Annual Report

2013

Annual Report
2013

3102 tropeR launnA

年
報
年 報

2010
2013

京都大学
福井謙一記念研究センター

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はじめに2013 年度(平成 25 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。専任教員定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。そして世界中からの公募による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。この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雇用であり、自分自身のアイディアで一定期間、自由闊達に研究できる身分を保証されています。
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 2006 年～2012
年(平成 18 年～24 年)の間、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専念されました。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として転出されました。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、2014 年(平成 26年) 3 月に日本化学会賞を受賞されました。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、そのメンバーもセンターで研究に励んでいます。私達は、センターが博士学位を取得した若手研究者のさらなる切磋琢
磨の場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を終えられた多くの方々が、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)にアジア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ように、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、九州大学、分子科学研究所、北京師範大学の教授になり、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－i－fukui2013.indb 3

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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)に本学に寄贈されて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。京都大学の部局となった後、森島 績、中辻 博、榊 茂好、田中 功の各先生にセンター長
としてご指導を頂きました。
本センターで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。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、一層の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～初冬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、現在本センターのシニアリサーチフェローである諸熊奎治先生は、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、本センターの名をさらに高めて頂いたことでもあり、大変喜ばしいことであります。
本センターは、上述のように規模は大きくありませんが、研究活動はきわめて活発です。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 26 年 11 月
京都大学福井謙一記念研究センター長

田中一義－ ii －

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目

はじめに

Ⅰ

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

専任教員・スーパーバイザー

２．教員プロフィール

Ⅱ

Ⅲ

Ⅳ

(1) センター長 �������������������������

2(2) 副センター長 ������������������������

4(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 �������������������

17(6) リサーチリーダー ����������������������

19

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

20

２．博士研究員プロフィール ���������������������

21

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 ��������������

49

２．福井謙一記念研究センターセミナー ����������������

50

３．社会へのアウトリーチ活動 ��������������������

50

４．その他（報告） ��������������������������

51

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

52

２．シニアリサーチフェロー ���������������������

57

３．リサーチリーダー ������������������������

69

４．博士研究員 ���������������������������

77－ iii －

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Ⅴ資料
１．外国人共同研究者受入れ状況 ………………………………………………… 191
２．海外渡航一覧 …………………………………………………………………… 192
３．研究業績一覧 …………………………………………………………………… 193
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 ……… 205
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 …………… 213
６．その他（報告） ………………………………………………………………… 214（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/AnnualReport2013.pdf）－ iv －

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Ⅰ 専任教員 ･ スーパーバイザー (2013)Ⅰ

専任教員・スーパーバイザー

１．教員組織平成２５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（欠員中）

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

理学研究科長有 賀

哲 也

理学研究科化学専攻

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

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

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

理学研究科物理学・宇宙物理学専攻

教

授

時 任

宣 博

化学研究所物質創製化学研究系

教

授

八 尾

誠

理学研究科物理学第一教室

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

教

林

重 彦

理学研究科化学専攻

授（工学研究科合成・生物化学専攻）

工学研究科材料化学専攻

総合研究部門准 教 授

池 田 昌 司専任

理論研究部門

准 教 授( 欠員中 )

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）－1－fukui2013.indb 1

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Ⅰ 専任教員 ･ スーパーバイザー (2013)

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

京都大学工学研究科石油化学専攻博士課程修了【学位】 1978 年 3 月

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）
3. 統計力学入門

化学者の視点から（単著 , 化学同人 , 2014）（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).

－2－

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Ⅰ 専任教員 ･ スーパーバイザー (2013)

6. Chemical Reactivity in Nucleophilic Cycloaddition to C 70: 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).
11. Vibronically Induced Activation Mechanism in Photocatalysis of Highly Dispersed
Vanadium Oxide Supported on Silica, V2O5/SiO2: Evidence in Phosphorescence
Spectra (N. Iwahara, T. Sato, K. Tanaka, and T. Tanaka) Chem. Phys. Lett., 584,
63-66 (2013).
12. Reaction Mechanism in the Mechanochemical Synthesis of Dibenzophenazine:
Application of Vibronic Coupling Density Analysis (N. Haruta, T. Sato, K. Tanaka,
and M. Baron) Tetrahedron Lett., 54, 5920-5923 (2013).
13. Redox Modulation of para-Phenylenediamine by Substituted Nitronyl Nitroxide
Groups and Their Spin States (A. Ito, R. Kurata, D. Sakamaki, S. Yano, Y. Kono,
Y. Nakano, K. Furukawa, T. Kato, and K. Tanaka) J. Phys. Chem. A, 117, 1285812867 (2013).
14. Vibronic Couplings in C60 Derivatives for Organic Photovoltaics (N. Iwahara, T.
Sato, K. Tanaka, and H. Kaji) Chem. Phys. Lett., 590, 169-174 (2013).
15. Preparation of D-A Polymer with Disilanobithiophene as New Donor Component
and Application to High-voltage Bulk Heterojunction Polymer Solar Cell (J.
Ohshita, M. Nakashima, D. Tanaka, Y. Morihara, H. Fueno, and K. Tanaka) Polym.
Chem., 5, 346-349 (2014).
16. Enhancement of Fluorescence in Anthracene by Chlorination: Vibronic Coupling
and Transition Dipole Moment Density Analysis (M. Uejima, T. Sato, K. Tanaka,and H. Kaji) Chem. Phys., 430, 47-55 (2014).
17. Pseudo Jahn-Teller Origin of Distortion in [6]Cycloparaphenylene (Y. Kameoka, T.
Sato, T. Koyama, K. Tanaka, and T. Kato) Chem. Phys. Lett., 598, 69-74 (2014).
18. Highly Coplanar (E)-1,2-Di(1-naphthyl)disilene Involving a Distinct CH-πInteraction with the Perpendicularly Oriented Protecting Eind Group (M.
Kobayashi, N. Hayakawa, K. Nakabayashi, T. Matsuo, D. Hashizume, H. Fueno, K.
Tanaka, and K. Tamao) Chem. Lett., 43, 432-434 (2014).
（以上学術論文）－3－

