Homolytic and Heterolytic Activations(FIFC) ĄGuixiang Zeng and Shigeyoshi Sakaki-6－ 253 －fukui2012_02.indb 253

14.1.9 1:47:59 PM

Ⅴ 資料 (2012)

57. A Theoretical study of Hydrogenation of Ketone by Ge(II) Hydride. Reaction

Mechanism, Comparison with Rh(I) Hydride, and Prediction in Expectation of a
Main-Group-Based Catalyst(FIFC) ĄNozomi Takagi, Shigeyoshi Sakaki
58. ÝD#8ĉĐē¥8ĔXĕăÎĥŒĳĘįĮ0ÞĊä8qÑĉâĀēÄ

ê
(

G¶

đ) Ą@ îą榊 ÍL

59. Heterodinuclear main-group/transition-metal complexes and their fluoride sensing

function: DFT study(FIFC) ĄWei Guan, Shinichi Yamabe, Shigeyoshi Sakaki

60. Electronic State and Bonding Nature of Nickel(I)- and Copper(I)- Dioxygen

Complexes: RASPT2 Study(FIFC) ĄYue Chen, Shigeyoshi Sakaki
61. v¯JSÓĊ Langevin Dynamics ĉĐēŉıŎŒġĈ§ËÕĊÀ£( G¶ đ[1]ą G0[2]ą8G§90[3]) Ą\Aö Ú5[1]ą ö WM[2]ą7`ö ²[3]62. ä8ÉQĊ±ěĶŏğŔæ: RISM-TDDFT {( G¶ đ) Ą_¢ö ÁÏ
63. °}ĊģőĘĳáĊfÒYē²ùê( G¶ đ[1]ą G¥[2]) Ą[ì[1]ąXÙ}[2]64. M¦9ĔÏĒUþēé8ßĊĭĘĴņĠĨóê ÏĒUþeáĊFĊĨĢŔŎŒġê
( G¶ đ[1]ąG¥[2])ąĄôÎ t[1]ą?ö Ú[2]-7－ 254 －fukui2012_02.indb 254

14.1.9 1:48:00 PM

Ⅴ 資料 (2012)

ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
ö
¿ûú=¶

ÕÒn²ºđĠĒģĎĠĚďĉěö

üúûücĤbpüþcĥûûýú|÷æøöãGO¶ÕÒn²ºđĠĒģö

ê

-8－ 255 －fukui2012_02.indb 255

14.1.9 1:48:02 PM

Ⅴ 資料 (2012)

５．福井謙一記念研究センター

セミナー

ポスター・プログラム

第１０回
福井センターセミナー
The 10th Fukui Center Seminar
2013年3月21日(木) 14:30-17:30

京都大学福井謙一記念研究センター1F 多目的室 (Room: 1F 106)
http://www.fukui.kyoto-u.ac.jp/〒606-8103 京都市左京区高野西開町34-4（℡075-711-7708)(at FIFC, Kyoto Univ. on March, 21(Thu.), 2013)
14:30～14:35 Opening by Professor Shigeyoshi Sakaki(Fukui Institute for Fundamental Chemistry)
14:35～15:30 Assistant Professor Satoshi Maeda(Hokkaido Univ.)“Development and Applications of Automated Reaction Path
Search Methods: The Global Reaction Route Mapping(GRRM) Strategy”
15:30 ～16:00 Dr. Miho Hatanaka(Fukui Institute for Fundamental Chemistry)“Mechanism of Mukaiyama Aldol Reaction Catalyzed by
Water-Tolerant Lanthanide Lewis Acid - An Artificial Force
Induced Reaction Study”
Break
16:15～17:30 Associate Professor Pradipta Bandyopadhyay(Jawaharlal Nehru Univ., India)“New Development in Monte Carlo Based Methods: Large
Water Cluster Optimization and Efficient Sampling”
多数の方のご来場を歓迎いたします
We welcome all of you to join.
－ 256 －

fukui2012_02.indb 256

14.1.9 1:48:03 PM

Ⅴ 資料 (2012)６������ ��の研究���の研究所����������の��の����� �
福井謙一記念研究センター長

田中一義

平成２４年９月５日、６日訪問
カリフォルニア大学サンタバーバラ分校 カブリ理論物理学研究所(UCSB,
KITP)： Kavli は財団の名称で、KITP は Kavli 研究所ネットワークの一つ。
Lars Bildsten 所長（今年６月から）・KITP には５つの Faculty （研究室）があり、５人の Permanent Member（教授）がいる。院生、PD18 名もいるが、学部生はいない。しかし学部講義は行う。
・ほかに１２名のスタッフ（計算機、Money, House 関連など）
・UC が土地・建物・職員の給与を負担。
・所長と UCSB の分校長(Chancellor)との関係は大事。UC 自身は巨大すぎる。
・研究資金は NSF から年に４６０万ドル（もとは５００万ドルあったが、不況のため減額）。５年毎に見直し。ほか Simons Foundation などからも補助。
・結局、合計６００万ドル／年で運営している。
・研究所の対外活動として非常に重要と位置づけているのは、”Program”である。
これはあるテーマのもとに研究者がグループを組んで KITP に滞在して研究に専念するためのもの。
・志願者グループは申請書を書く。
・志願者は全世界から（40%が米国外）。中国からはまだ多くない。
・KITP の Advisory Board（所外研究者１５～１７名：米国、カナダ、欧州在）が申請書を審査する。採用に当たっては Coordinator３～４名を決める（志願者
グループの自薦から選ぶことも、Advisory Board が適切な人を持ってくることもある）。
・ちなみにこの Advisory Board Members は年１回開催の Steering Committee@KITP にやってくる。
・採用倍率は 1.5～2 倍・志願者は PD～シニア教授までいろいろ。
・ホテル滞在はあまり精神的にもよくないようなので、貸家、アパートを見つ
けて斡旋する。(House Coordinator の仕事)
・滞在期間は３週間～３ヶ月。滞在中に１回は 100 名規模の Conference を開く
ことが義務。
1－ 257 －

fukui2012_02.indb 257

14.1.9 1:48:03 PM

Ⅴ 資料 (2012)

・１年に１０～１２個の Program が走る。並走することもある。
・給料はなし。KITP からの補助は所内の居場所確保: Allocate space、渡航・滞在費の補助程度のみ。家族を連れてくることも可能。とはいえ、いろいろな世話を実施。Simons Foundation などから補助を貰うための申請もする。
・この Program を走らせることは、結局、KITP の活性化につながるメリットあり。
・http://www.kitp.ucsb.edu/for-scientists
・http://www.kitp.ucsb.edu/for-scientists/suggestions/guidelines
Walter Kohn 元所長（KITP 設立者: 1998 年度ノーベル化学賞）
・1990 年に福井先生に会ったときに、彼の研究所（旧基礎化学研究所）を世界水準にするにはどうしたら良いか聞かれたので、global に考えたときには英語使用が不可避であるため、「活動」を英語中心にすべきと言った。
Cf: おおげさに言えば、Kohn さんはもともと田中の知己。
David Gross 前所長（2004 年度ノーベル物理学賞）

・Asymptotic Freedom in Quantum Chromodynamics (QCD)により受賞。
・東大の国際高等研究所のカブリ数物連携宇宙研究機構（@柏キャンパス）は何かの参考になると思うので、調べることを勧める（Gross 氏も関与している）。
・北京に KITP との連携研究機構が２つある。ひとつは北京大学、もう一つは
中国科学院との合弁。
・現在の京大湯川記念館（基礎物理研）の所長は？という質問もあった（当時は九後先生であると回答）。
Program 関連スタッフからの聞き取り
Marty Einhorn (Deputy Director)+ Michelle Keuper (MSO; Management and Service Officer)
Housing Coordinator（この人は不動産屋でもあるらしい）はこの日不在（休暇？）。
・北野先生（工学研究科長）は 2002 年に走ったうちの Program で２週間 KITPに滞在されたとのこと。
・年に１２個の Program が走り、週当たり２３名（のべ８００名／年）の参加者がいる。
・予算、場所とも制限があるので、この数程度が限界か。
・Program のテーマには理論物理のほかに、数学、生物学、物理化学まで含む。
・基本は、参加者どうし、さらに KITP とも新しい Collaboration が始まること
2－ 258 －

fukui2012_02.indb 258

14.1.9 1:48:04 PM

Ⅴ 資料 (2012)を強く期待している。
・Program の参加者は、通常、車を持っていない。レンタカーも高いので、自転車使用が多い。ダウンタウンからのバスも便利（２０分程度）。
・Program の参加者は４５％が非米国人。
・H1（労働）ビザは不要。
・日・独には研究所も多く、講義義務がないので、そういうところからは Programに参加しやすいのではないだろうか。
・Program の参加者のためのアパートとしては、２Bed Rooms + Common
Kitchen などを使う。常に１室は余分に確保。他にレンタルハウス、下宿なども活用。下宿なら食事も作ってくれるメリットあり。
・ほかに West Cottage（と称する短期滞在型宿泊所？）を（たぶん）UCSB が持っている。２８室あり。
・参加者のアパートにスタッフが出向いて、書類を書かせることもある（細かい気配り）。金銭的なやりとり・交渉を手伝うことも必要。
・参加者の滞在は平均して４週間程度。
・所内各室には基本的に黒板を多く設置。理論家にとっては必須のアイテム。
・建物内部の色はオレンジを基調としている（暖色系：雰囲気つくり）。
・理論物理学者は、気分的には開放的な人が多い。
・午後３時頃にクッキータイム／日を設ける。このような場所にも黒板を置いている。
・そのほかにもピクニック、海水浴、共同晩御飯（割り勘）、ビアパーティなどの行事を多くして（１週間に一度くらい）、全員が溶け込む仕掛けを作っている。
・この意味では、格式ばった Gordon Conference とは違う。
・小規模の Discussion が非常に大事。２０名程度の参加者の Program ではこれが可能。この人数を超えると、「Social Dynamics」が変わってくる。
以上のような質疑で時間切れ。Conference のこと（ネットで、ある程度分かる）
はあまり聞けなかったが、上記 Program が最重要と見える。
ほかに KITP の所謂 Outreach 活動としては、Friends of KITP： 外から著名な学者を呼んで、一晩 Discussion など。
Public Lecture Series：年に３～４回。
Art, Image, Science：非専門家向けのアピール。物理と芸術との関連
Writers & Science：年に最大５カ月程度、科学ライターを呼ぶ。
High School Physics：年に１日、高校の先生を呼んで Conference を行う。などがある。
3－ 259 －

fukui2012_02.indb 259

14.1.9 1:48:04 PM

Ⅴ 資料 (2012)

田中の個人的感想：・これまでの６名の所長のうち、３名がノーベル賞を受賞している。
・大きな研究ダイナミズムは、残念ながら日本の各研究所とはケタが違う感あり。
・それでもこのたび田中が訪問できていろいろな人が会ってくれたのは、福井センターのネームバリューによるのであろう（つまり福井センターにはそういう意味のステータスがある）。

4－ 260 －

fukui2012_02.indb 260

14.1.9 1:48:04 PM

Ⅴ 資料 (2012)