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Ⅰ 専任教員 ･ スーパーバイザー (2013)⑵

副センター長【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】 カリフォルニア大サンタバーバラ校交換研究員、コーネル大客員研究員【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 on Science andTechnology of Synthetic Metals (2010).
【主な著書、学術論文】 1. J. Bu, K. Watanabe, H. Hayasaka, K. Akagi, “Photochemically Colour-Tuneable
White Fluorescence Illuminants consisting of Conjugated Polymer Nanospheres”,（過去 5 年以内）
Nat. Commun. 5, 3799 (2014).
2. S. Matsushita, B. Yan, S. Yamamoto, Y. S. Jeong, K. Akagi, “Helical Carbon andGraphite Films Prepared from Helical Poly(3,4-ethylenedioxythiophene) Films
Synthesized by Electrochemical Polymerization in Chiral Nematic Liquid Crystals”,
Angew. Chem., Int. Ed., 53, 1659 (2014).
3. B. A. San Jose, S. Matsushita, K. Akagi, “Lyotropic Chiral Nematic Liquid
Crystalline Aliphatic Conjugated Polymers Based on Di-Substituted Polyacetylene
Derivatives that Exhibit High Dissymmetry Factors in Circularly Polarized
Luminescence”, J. Am. Chem. Soc., 134, 19895 (2012).
4. 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).
5. 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).
【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－fukui2013.indb 4

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Ⅰ 専任教員 ･ スーパーバイザー (2013)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【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. “Mesoscopic architectures of porous coordination polymers fabricated by（過去 5 年以内）
pseudomorphic 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)
2. “Shape-Memory Nanopores Induced in Coordination Frameworks by Crystal
Downsizing”, Y. Sakata, S. Furukawa, M. Kondo, K. Hirai, N. Horike, Y.
Takashima, H. Uehara, N. Louvain, M. Meilikhov, T. Tsuruoka, S. Isoda, W.
Kosaka, O. Sakata, and S. Kitagawa, Science, 2013, 339, 193.
3. “Self-Accelerating CO Sorption in a Soft Nanoporous Crystal”, H. Sato, W.
Kosaka, R. Matsuda, A. Hori, Y. Hijikata, R.V. Belosludov, S. Sakaki, M. Takata,and S. Kitagawa, Science, 2014, 343, 167-170.
【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
7. 2013 英国王立化学会 de Gennes Award, 第 10 回江崎玲於奈賞－5－fukui2013.indb 5

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Ⅰ 専任教員 ･ スーパーバイザー (2013)【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】 新規酸化物固体の合成と磁気的性質・誘電的性質・光学的性質【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【主な著書、学術論文】 1. H. Akamatsu, K. Fujita, S. Murai, and K. Tanaka, “Ferromagnetic Eu2+-Based
Oxide Glasses with Reentrant Spin Glass Behavior”, Physical Review B 81 (2010)（過去 5 年以内）
014423-1-9.
2. 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.
3. 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.
4. 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.
5. 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.
6. X. Meng, A. V. Kildishev, K. Fujita, K. Tanaka, and V. M. Shalaev, “Wavelengthtunable spasing in the visible”, Nano Letters 13 (2013) 4106−4112.
7. H. Akamatsu, K. Fujita, T. Kuge, A. S. Gupta, A. Togo, S. Lei, F. Xue, G. Stone, J.
M Rondinelli, L. Chen, I. Tanaka, V. Gopalan, and K. Tanaka, “Inversion symmetry
breaking by oxygen octahedral rotations in Ruddlesden-Popper NaRETiO4 family”,
Physical Review Letters 112 (2014).187602-1-5.
【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 )、Award of the
Outstanding Papers Published in the JCerSJ in 2013（2013 年）－6－fukui2013.indb 6

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Ⅰ 専任教員 ･ スーパーバイザー (2013)【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
日本分光学会、日本レーザー学会【学会活動】 日本分光学会関西支部長【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)【学術関係の受賞など】 ○平成 26 年度文部科学大臣表彰 科学技術賞 研究部門 2014,4/7○平成 26 年度レーザー学会 業績賞・論文賞（研究部門）2014,4/18－7－

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Ⅰ 専任教員 ･ スーパーバイザー (2013)【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); Visiting Prof.at Universität
Bonn, Germany (2013-present)【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)
2013 Alexander von Humboldt Research Award Reinvitation－8－

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Ⅰ 専任教員 ･ スーパーバイザー (2013)【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
1982 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
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
1990 年 12 月
1993 年 3 月
2003 年 6 月

京都大学理学部 助手 採用
京都大学理学部 講師 昇任
京都大学理学部 助教授 昇任
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－

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Ⅰ 専任教員 ･ スーパーバイザー (2013)【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 －

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Ⅰ 専任教員 ･ スーパーバイザー (2013)【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・光触媒による人工光合成【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】 触媒学会理事（西日本支部長）【主な著書、学術論文】 1. A Doping Technique Suppressing Undesirable H2 Evolution Derived from Overall
Water Splitting in Highly Selective Photocatalytic Conversion of CO2 in and by（過去 5 年以内）
Water, Kentaro Teramura, Zheng Wang, Saburo Hosokawa, Yoshihisa Sakata,
Tsunehiro Tanaka, Chemistry –A European Journal, 2014, in press.
2. Effect of High-Temperature Calcination on the Generation of Brønsted Acid Sites on
WO3/Al2O3, Tomoyuki Kitano, Tomohiro Hayashi, Toshio Uesaka, Tetsuya Shishido,
Kentaro Teramura, and Tsunehiro Tanaka, Chem.Cat.Chem., 2014, in press.
3. Local Structure and La L1, and L3-edge XANES Spectra of Lanthanum Complex
Oxides, Hiroyuki Asakura, HideoTetsuya Shishido, Kentaro Teramura, Tsunehiro
Tanaka, Inorg. Chem., 2014, in press
4. Ultrathin Rhodium Nanosheets, Haohong Duan, Ning Yan, Rong Yu, Chun-Ran
Chang, Gang Zhou, Jie Zhang, Han-Shi Hu, Hongpan Rong, Junjie Mao, Zhiqiang
Niu, Yuen Wu, Shuo Zhang, Liwei Chen, Hiroyuki Asakura, Tsunehiro Tanaka,
Paul Joseph Dyson, Jun Li, Yadong Li, Nature Commun., 2014, 5:3093.
5. Vibronically Induced Activation Mechanism in Photocatalysis of Highly Dispersed
Vanadium Oxide Supported on Silica, V2O5/SiO2: Evidence in Phosphorescence
Spectra, Tohru Sato, Naoya Iwahara, Kazuyoshi Tanaka and Tsunehiro Tanaka,
Chem. Phys.Lett., 2013, 584, 63-66.
6. 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.
7. 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.
8. 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.
－ 11 －

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Ⅰ 専任教員 ･ スーパーバイザー (2013)【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. Kato and Y. Tanimura, Quantum Suppression of Ratchet Rectification in a
Brownian System Driven by a Biharmonic Force, J. Phys. Chem. B 117, 13132（過去 5 年以内）
13144 (2013).
2. A. Sakurai and Y. Tanimura, Self-excited current oscillations in a resonant
tunneling diode described by a model based on the Caldeira-Leggett Hamiltonian,
New J. of Phys. 16, 015002 [24 pages] (2014)
3. M. F. Gelin, Y. Tanimura, and W. Domcke, Simulation of femtosecond“ double slit”
experiments for a chromophore in a dissipative environment, J. Chem. Phys. 139,214302 (2013).
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 －

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Ⅰ 専任教員 ･ スーパーバイザー (2013)【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 / アクティブマターの計算科学【現在の研究課題】 生体組織の物理モデリング / 自己泳動する微生物のシミュレーション【研究内容キーワード】 ソフトマター、アクティブマター、シミュレーション、移動現象【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. John J. Molina and Ryoichi Yamamoto, Direct numerical simulations of rigid body
（過去 5 年以内）
dispersions. I. Mobility/Friction tensors of assemblies of spheres, J. Chem. Phys.,
139, 234105 (2013).
2. Adnan Hamid, John J. Molina, and Ryoichi Yamamoto, Sedimentation of nonBrownian spheres at high volume fraction, Soft Matter, 9, 10056-10068 (2013).
3. Rei Tatsumi and Ryoichi Yamamoto, Velocity relaxation of a particle in a confinedcompressible fluid, J. Chem. Phys., 138, 184905 (2013).
4. John J. Molina, Yasuya Nakayama, and Ryoichi Yamamoto, Hydrodynamic
interactions of self-propelled swimmers, Soft Matter 9, 4923-4936 (2013).
5. Rei Tatsumi and Ryoichi Yamamoto, Propagation of hydrodynamic interactions
between particles in a compressible fluid, Phys. Fluids 25, 046101 (2013).
6. Hideyuki Mizuno and Ryoichi Yamamoto, General constitutive model forsupercooled liquids: Anomalous transverse wave propagation, Phys. Rev. Lett. 110,095901 (2013).
【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 －