福井謙一記念研究センター長

田中一義

平成２４年１０月１２日、１３日訪問
マックス・プランク固体化学物理学研究所 (MPfS)： Dresden 市にある。
MPfS = Max-Planck-Institut für Chemische Physik fester Stoffe
Liu-Hao Tjeng 所長 (Managing Director)
・この人は在欧の中国人の２（あるいは３）世で、中国語は話せない。オラン
ダで教育を受けている。ドイツ語・英語は当然堪能。専門は固体物理学で、無機物の分光学・強相関現象を研究。管理者というよりは、端正な学者のイメージを受ける。
・MPfS には４つの研究室があり、それを担当する４人の Permanent Member(Director) がいる。
・そのうち２名は固体化学、２名は固体物理学専門。この Director というのは
マックス・プランク研究所 (MPI) 独特の呼称か。大学でいう Professor に相当。
・Director は、J. Grin 氏（固体化学）, C. Felser 氏（固体化学）, F. Steglich氏（固体物理）, L.-H. Tjeng 氏（固体物理）の４名。通常は Prof. Dr.と呼ぶ。
こ れ は 近 隣 の 大 学 （ Dresden 市 内 か ） の 教 授 を も 兼 ね て い て (Honorary
Professor)、学生（４回生、大学院生）を受け入れて研究をさせているため。
・大学での講義義務はない（Tjeng 氏はあった方がよいと少し思っている）。
・Director は人事管理と研究の両方を行う。（Tjeng 氏によると、例えば韓国の研究所ではスタッフ２００名くらいのところに Director１名という体制でやっているが、これでは人事管理が行き届かないと思うとのこと）・MPfS にはもう一人くらい、固体理論専門の Director が欲しいと思っている。
・MPfS には約２００人が在籍し、Scientist, Technician, Assistant（秘書）、ポ
スドク、院生、学部生などを含む。Scientist は１００人以上。うちポスドクは４０名。院生（修士課程１０名、博士課程４０名の計５０名）と学部生は、ドレスデン市内の大学から預かっている。
・諮問委員（Scientific Advisory Board）は７名おり、うち４名がドイツ以外。
・予算は、基本的にドイツ国家が（90-95 %以上）保証していて恵まれており、財団申請などによる外部資金を積極的に取りに行くことは必要ない（テーマが合えば、取りに行くことがある程度）。
・MPfS 自身の自己資産はない。
・ 研 究 所 の 土 地 は 州 政 府 、 建 物 は マ ッ ク ス ・ プ ラ ン ク 協 会 (Max-Planck
Gesellschaft; MPG)所有。
・各 MPI の Director の選考は、MPG が当該 MPI とは完全に独立した人事委
1－ 261 －

fukui2012_02.indb 261

14.1.9 1:48:05 PM

Ⅴ 資料 (2012)

員会を作って行う（これが重要と強調していた）。
・世界的に興味深い研究施設があればすぐにそこに行って、測定をしたり共同研究を行っている。Director 自身が研究には大変アクティブである印象。Tjeng
氏も SPring 8 に測定に数週間来たり、広島大学（先端物質科学研究科：田中 新教授）と共同研究をしている。

資金の流れ
ドイツ連邦政府＋州政府（半々ぐらい出資）
年間１５億ユーロ＝約１６００億円

マックス・プランク協会(Max-Planck Gesellschaft; MPG)＠ミュンヘン

ドイツ全国に８０ある研究所(MPI：合計約２６０名の Directors がいる)と、協会本部運営＋新しい研究所の計画などにすべて予算を配付。これによって各
MPI の人件費や研究費はほぼすべて賄える。
・ドイツ政府と MPG の間には強い関係がある。このことは非常に重要。
・産業の生産部門をドイツで持っていると高額である。ルーマニア等の賃金の安い国で行う方が遥かに効率がよい。従ってドイツでは、基本的な研究知見を貯める方が得策。ただし製品のデザイン的なプロセスは行う。
・博士一人を養成するのにかかる費用は膨大であり、これを多く輩出するのがドイツの国力に繋がる。
・以上のように、ドイツ国内で基礎科学を進展させることは国是でもあり、これが欧州不況のおりでも政府が MPG に大量に資金投下をする理由である。
（日本も見習うべきか）・MPfS も基本的には無機固体物理の基礎研究がメイン。しかし無機固体化学のDirector は企業と共同研究をして、特許などを取得することもある。
・MPfS と他研究機関との共同研究は平均９機関ぐらいと（Partner Group と呼称。ドイツ以外の国も多くある。日本では物材機構など。アジアでは中国、台湾、韓国の研究機関などとも展開)。
・ロシアからのポスドクは一人２～３年間滞在させている。彼らがロシアに帰国してからも、２～３万ユーロ／年を「仕送り」して、研究助成をしている。
・外国からの訪問研究者(Visitor)は MPI と契約をし、１年間くらい滞在できる
2－ 262 －

fukui2012_02.indb 262

14.1.9 1:48:05 PM

Ⅴ 資料 (2012)（実際に決裁するのは各 Director）。月２５００ユーロくらいを支給（近隣のアパートには月５００ユーロくらいで入れる）。
・近々、東大・理・物理の高木英典教授が Stuttgart の MPI の Director に着任される。
・対外活動としては、年４～５回のワークショップ開催、コンファレンス開催、
ユーロスクール（若手院生向けか？）など。田中の滞在期間にも超伝導のワー
クショップ(LEMSUPER)が開かれていたので、勧められて部分的に出席した。
・社会へのアウトリーチ活動としては、ドレスデン市共催で、年に１回 Long
Night of Science という催しを行っている（７月の第１金曜の夜の時から深夜まで）。これは MPfS だけではなく、在ドレスデンの大学・研究所がほぼすべて参
加して、演示実験や科学イベントを行う。一般市民が３５００人程度参加。

参考：
ドイツには４つの協会があって、相補的に動いている。
① マックス・プランク協会(Max-Planck Gesellschaft)はほぼ基礎研究専一。
② フラウンホーファ協会（Fraunhofer Gesellschaft）（年間予算１２億ユーロ）
は応用研究専門。起業向け。
③ ヘルムホルツ協会（Helmholtz Gemeinschaft）（年間予算２８億ユーロ）は工業化前段階の技術開発など。ここの機器設備は充実している。
④ ライプニッツ協会（Leibniz Gemeinschaft）は社会科学専門。

田中の個人的感想：
・自分自身にとっては全く初めてのマックス・プランク研究所(MPI)訪問であったが、その財務・管理・研究体制の大枠が理解できた。
・前回に訪問した米国 UCSB のカブリ理論物理学研究所とは全く異なった印象。
ドイツの国力を感じさせる研究所で、恐らく他の MPI もこのようなイメージかと思える。
・改めて基礎研究の重要さに対する国家あげてのバックアップ精神の認識ができた感あり。「研究かくあるべし」
・この Tjeng 所長は大変研究好きな人であり、上記の話のほかに、無機物質の構造と磁性の関係、強相関現象、マルチフェロイック現象、多体効果、動的平
均場理論、トポロジカル絶縁体、マヨラナ場、などの議論をいっぱいさせられた（かなりの時間を費やした）。これはあまり期待しなかったことであるが、良い頭の体操になりました。
3－ 263 －

fukui2012_02.indb 263

14.1.9 1:48:06 PM

Ⅴ 資料 (2012)