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Ⅰ 専任教員 ･ スーパーバイザー (2013)【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 forthe substrate translocation by AAA+ motor revealed by multiscale molecularsimulations, Proc Nat Acad Sci USA, 106: 18237-18242, 2009.
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Ⅰ 専任教員 ･ スーパーバイザー (2013)【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. A blue-shifted light-driven proton pump for neural silencing. Yuki Sudo*, Ayako（過去 5 年以内）
Okazaki, Hikaru Ono, Jin Yagasaki, Seiya Sugo, Motoshi Kamiya, Louisa Reissig,
Keiichi Inoue, Kunio Ihara, Hideki Kandori, Shin Takagi and Shigehiko Hayashi, J.
Biol. Chem. 288, 20624-20632 (2013).
2. Structural and spectral characterizations of C1C2 channelrhodopsin and its mutantsby molecular simulations. Motoshi Kamiya, Hideaki E. Kato, Ryuichiro Ishitani,
Osamu Nureki, and Shigehiko Hayashi*, Chem. Phys. Lett. 556, 266-271 (2013).
3. Molecular mechanism of ATP hydrolysis in F1-ATPase revealed by molecularsimulations 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).
4. 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).
5. 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).
6. Protein collective motions coupled to ligand migration in myoglobin. Yasutaka
Nishihara, Shigeki Kato, and Shigehiko Hayashi*, Biophys. J. 98, 1649-1657(2010).

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Ⅰ 専任教員 ･ スーパーバイザー (2013)

⑷

専任教員

【氏名（ふりがな）】 池田

昌司 （いけだ

あつし )【職名】 准教授【所属】 福井謙一記念研究センター

総合研究部門【研究室】 福井謙一記念研究センター 205【直通電話】 075-711-7838【FAX】 075-781-4757【電子メールアドレス】 Atsushi.Ikeda@fukui.kyoto-u.ac.jp【ホームページ】 http://www.fukui.kyoto-u.ac.jp/users/ikeda/index.html【研究分野】 理論化学、統計力学【現在の研究課題】 ガラス転移・ジャミング転移の統計力学研究【研究内容キーワード】 相転移、非平衡、ソフトマター【学歴】 2003 年 3 月 京都大学工学部工業化学科卒業
2005 年 3 月 京都大学大学院工学研究科分子工学専攻修士課程修了
2008 年 3 月 京都大学大学院工学研究科分子工学専攻博士後期課程修了、京都大学【学位】 2008 年 3 月 博士（工学）【略歴】 2008 年 4 月 日本学術振興会特別研究員 PD（筑波大学物理学専攻）、2011 年 4月 モンペリエ第二大学シャルルクーロン研究所博士研究員、2012 年 12 月 日
本学術振興会海外特別研究員（モンペリエ第二大学シャルルクーロン研究所）、
2014 年 2 月 京都大学福井謙一記念研究センター准教授【所属学会】 日本物理学会、日本化学会【主な著書、学術論文】 1. Atsushi Ikeda and Kunimasa Miyazaki, “Mode-coupling theory as a mean-field
description of the glass transition” Phys. Rev. Lett. 104, 255704 (2010).
（過去 5 年以内）
2. Atsushi Ikeda and Kunimasa Miyazaki “Glass transition of the monodisperse
gaussian core model” Phys. Rev. Lett. (Editors’ Suggestion) 106, 015701 (2011).

3. Atsushi Ikeda and Kunimasa Miyazaki “Slow Dynamics of the High Density
Gaussian Core Model” J. Chem. Phys. 135, 054901 (2011).
4. Patrick Charbonneau, Atsushi Ikeda, Giorgio Parisi and Francesco Zamponi “Glass
Transition and Random Close Packing above Three Dimensions” Phys. Rev. Lett.
107, 185702 (2011).
5. Atsushi Ikeda, Ludovic Berthier and Peter Sollich ”Unified study of glass andjamming rheology in soft particle systems” Phys. Rev. Lett. (Editors’ Suggestion)
109, 018301 (2012).
6. Atsushi Ikeda, Ludovic Berthier and Giulio Biroli “Dynamic criticality at the
jamming transition” J. Chem. Phys. 138, 12A507 (2013).
7. Atsushi Ikeda, Ludovic Berthier and Peter Sollich “Disentangling glass andjamming physics in the rheology of soft materials” Soft Matter (Highlight Article) 9,7669 (2013).
【学術関係の受賞など】 2007 年 9 月 分子科学会優秀講演賞、2008 年 -2011 年 日本学術振興会特別研究員 PD、2012 年 -2014 年 日本学術振興会海外特別研究員、2013 年 3 月日本物理学会若手奨励賞（領域 12）－ 16 －

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Ⅰ 専任教員 ･ スーパーバイザー (2013)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, nagase@ims.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., 46, 1627-1635 (2013).
6. M. Yamada, T. Akasaka, and S. Nagase, Carbene Additions to Fullerenes, Chem.
Rev., 113, 7209-7264 (2013).
7. S. Nagase, Theory and Calculations of Molecules Containing Heavier Main Group
Elements and Fullerenes Encaging Transition Metals: Interplay with Experiment,
Bull. Chem. Soc. Jpn., (Award Accounts), 87, 167-195 (2014).
【学術関係の受賞】 2012 年 文部科学大臣表彰科学技術賞（研究部門）、2012 年 福井メダル (AsiaPacific Association of Theoretical & Computational Chemists) 、2013 年 日本化学会賞