福井謙一記念研究センター長

田中一義

平成２４年１１月２３日、２４日訪問
キャベンディッシュ研究所： Cambridge 市にある。
総��キャベンディッシュ研究所はケンブリッジ大学の物理学教室と１００％同じである。その意味で、通常の研究所の概念とは異なっており、むしろ大学の一学科と理解する方が当たっている。
なぜことさらに「キャベンディッシュ研究所」という名称を冠するかと言うと、当該物理学教室の発祥が 1871 年に H. Cavendish を記念して作られたキャベ
ンディッシュ研究所（初代所長は J. C. Maxwell）にあるため、この名称を頑なに守っていることが理由である。
これまでに２９名のノーベル賞受賞者を輩出しており、このことを非常に誇りとしているように見える。なおすべてが物理学賞受賞者ではなく、Rutherford,
Aston のように化学賞受賞者が６名、Watson, Crick のように医学・生理学賞受賞者が３名含まれていることは興味深い。
James Stirling 所長 (Head of the Cavendish)・上記の意味で、Stirling 所長は物理学教室の主任を兼ねている。この人の専門は高エネルギー物理学である。典型的な英国人紳士で好感が持てる。
・キャベンディッシュ研究所は 1871 年～1974 年まではケンブリッジ旧市内の中心部分にあったが、その後同市の西郊外の広大な牧草地近隣のキャンパスに移り、現在も建物を増築中である。しかしケンブリッジ旧市街中心地までは乗換なしの市バス１本で繋がっていて便利である。
・本研究所（学科）の研究スタッフは約１７０名（教員＋博士研究員）で、教員（教授、講師など）では約７０名が在籍している。その他事務スタッフ、技術スタッフが在籍。
学部学生は約１０００名（１年生４５０名、２年生２００名、３年生２００名、４年生１５０名）で、大学院には年間に６０～７０名が進学する。このう
ち英国外からの学生は約１０％であり、そのうちの半数は中国人学生でかなりよくできるが、彼らの主たる興味は Engineering 寄りである。なお日本人学生は非常に少ない。上記の学生数規模は、ちょうど本学の工学部工業化学科およびその上部の化学系専攻を合わせたものと似ているとも言える。
・本研究所（学科）の総予算は 2200 万ポンド／年（日本円で 28 億 6 千万円／年）であり、かなり潤沢と言える。その内訳は、学生からの授業料（一人 9000
ポンド／年（日本円で 117 万円／年））、私学としてのインフラ・人件費予算、
1－ 264 －

fukui2012_02.indb 264

14.1.9 1:48:06 PM

Ⅴ 資料 (2012)

国(Research Council)からのプロジェクト研究費予算、さらに同窓会組織からの寄附などである。
・以前の Cambridge 大学生は物理学にあまり興味がなかったが、最近の国策および研究所自身のアウトリーチ活動（後述）の効果が出てきて、物理学をやりたい学生が増えてきている。なおご多分に漏れず、英国でも子供数が減ってきているので、今後良い素質を持つ物理学志望の学生獲得にはなお注力する予定とのこと。
・本研究所（学科）の物理学研究は多岐に亘るが、特色は、通常の物理学のほかに、宇宙物理学、高エネルギー物理学、薬理物理学、原子・メソスコピック・
光物理学、および計算物理学などにある。薬理物理学を含むのは Watson, Crickなどからの伝統、また原子系を含むのは化学的な Rutherford, Aston, Hodgkin,
Klug などからの伝統であるらしい。
・９月に訪問した、米国カリフォルニア大学サンタバーバラ分校のカブリ理論
物理学研究所と同じカブリ財団が寄与して作ったカブリ宇宙学(Cosmology)研究所もある（広大な敷地ならでは）。
・日本の日立や東芝ともコラボ研究契約を結んで研究室を設置し、前者とはマイクロエレクトロニクス・オプトエレクトロニクス、後者とは半導体物理学・
量子情報理論の共同研究を展開している。
・高校生および高校教員に対して、Educational Outreach という高大連携活動
を 頻 繁 に 実 施 し て い て 、 そ の た め の 専 任 ス タ ッ フ を 置 い て い る (Lisa
Jardine-Wright 博士)。年間６００名程度の高校生を受け入れて、物理学についての分かりやすい講義や体験実験を受講させるようにしている。また各高校への出前講義も行っている。これらのためのグッズ（パンフレットやテキストを始めとする種々のコンファレンスキットのようなものまで）も充実している。

田中の個人的感想：
・自分自身にとっては全く初めての Cavendish 研究所訪問であり、ケンブリッ
ジ大学の物理学教室と同一であることや、その財務・管理・研究体制の大枠が理解できた。
・この意味では、これまでに訪問した米国 UCSB のカブリ理論物理学研究所やドイツのマックス・プランク研究所とは全く異なった印象であり、むしろ大学の一学科の運営方針の勉強になった面が強い。
・自然科学全般に関する英国の誇りと、その教育・研究持続のための具体例として Cavendish 研究所は充分興味深い意味を持つと思えた。
・特に優秀な研究者の予備軍としての高校生への物理学の啓蒙の徹底には瞠目
2－ 265 －

fukui2012_02.indb 265

14.1.9 1:48:06 PM

Ⅴ 資料 (2012)

すべきものがあり、これぐらい積極的な高大連携をとるべきかと考えさせられた。
・田中自身が工学のなかの化学系所属であるということが、Stirling 所長には非常に奇異に映ったと見える。彼らのマインドからすると、恐らく工学は一段低
いものであり、そこで化学をやっていることはあり得ないことのようである。
かつて福井先生がノーベル賞をとられたときに、欧米の多くの研究者は福井先生の所属が理・物理であると思ったらしいことと一脈通じるものがある。

3－ 266 －

fukui2012_02.indb 266

14.1.9 1:48:07 PM

Ⅴ 資料 (2012)

平成 25 年 3 月 6 日

ྎ‴ࡢ◊✲ᶵ㛵࡜ࡢ஺ὶሗ࿌᭩
福井謙一記念研究センター国際連携研究室
石田俊正
平成 25 年 2 月 25 日から 27 日まで、当センター国際連携強化プロジェクトの一環として、
台湾大学擬態科学研究中心・中央研究院原子與分子科学研究所・台湾交通大学分子科学研
究所の３研究所で、将来の共同研究への可能性を探るために実験家との交流を行った。それぞれの英語名は、台湾大学擬態科学研究中心が Center for Condensed Matter Sciences,
National Taiwan University、中央研究院原子與分子科学研究所が Institute of Atomic andMolecular Sciences, Academia Sinica、台湾交通大学分子科学研究所が Institute of Molecular
Science, National Chiao Tung University である。今回の交流に際して、台湾大学擬態科学研究
中心の林倫年研究員に仲介をお願いした。
 ᅜ❧ྎ‴኱Ꮫᨃែ⛉Ꮫ◊✲୰ᚰ
林研究員から、台湾大学擬態科学
研究中心に概略を説明いただいた。
ファカルティメンバーは 12 名であり、林研究員を除いて、全員が実験研究を行っている。そのため、実験と理論研究の共同研究が盛んに行われている。3 人の実験研究員を紹介いただき、お話を伺うとともにディスカッ
ションを行った。
(1)

Juen-Kai Wang（王俊凱）研究員

研究分野は多岐で、基礎的な高速分光から、実用に近い有機太陽電池までにわたっている。
現在、実験からわからないこととして具体的に２つのことを提起された。一つは、有機太陽電池でのモーフォロジーの変化によって反応性がどのように変化するかについてである。（有機太陽電池では、ドナーとアクセプターが平面の境界面を構成せず、表面積を稼ぐため入り組んだ界面を構成する）
1－ 267 －

fukui2012_02.indb 267

14.1.9 1:48:07 PM

Ⅴ 資料 (2012)

もう一つは、表面増強ラマン分光の実験において大腸菌 E. Coli によるピークがいくつか出現するが、そのピークが E. Coli のどの部分構造によるものかということであった。
どちらも応用に大きく結びついた実験に関連する解釈であり、よい共同研究ができれば、理論の価値が大きく高まる可能性があると思われる。
(2)

F. C. Chou（周方正）研究員

スピンに興味をもつ固体物理の実験家。物理では、バンド計算が多用されているが、実験の解釈には、化学で使われている混成や共鳴などの概念が重要に思えると語っていた。混成・共鳴などの概念を周期系または固体の電子構造にどのような形で生かしうるかを知りたがっていた。
(3)

Woei-Wu Pai（白偉武）研究員

走査プローブ顕微鏡を用いた表面の実験をしている。固体表面での反応に興味をもっているが、反応により周期性境界条件が成り立たなくなっているため、固体物理で用いるバンド計算を適用するのが難しいとのことであり、化学で用いるクラスター計算手法に興味を持っていた。
 ୰ኸ◊✲㝔ཎᏊ⯅ศᏊ⛉Ꮵ◊✲ᡤ
台湾大学の中にあるが、大学とは別組織で政府直轄の研究所である。29 名のファカルティメンバーを有している。
ファカルティには、台湾で唯一のノーベル賞受賞者である Yuan-She Lee(李遠 哲 ) 氏 も 特 聘 研 究 員 (Distinguished
Research Fellow)として名を連ねている。
(1)

Kopin Liu（劉國平）特聘研究員

配向を制御した CDH2 と Cl 原子との衝突実験から、配向の違いにより生成物が異なり、それが CD の振動励起、回転励起に依存することを見いだした最近の研究（Science, Nature
Chemistry に掲載）、さらには、CH4 と Cl 原子の場合、CDH2+Cl とは全く異なる機構であることを見いだしたことを伺った。CH4 と CDH2 では、H と D の違いがあるだけだが、分子が正四面型から対象コマ分子に変化することで大きな変化が起こるようで理論の寄与が期待されるところである。
(2)

Jim Jr-Min Lin（林志民）研究員
2－ 268 －

fukui2012_02.indb 268

14.1.9 1:48:08 PM

Ⅴ 資料 (2012)

オゾン層破壊に関わる ClOOCl の関わる反応の分子線を使った精密実験のほか、いくつかの気相分子の反応の結果を伺った。実験室で研究内容の説明をいただき、実験装置（真空チェンバー、レーザー、装置構成）の説明もしていただいた。
(3) Chi-Kung Kenny Ni（倪其焜）教授
３つのテーマについてお話しいただいた。振動・回転エネルギーが運動エネルギーへ移行する過程の研究、水素結合の励起状態のポテンシャル面への影響の研究、MALDI(マトリックス支援レーザー脱離イオン化法)の機構の解明についてである。MALDI はノーベル賞を受賞した田中耕一氏の貢献が大きい手法であるが、機構に未解明なところが多かったのが Ni 教授らによって解明されつつあるとのことであった。
昼食をご一緒させていただいたが、日本の科学だけでなく、政治にも興味を持っておられるようで、最近できた第二次安倍政権のことをよく訊かれた。
(4) 高橋開人助研究員
専門は理論計算で、原子與分子科學研究所にどのような人がいてどのような研究が行われているかの話をしてくださった。理論家は 3 名で、ほかの 26 名は実験研究を行っているとのことであった。そののち、高橋助研究員自身の研究、OH-(H2O)n クラスターの構造の話等を伺った。
 ᅜ❧஺㏻኱ᏛศᏊ⛉Ꮫ◊✲ᡤ
国立交通大学に関しては、Yuan-Pern Lee（李遠鵬）応用化学科長が窓口になってくださり、実験研究者 3 名、理論研究者 3
名のお話を伺うとともに、ディスカッションを行った。分子科学研究所には、20 人のファカルティが所属している。Lee 教授には、車で駅まで迎えに来てくださった際、学内を車で案内くださった。交通大学は理科系中心の大学であり、日本で言うと東京工業大学に当たるような大学のようである。また、隣接して総合大学的な清華大学があり、そちらの方が一般的には有名である。しかし、最近の論文数などを示すグラフを用いて、最近は研究面で清華大学をしのぐ成果を分子科学
研究所では出しているとの説明をしていただいた。（これは、あとで話を伺った中村教授によると、Lee 学科長のてこ入れによるものであるとのことであった。）この Lee 教授はノーベル賞受賞者の Yuan Tseh Lee 氏の弟に当たる。
(1)