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Ⅰ 専任教員 ･ スーパーバイザー (2013)【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. M. Isegawa, S. Maeda, D. J. Tantillo and K. Morokuma, Predicting Pathways
for Terpene Formation from First Principles – Routes to Known and New
Sesquiterpenes, Chem. Sci. 5, 1555-1560 (2014).
2. T. V. Harris, Y. Kurashige, T. Yanai, and K. Morokuma, Ab Initio Density Matrix
Renormalization Group Study of Magnetic Coupling in Dinuclear Iron and
Chromium Complexes, J. Chem. Phys. 140, 054303/1-10 (2014).
3. L. Ding, N. Ishida, M. Murakami, and K. Morokuma, sp3–sp2 vs sp3–sp3 C-C SiteSelectivity in Rh-Catalyzed Ring Opening of Benzocyclobutenol: A DFT Study, J.
Am. Chem. Soc. 136, 169–178 (2014).
4. S. Maeda, T. Taketsugu, and K. Morokuma, Exploring Transition State Structures
for Intramolecular Pathways by the Artificial Force Induced Reaction (AFIR)
Method. J. Comp. Chem. 35, 166-173 (2014).
5. S. Komagawa, C. Wang, K. Morokuma, S. Saito and M. Uchiyama, Mechanistic
Origin of Chemo- and Regioselectivity of Nickel-Catalyzed [3+2+2] Cyclization
Reaction. J. Am. Chem. Soc. 135, 14508–14511 (2013).
6. H.-B. Li, A. J. Page, S. Irle, and K. Morokuma, Temperature Dependence ofCatalyst-Free Chirality-Controlled Single-Walled Carbon Nanotube Growth from
Organic Templates, J. Phys. Chem. Lett. 4. 3176-3180 (2013).
7. F. Liu, Y, Kurashige, T. Yanai, and K. Morokuma, Multireference Ab Initio Density
Matrix Renormalization Group (DMRG)-CASSCF and -CASPT2 Study on the
Photochromic Ring-Opening of Spiropyran, J. Chem. Theo. Comp. 9, 4462–4469(2013).
8. M. Hatanaka and K. Morokuma, Theoretical Study of Mukaiyama-Aldol Reaction
Catalyzed by Water-Tolerant Lanthanide Lewis Acid, J. Am. Chem. Soc. 135,
13972–13979 (2013).
9. F. Liu and K. Morokuma, Multiple Pathways for Primary Step of Spiropyran
Photochromic Reaction: a CASPT2//CASSCF Study, J. Am. Chem. Soc. 135,
10693–10702 (2013).

【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－ 18 －

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Ⅰ 専任教員 ･ スーパーバイザー (2013)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

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【学位】 1974 年 11 月

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【主な著書、学術論文】 1. Multi-State CASPT2 Study of Native Iron(III)-dependent Catechol Dioxygenase（過去 5 年以内）
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).
2. 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).
3. 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).
4. 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 target QM 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. Absorption of CO2 and CS2 into the Hofmann-Type Porous Coordination Polymer:
Electrostatic versus Dispersion Interactions, M. M. Deshmukh, M. Ohba, S.
Kitagawa, and S. Sakaki, J. Am. Chem. Soc., 135, 4840-4849 (2013).
17. 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, S. Sakaki, J. Am. Chem. Soc., 135, 8955-8965 (2013).
18. Unexpected Electronic Process of H 2 Activation by a New Nickel Borane
Complex: Comparison with the Usual Homolytic and Heterolytic Activations, G.
Zeng and S. Sakaki, Inorg. Chem., 52, 2844-2853 (2013).
19. 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, Y. Chen and S. Sakaki, Inorg. Chem., 52, 13146-13159 (2013).
20. Theoretical Study of One-Electron Oxidized Mn(III)- and Ni(II)-Salen Complexes:
Localized vs Delocalized Ground and Excited States in Solution, S. Aono, M.
Nakagaki, T. Kurahashi, H. Fujii, and S. Sakaki, J. Chem. Theory Comput., 10,1062-1073 (2014).
【学術関係の受賞など】 第１回分子科学会賞（2009 年 9 月） 第 66 回日本化学会賞（2014 年 3 月）
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Ⅱ 博士研究員 (2013)

Ⅱ

博士研究員

１．博士研究員組織
平成２５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
Jingdong GUO

永瀬グループWei-Wei WANG

福井センターフェロー

畑中美穂

Fengyi. Liu
Lina Ding
Hai-bei Li
Lung Wa Chung

諸熊グループ研究フェローGalina Petrova
Travis HARRIS
伊勢川

美穂

W.M.C. SAMEERA
Julong. JIANG
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

Milind Madhusudan Deshmukh
Guixiang Zeng（會
榊グループ

髙木

望

中垣

雅之

桂 香）

Wei GUAN
Yue CHEN
Sayyed Farred Bhasha
山田

健太－ 20 －

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Ⅱ 博士研究員 (2013)

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】 助教【所属】 大分大学医学部物理【研究室】 講義棟 403 号室【直通電話】 097-586-5604【電子メールアドレス】 Iwaki48@oita-u.ac.jp【ホームページ】 http://www.med.oita-u.ac.jp/butsuri/site/Top.html【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
Apr. 2010, Fukui Institute for Fundamental Chemistry, Kyoto University
July 2013, Faculty of Medicine, Oita University【所属学会】 The Physical Society of Japan【主な著書、学術論文】 1. T. Iwaki, “Effect of internal flow on the photophoresis of a micron-sized liquid
droplet”, Physical Review E 81, 066315 (13 pages) (2010)（過去 5 年以内）
2. 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

3. 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 view l a,T. gedena, PEMS for polymer folding 84, 021924 (5 pages)
4. Shun N. Watanabe, Takafumi Iwaki, Masahiro I. Kohira, Nobuyuki Magome, andKenichi Yoshikawa, “Negative photophoresis of smoke particles observed under
microgravity”, Chemical Physics Letters 511, 447–451 (2011)

5. Masatoshi Ichikawa, Fumi Takabatake, Keitaro Miura, Takafumi Iwaki, Nobuyuki
Magome, and Kenichi Yoshikawa, “Controlling negative and positive photothermal
migration of centimeter-sized droplets”, Phys. Rev. E 88, 012403 (2013)－ 21 －

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Ⅱ 博士研究員 (2013)【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】 理論化学・計算化学【現在の研究課題】 時間依存密度汎関数法を用いた溶液における光化学反応の解析【研究内容キーワード】 時間依存密度汎関数法・積分方程式・円錐交差・自由エネルギー【学歴】 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【学位】 2008 年 3 月京都大学理学博士【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. N. Minezawa, “Excited-state free energy surfaces in solution: Time-dependent
density functional theory/reference interaction site model self-consistent field（過去 5 年以内）
method”, J. Chem. Phys. 138, article No. 244101 [8 pages] (2013).
2. Y. Harabuchi, S. Maeda, T. Taketsugu, N. Minezawa, and K. Morokuma,“Automated search for minimum energy conical intersection geometries between
the lowest two singlet states S0/S1-MECIs by the spin-flip TDDFT method”, J.
Chem. Theory Comput. 9, 4116-4123 (2013).
3. N. De Silva, N. Minezawa, and M. S. Gordon, “Excited-state hydrogen atomtransfer reaction in solvated 7-hydroxy-4-methylcoumarin”, J. Phys. Chem. B 117,
15386-15394 (2013).
4. 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, 5008-5012 (2012).
5. 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).

－ 22 －

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Ⅱ 博士研究員 (2013)【氏名（ふりがな）】 岡本

隆一 （おかもとりゅういち）【職名】 特任助教【所属】 首都大学東京【研究室】 ８号館 348 号室【直通電話】 042-677-2538【FAX】 042-677-2525【電子メールアドレス】 okamotor@tmu.ac.jp【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 - 2014 年 3 月 京都大学福井謙一研究センター FIFC フェロー2014 年 4 月 - 首都大学東京理工学研究科 特任助教
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: “Precipitation in aqueous mixtures with addition ofstrongly hydrophilic or hydrophobic solute”, Phys. Rev. E 82, 051501 (2010). (Also（過去 5 年以内）
in Virtual Journal of Nanoscale Science and Technology, November 22, 2010).
2. R. Okamoto and A. Onuki: “Charged Colloids in an aqueous mixture with asalt”, Phys. Rev. E 84, 051401 (2011).
3. 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).
4. R. Okamoto, Y. Fujitani and S. Komura: “Drag coefficient of a rigid sphericalparticle in a near-cirtical binary fluid mixture”, J. Phys. Soc. Jpn. 82, 084003 (2013).
(Selected as an editors’ choice paper.)5. R. Okamoto and A. Onuki: “Attractive interaction and bridging transition between
between neutral colloidal particles due to preferential adsorption in a near-criticalbinary mixture”, Phys. Rev. E 88, 022309 (2013)－ 23 －

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Ⅱ 博士研究員 (2013)【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 Single Polymeric Chain【研究内容キーワード】 Dynamics of Deformation, Fluctuation of polymer dynamics【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, “Cis-trans dynamical asymmetry in driven polymertranslocation”, Phys. Rev. E, 88, 042606 (5 pages total) (2013).
（過去 5 年以内）
2. Takuya Saito, Takahiro Sakaue, “Process time distribution of driven polymertransport”, Phys. Rev. E, 85, 061803 (7 pages total) (2012).

3. 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).

4. 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」【学術関係の受賞など】 JSPS Research Fellowships for Young Scientists(DC2) 2005.4-2007.3－ 24 －

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Ⅱ 博士研究員 (2013)【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/html/baifuquan.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】 Excited state, Spectroscopy, Photo-reaction, ,TDDFT, MCSCF【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- Apr. 2013, FIFC Fellow, Kyoto University【所属学会】 Chinese Chemical Society【主な著書、学術論文】 1. Juan Jin, Fu-Quan Bai, Ming-Jun Jia, Yan-Ning Wang, Hong-Li Jia, Jie-Hui Yu,
Ji-Qing Xu, “New Cd2+, Pb2+ complexes with acylhydrazidate molecules from in（過去 5 年以内）
situ acylation reactions”, Dalton Transactions, 42(24), 8771-8780. (2013).
2. Jie Chen, Jian Wang, Fu-Quan Bai, Li Hao, Qing-Jiang Pan*, Hong-Xing Zhang*,“Connection style and spectroscopic properties: Theoretical understanding of theinterface between N749 and TiO2 in DSSCs”, Dyes and Pigments, 99(1), 201-208,(2013).
3. Qi Cao, Jing Wang, Zhao-Shuo Tian*, Zai-Feng Xie*, Fu-Quan Bai*, “Theoreticalinvestigation 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).
4. 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, 41(27), 8441-8446, (2012).
5. 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, 115(42), 11689-11695, (2011).
【学術関係の受賞など】 NSFC Young Scholar, 2010－ 25 －