Yuan-Pern Lee（李遠鵬）教授（応用化学科研究科長）
実験室を案内していただき、レーザー誘起蛍光を使ったラジカル種の動力学的研
究、マトリックスの影響の非常に少ないスペクトルのとれる、パラ水素を使ったマ
3－ 269 －

fukui2012_02.indb 269

14.1.9 1:48:08 PM

Ⅴ 資料 (2012)

トリックス単離実験、通常のフーリエ変換赤外分光と異なり高速な測定が可能な、ステップスキャン時間分解フーリエ変換法の説明とその応用を説明いただいた。
(2) 重藤真介副教授
水クラスター、ラマン顕微分光による細胞構造のイメージングの話を伺った。ラマ
ン顕微分光では、波数成分に対して主成分分析のような手法を適用することにより、細胞の内部構造に特徴的なイメージングができることを見せていただき、個人的にとても印象的であった。
(3)

Eric, Wei-Guang Diau （刁維光）教授

実験も理論計算も行う研究者であるが、現在は色素増感太陽電池の実験を行っている。色素からの酸化チタン電極への電子移動に理論的な問題があり、取り組んでいるとのことであった。以前教授が行っていたアゾベンゼンの光異性化の計算についても意見を交換し、理論家と実験家の間で論争になっている点、すなわち、異性化の時に、ベンゼン環が平面に沿って動くか回転して動くかについて議論を行うことができて有意義であった。
ほかに、3 人の理論研究者と交流した。反応動力学が専門の中村宏樹教授は分子科学研究所長当時、特別推進研究を行い、石田も参加させていただいていた。同じく反応動力学が専門の Chaoyuan Zhu （朱超原）教授は以前からの知己であり、最近の研究成果を紹介いた
だいた。3 人目は、Sheng Hsien Lin （林聖賢）教授である。Lin 教授は計算機を使わず、密度行列に興味を持って純粋的な理論研究を行っている。

以上台湾の 3 研究所、台湾大学擬態科学研究中心・中央研究院原子與分子科学研究所・
台湾交通大学分子科学研究所をまわっての印象は、いずれも実験研究者のレベルは、理論研究者とともに高く、国際連携研究にふさわしい研究所であるということである。今回の交流が今後の共同研究につながっていけば幸いである。

4－ 270 －

fukui2012_02.indb 270

14.1.9 1:48:09 PM

Ⅴ 資料 (2012)

平成 25 年 3 月 6 日

ユトレヒト大学訪問
国際連携研究室 池野豪一

平成 25 年 2 月 18 日から 2 月 22 日の間，
オランダにあるユトレヒト大学化学科，
Debye
ナノ材料科学研究センター，無機化学・触媒研究グループ (Inorganic Chemistry and
Catalysis, Debye Institute for Nanomaterials Science, Utrecht University) の Frank de Groot
教授を訪問した．今回の訪問の目的は国際連携機能強化プロジェクトの活動の一環として，将来的な共同研究の可能性を探ることにある．また，2 月 21，22 日の両日は同教授の呼び掛けにより，”Workshop on Fundamental Aspects of X-ray Spectroscopies: the roleof the 2p core hole in XAS and RIXS (FXS2013)” が開催された．本ワークショップには主にヨーロッパ，アメリカの X 線分光実験，理論の研究者が集まり活発な議論が行われた．私も本ワークショップに参加し，各国の研究者と交流を行った．

Debye ナノ材料科学研究センター (Debye Institute for Nanomaterials Science)
同センターは 1936 年にノーベル化学賞を受賞したオランダ人物理化学者，Peter J. M.
Debye の名を冠する研究センターであり，1989 年に設立された．同センターは化学科(Department of Chemistry)，および物理・天文学科(Department of Physics & Astronomy)に属する 6 つの研究グループによって構成されている．
無機化学・触媒研究グループ
前述の Debye ナノ材料科学研究センターに属する研究グループの 1 つである．同グル
ープは Krijn de Jong 教授，Bert Weckhuysen 教授，Frank de Groot 教授 3 名のフルプロフ
ェッサーが中心となり，パーマネント教員 5 名，技術職員 6 名，ポスドク 18 名，Ph.D
学生 40 名，他学部学生合わせて約 80 名からなる巨大な研究グループである．その名が表す通り，無機触媒の合成と特性評価，さらに分光法を用いた触媒反応プロセスの解析に関する研究を中心に行っている．研究資金はオランダ政府，EU からの競争的資金の他に，石油エネルギー企業との共同研究プロジェクトを実施することで獲得しているとのこと．
Frank de Groot 教授
Frank de Groot 教授の専門は触媒科学ではなく，無機化学である．特に放射光を用いた X 線分光の分野においては世界をリードする研究者の一人であり，世界各地の実験・
1－ 271 －

fukui2012_02.indb 271

14.1.9 1:48:09 PM

Ⅴ 資料 (2012)

理論研究者と繋がりがある．無機化学・触媒グループにおいて，同教授のグループは少人数であるが，X 線分光を利用した触媒反応プロセスの解析に関する重要な役割を担っている．それ以外にも，X 線分光の理論の確立，新しい X 線分光実験の開発といった基礎的な研究も行っている．

—— 研究テーマについて ——現在，Frank de Groot 教授のグループで行われている研究テーマについて伺った．
(1) X 線吸収分光(XAS)の理論解析
XAS は X 線と物質の相互作用により，内殼軌道から非占有軌道へ電子が遷移することに対応するスペクトルである，その解釈には量子論に基づく理論計算が欠かせない．
同グループではスペクトル測定と同時に時間依存密度汎関数理論(TD-DFT)を用いたス
ペクトルの理論計算を行っている．3d 遷移金属化合物の L 端(2p→3d 遷移)や希土類元素の M 端(3d→4f 遷移)においては，強い電子相関をあらわに取り扱う必要がある．その場合には，配位子場理論に基づく半経験的な手法を用いた理論計算を利用している．
(2) 共鳴非弾性 X 線散乱(RIXS)法の開発
RIXS は，元素の吸収端に近いエネルギーの X 線で内殼の電子が励起させ，その緩和過程で放出される蛍光 X 線を分光する測定法である．遷移金属化合物においては，格子振動，d-d 遷移から内殼励起過程まで，硬 X 線を用いたでバルク敏感な測定が可能である．同グループでは，測定法とその解析理論の開発といった基礎的な研究，触媒科学への応用研究の両方を行っている．

(3) ナノ粒子の化学吸着過程の解析
遷移金属ナノ粒子の合成，および X 線分光と理論計算を利用したナノ粒子の電子状態の解析を行っている．化学吸着による電子状態の変化やナノ粒子のサイズ効果，合金効
果について系統的な研究を行っているとこと．また，顕微 X 線分光を利用した化学吸
着過程の動的観察も行っているとのこと．

(4) 走査型透過型 X 線顕微鏡(STXM)の開発
集光した X 線を走査プローブとして X 線吸収スペクトルの測定を行う方法で，約 20nmの空間分解能で試料内部の化学種のマッピングが可能である．これまでに反応中の触媒のナノスケールイメージングに成功している．

2－ 272 －

fukui2012_02.indb 272

14.1.9 1:48:10 PM

Ⅴ 資料 (2012)—— 量子化学計算に対するニーズ ——上記の研究テーマと別に X 線分光実験の研究者としての立場から，量子化学計算に対するニーズについてお話を伺った．

(1) 遷移金属化合物における XAS, RIXS の第一原理計算
配位子場理論に基づく半経験的計算は有用ではあるが，対称性の低い系や表面，界面といった系を解析するにはフィッティングパラメータが多くなり，解釈が困難となる問題がある．実際の原子構造と電子状態，スペクトルを直接結びつけることができる第一原理計算からのアプローチが望ましい．本テーマについては，池野と共同研究を実施しているが今後も継続することで合意した．

(2) 遷移金属錯体/遷移金属タンパク質の X 線分光と電子状態
複数原子からなる配位子を持つ遷移金属錯体において，中心金属の電子状態を X 線
分光と理論計算から解明する．特に遷移金属のスピン状態や，配位子と金属原子間の電荷移動について関心があるとのこと．また遷移金属元素を含む金属タンパク質の電子状態について，幾つかの研究グループが測定を行っているが，理論計算はまだまだ不十分とのこと．
(3) 自由電子レーザー(FEL)を用いた励起状態の解明
分光用の X 線と同時にレーザー光を同時に入射させて行う XAS,RIXS 法が開発されている．通常の XAS, RIXS 測定において，遷移の始状態は系の基底状態であるが，レーザー光を照射することで，系を基底状態から励起させ，その準位を始状態としたスペクトルを測定することができる．しかし，スペクトルの解析には励起状態の高精度計算が必要となると考えられる．

(4) パルスレーザーを用いた分子のダイナミクス
測定方法としては(3)と類似のものである．分子に対し，フェムト秒パルスレーザーを入射し，時間分解のスペクトルを測定することで，分子のダイナミクス(解離，拡散，化学反応)を追跡することが目的とのこと．スペクトルの時間発展をシミュレートした計算ができるかどうか知りたいとのこと．

3－ 273 －

fukui2012_02.indb 273

14.1.9 1:48:10 PM

Ⅴ 資料 (2012)

Pieter Glatzel (Dr.)
FXS2013 ワークショップ参加者の一人．現在はフランスのグルノーブルにある放射光施設, European Synchrotron Radiation Facility (ESRF), ID26 ビームライン責任者．Frankde Groot 教授とはよく共同研究を行っている．最近は．硬 X 線を用いた RIXS 実験を主に行っている．講演内容は硬 X 線 RIXS の原理についての説明と最近の研究成果についてである．講演後他の理論研究者も交えて議論を交わした．特に物性物理で長年議論の対象となっている Ce 酸化物の価数について興味があるようで，RIXS 実験結果を理論的にどう解釈すれば良いか，特に Ce の 4f 電子数はどうなっているのか知りたがっていた．

Amelie Juhin (Dr.)
FXS2013 ワークショップ参加者の一人．フランスのピエール・マリー・キュリー大学(パリ第 6 大学)の研究員．RIXS の磁気円二色性(MCD)の実験を行っている．MCD は磁化させた磁性体に左右偏光方向の異なる円偏光 X 線を用いて得られるスペクトルの差として定義され，磁気構造に関する情報が得られる．様々な Fe 化合物の RIXS-MCD 結
果と sum-rule を用いた解析結果について話を伺った．
Philippe Wernet (Dr.)
FXS2013 ワークショップ参加者の一人．Helmholtz Zentrum Berlin (HZB)の研究員．HZBにある放射光施設 BESSY II で自由電子レーザーを利用した RIXS 測定から遷移金属を含む分子のダイナミクスの観察を行っている．反応パスの解析を始めとする分子のダイ
ナミクスに興味があるとのこと．遷移金属を含む分子の L2,3 端 XAS,RIXS の理論計算について相談を受けた．
Piter Miedema (Dr.)
FXS2013 ワークショップ参加者の一人．de Groot 教授の下で Ph.D を取得した．3d 遷移金属錯体の電子状態と触媒反応について研究を行っていた．現在はドイツのHelmholtz Zentrum Berlin (HZB)のポスドク研究員．HZB にある放射光施設 BESSY II で
自由電子レーザーを利用した固体の RIXS 測定から物質の素励起過程を調べる研究を行っているとのこと．理論計算も自身で行っており，他の実験研究員からも良く相談を受けるとか．使い易いインターフェイスを持った計算プログラムの重要性について語ってくれた．