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Ⅱ 博士研究員 (2013)【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 study of the Diels − Alder reaction of La@C82 with 1,2,3,4,5-Pentamethylcyclopentadiene.
【研究内容キーワード】 Reaction mechanism, regioselectivity【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
2012-2014, Postdoctoral Fellow, Fukui Institute for Fundamental Chemistry, Kyoto
University【主な著書、学術論文】 1. Vladimir Ya. Lee, Shinji Aoki, Taka Yokoyama, Satoru Horiguchi, Akira Sekiguchi,
Heinz Gornitzka, Jing-Dong Guo, and Shigeru Nagase, “Toward a Silicon Version（過去 5 年以内）
of Metathesis: From Schrock-Type Titanium Silylidenes to Silatitanacyclobutenes”,
J. Am. Chem. Soc., 135, 2987-2990 (2013)
2. 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)
3. Takuya Kuwabara, Masaichi Saito, Jing-Dong Guo, Shigeru Nagase, “Unexpected
Formation of Ru2Sn2 Bicyclic Four-Membered Ring Complexes with Butterfly andInverse-Sandwich Structures”, Inorg. Chem., 52, 3585-3587 (2013)
4. Chun-Yi Lin, Jing-Dong Guo, James C. Fettinger, Shigeru Nagase, Fernande
Grandjean, Gary J. Long, Nicholas F. Chilton, and Philip P. Power, “Dispersion
Force Stabilized Two-Coordinate Transition Metal−Amido Complexes of the−N(SiMe3)Dipp (Dipp = C6H3‑2,6-Pri Structural, Spectroscopic, Magnetic, andComputational Studie”, Inorg. Chem., 52, 13584-13593 (2013)
5. Jessica N. Boynton, Jing-Dong Guo, James C. Fettinger, Christopher E. Melton,
Shigeru Nagase, and Philip P. Power, “Linear and Nonlinear Two-Coordinate
Vanadium Complexes: Synthesis, Characterization, and Magnetic Properties of
V(II) Amides”, J. Am. Chem. Soc., 135, 10720-10728, (2013)－ 26 －

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Ⅱ 博士研究員 (2013)【氏名】 Wei-Wei Wang
【職名】 SPR Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 104【直通電話】 075-711-7792【FAX】 075-711-7792【電子メールアドレス】 wangweiwei@fukui.kyoto-u.ac.jp【研究分野】 Theoretical Chemistry【現在の研究課題】 Theoretical study of functionalized nanomaterials【研究内容キーワード】 Fullerene, Graphene, Formation mechanisms【学歴】 Jun. 2007, B. Sc. in Applied Chemistry, Xi'an Jiaotong University, China
Dec. 2012, Ph, D. in Materials Physics and Chemistry, Xi'an Jiaotong University,
China【学位】 Ph.D. in Materials Physics and Chemistry, Xi'an Jiaotong University, China【主な著書、学術論文】 1. W. W. Wang, J. S. Dang, J. J. Zheng, X. Zhao, E. Ōsawa and S. Nagase, “MetalPromoted Restoration of Defective Graphene” J. Mater. Chem. 2012, 22, 16370.
（過去 5 年以内）

2. W. W. Wang, J. S. Dang, J. J. Zheng, X. Zhao, “Heptagons in C 68: Impact on
Stabilities, Growth, and Exohedral Derivatization of Fullerenes” J. Phys. Chem. C.
2012, 116, 17288.

3. W. W. Wang, J. S. Dang, X. Zhao, “Role of Four-Membered Rings in C32 Fullerene
Stability and Mechanisms of Generalized Stone-Wales Transformation: a Density
Functional Theory Investigation” Phys. Chem. Chem. Phys. 2011, 13, 14629.
4. W. W. Wang, J. S. Dang, X. Zhao, “Impact of Tetragonal Rings on the Stabilityof Small Fullerenes Encapsulated with Noble Gas: a Density Functional Theory
Survey” Chem. Phys. Lett. 2012, 536, 77.
5. W. W. Wang, J. S. Dang, J. J. Zheng, X. Zhao, S. Nagase, “Selective Growth of
Fullerenes from C60 to C70: Inherent Geometrical Connectivity Hidden in DiscreteExperimental Evidence” J. Phys. Chem. C, 2013, 117, 2349.

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Ⅱ 博士研究員 (2013)【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】 理論化学