4－ 274 －

fukui2012_02.indb 274

14.1.9 1:48:10 PM

Ⅴ 資料 (2012)

Matti M. van Schooneveld (Ph.D 学生)
FXS2013 ワークショップ参加者の一人．de Groot 教授の学生で，ナノ粒子の合成と X
線分光を用いた解析に関する研究を行っている．現在の所属は Max Planck 研究所(Mulheim)である．2 月 25 日ユトレヒト大学において学位論文の公聴会が開催されたとのこと．学位論文の内容から特に Co 化合物における RIXS の測定結果とその解釈について説明を受け，議論を交わした．Co ナノ粒子のスペクトルの第一原理計算について知りたがっていた．

Josh Vura-Weis (Dr.)
FXS2013 ワークショップ参加者の一人．アメリカ，UC Berkley のポスドク研究員．
テーブルトップのパルス X 線源を開発し，低エネルギー(30-100eV)の光子を利用して X
線分光実験を行う装置を開発したとの説明を受けた．遷移金属化合物の M2,3 端(3p→3d遷移)の測定結果について紹介された．その後，M2,3 端の理論解析をしたいとのことで，第一原理計算による計算について相談を受けた．
FXS2013 ワークショップにおいては，実験研究者の他，理論計算の専門家も多数集まっており，活発な議論が行われた．

池野の個人的感想：
近年の X 線分光実験の技術の進歩は目覚しいものがある．最近は，RIXS 法と自由電子レーザーを利用した励起状態，分子ダイナミクスの探索が流行っているようである．
一方で，スペクトルを解析する理論計算手法の進展はまだまだこれから，といった印象
で あ る ． 理 論 面 で の キ ー ワ ー ド と し て は ， 電 子 相 関 ， 巨 大 な 活 性 空 間 ， beyond
Born-Oppenheimer 近似，フォノン，マグノン，電子・格子相互作用，巨大分子などが挙げられるであろうか．いずれも計算分野において挑戦的な内容であるが，同時に X 線
分光のコミュニティにおいて量子化学研究者が貢献する余地は大いに存在すると感じた．実験研究者からのスペクトルの理論計算に関する要求は非常に強く，今回の訪問においても多数の実験研究者から同様の相談を受けた．研究対象となる物質についても理論研究者と共通する部分が多く，スムーズに共同研究を行うことができると期待される．

5－ 275 －

fukui2012_02.indb 275

14.1.9 1:48:11 PM

Ⅴ 資料 (2012)
差出人: Windows Internet Explorer 8 ﾅﾛｶｳ・｢ﾜｷ７．社会へのアウトリーチ活動紹介記事
件名: 出張講義のご案内
日時: 2013年12月11日 09:51:32JST

宛先: Windows Internet Explorer 8 ﾅﾛｶｳ・｢ﾜｷ出張講義
福井謙一記念研究センターでは出張講義を承っております。

現在の講師
諸熊奎治（リサーチリーダー）
お申し込みはlecture＠fukui.kyoto-u.ac.jp （＠を@に変えて下さい）
075-711-7708（事務室）
までお願いいたします。

コンピュータで化学反応の世界を探る
京都大学福井謙一記念研究センター!

リサーチリーダー

諸熊奎治

福井謙一先生のフロンティア軌道理論が出て６０年経ちました。手回し計算機で化学反応の容易さを明らかにされた先生の慧眼には感嘆するばかりです。コンピュータの進歩によって今ではその１兆倍の速さで計算ができるようになり、化学反応がどのようにして起っているかを明らかにすることができる
ようになりました。60サッカーボール分子はどのように生成されるのか、触媒反応はどのようにむのに進むのか、クラゲの緑色蛍光タンパクはなぜ光るのかなど、化学反応が起る様子を、コンピュータを使って“眼で見たように”追跡したいと思います。

滋賀県立守山高等学校での講義風景－ 276 －

fukui2012_02.indb 276

14.1.9 1:48:11 PM

Ⅴ 資料 (2012)

滋賀県立守山高等学校での講義風景

京都府立南陽高等学校での講義風景

!
諸熊奎治

略歴

京都大学福井謙一研究室出身。分子科学研究所、アメリカエモリー大学教授などを経て、平成１８年から福井謙一記念研究センターリサーチリーダー。

－ 277 －

fukui2012_02.indb 277

14.1.9 1:48:11 PM

Ⅴ 資料 (2012)

８．諸熊奎治シニアリサーチフェローに文化功労者の顕彰に関する記事－ 278 －

fukui2012_02.indb 278

14.1.9 1:48:13 PM

Ⅴ 資料 (2012)－ 279 －

fukui2012_02.indb 279

14.1.9 1:48:13 PM

1/2
Ⅴ 資料 (2012)－ 280 －

mhtml:file://C:\Users\matsumura\Desktop\
fukui2012_02.indb 280

NGP\... 2013/12/10
14.1.9 1:48:14 PM

2/2
Ⅴ 資料 (2012)－ 281 －

mhtml:file://C:\Users\matsumura\Desktop\
fukui2012_02.indb 281

NGP\... 2013/12/10
14.1.9 1:48:14 PM

fukui2012_02.indb 282

14.1.9 1:48:14 PM京都大学福井謙一記念研究センター

年報

2012

2013 年 12 月発行
発行人

田 中 一 義編

田 中 一 義者

発行所

京都大学福井謙一記念研究センター（京都市左京区高野西開町 34-4）

印刷所

株式会社 エヌジーピー（京都市右京区太秦森ヶ東町 21-10）（無断転載を禁ず）

fukui2012_02.indb 283

14.1.9 1:48:14 PM

fukui2012_02.indb 284

14.1.9 1:48:14 PM

Annual Report

2012

Annual Report
20122102 tropeR launnA