計算化学

【現在の研究課題】 ・ 柔らかなランタノイド不斉触媒を用いる向山アルドール反応の立体選択性発現機構の解明及び触媒設計
・ Y3+ 触媒を用いるイソプロペン重合反応のレジオ選択性の理論的研究
・ 4fN エネルギーシフト法を用いる感温性ランタノイド発光プローブの励起
エネルギー移動の機構解明
・ Gd3+ を含む MRI コントラスト剤の構造分布と水交換反応の理論的研究
・ 星間空間における炭化水素アニオンの生成機構の解明【研究内容キーワード】 ランタノイド・自動反応経路探索 (GRRM)・触媒反応・発光プローブ【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, M. Saito, M. Fujita, K. Morokuma, “σ-Aromaticity in Hexa-Group
16 Atom Substituted Benzene Dications. A Theoretical Study”, J. Org. Chem. 79,（過去 5 年以内）
pp 2640-2646 (2014).
2. M. Hatanaka, K. Morokuma, “Role of Water in Mukaiyama-Aldol Reaction
Catalyzed by Lanthanide Lewis Acid: A Computational Study” J. Am. Chem. Soc.
135, pp 13972-13979 (2013).
※Spotlights on Recent JACS Publications, 135, pp. 13999-13999 (2013)に掲載
3. M. Hatanaka, S. Maeda, K. Morokuma, “Sampling of Transition States for
Predicting Diastereoselectivity Using Automated Search Method —Aqueous
Lanthanide-Catalyzed Mukaiyama Aldol Reaction” J. Chem. Theory. Comput. 9, pp
2882-2886 (2013).

4. 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, pp
5058-5063 (2012).
5. M. Hatanaka, S. Yabushita, “Mechanisms of f-f hypersensitive transition intensitiesof lanthanide trihalide molecules: a spin-orbit configuration interaction study”
Theor Chem Acc (in press)
6. 前田理, 畑中美穂, 植松遼平, 武次徹也, 諸熊奎治, “人工力誘起反応法による化学反応経路の自動探索：有機合成化学への応用と展望”, 有機合成化学協会誌 72, pp567-579 (2014)（総説）【学術関係の受賞など】 2013 年 9 月
2013 年 6 月
2011 年 4 月

第 7 回分子科学討論会 ( 京都 )2013 分子科学会優秀講演賞
The Best Poster Award in“The 6th Asia Pacific Conference ofTheoretical and Computational Chemistry”
京都大学福井謙一記念研究センターフェロー－ 28 －

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Ⅱ 博士研究員 (2013)【氏名（ふりがな）】 Fengyi Liu（ふぉんいりお）【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. F.Y. Liu, K. Morokuma, Multiple Pathways for Primary Step of Spiropyran（過去 5 年以内）
Photochromic Reaction: A CASPT2//CASSCF Study, J. Am. Chem. Soc., 2013,
135, 10693–10702
2. F.Y.Liu, K.Yuki, T. Yanai, K. Morokuma, Multireference Ab Initio Density
Matrix renormalization Group (DMRG)-CASSCF and -CASPT2 Study on the
Photochromic Ring-Opening of Spiropyran, J. Chem. Theory Comput., 2013, 9,4462–4469.
3. W. Piao, S. Tsuda, Y. Tanaka, S. Maeda, F.Y. Liu, S. Takahashi, Y. Kushida, T.
Komatsu, T. Ueno, T. Terai, T. Nakazawa, M. Uchiyama, K. Morokuma, T. Nagano,and K. Hanaoka, Development of a New Class of Azo-based Fluorescence Probes
to Detect Different Levels of Hypoxia. Angew. Chem. Int. Ed., 2013, 52, 13028–
13032.
4. Fengyi Liu and Keiji Morokuma, Computational Study on the Working Mechanismof a Stilbene Light-Driven Molecular Rotary Motor: Sloped Minimal Energy Pathand Unidirectional Nonadiabatic Photoisomerization, J. Am. Chem. Soc., 2012, 134,
4864–4876.

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Ⅱ 博士研究員 (2013)【氏名】 Lina Ding （丁麗娜）【職名】 Research Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 the Morokuma Group【電子メールアドレス】 dingln@zzu.edu.cn【現在の研究課題】 biology【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", J. Chem. Theory Comput., 2014, 10, 668–
675
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", J. Am. Chem. Soc., 2014, 136, 169–178.
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, 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.

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Ⅱ 博士研究員 (2013)【氏名】 Hai-Bei Li【職名】 Associate Professor【所属】 Shandong University【研究室】 Room 515-B【直通電話】 0631-5677365【電子メールアドレス】 lihaibei@sdu.edu.cn【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, Christian Hettich, Bálint Aradi, Christof Köhler, Thomas
Frauenheim, Stephan Irle, and Keiji Morokuma, Graphene Nucleation on a Surface（過去 5 年以内）
Molten Copper Catalyst: Quantum Chemical Molecular Dynamics Simulations.
Chem. Sci. accepted, 2014
2. Hai-Bei Li, Alister J Page, Stephan Irle*, Keiji Morokuma*, “The Dual Role of
Hydrogen Atoms during Polycyclic Aromatic Hydrocarbon Formation” J. Phys.
Chem. Lett., 4(14), 2323-2327, 2013
3. Hai-Bei Li, Alister J Page, Stephan Irle*, Keiji Morokuma*, “Temperature
Dependence of the Catalyst-free Growth of Single-Walled Carbon Nanotubes” J.
Phys. Chem. Lett., 4(18), 3176-3180, 2013
4. Hai-Bei Li, Alister J Page, Ying Wang, Stephan Irle*, Keiji Morokuma*, “Subsurface nucleation of graphene precursors near a Ni(111) step-edge” Chem. Comm.,
48(64), 7937-7939, 2012
5. Hai-Bei Li, Alister J Page, Stephan Irle*, Keiji Morokuma*, “Single-walled Carbon
Nanotube Growth from Chiral Carbon Nanorings: Prediction of Chirality andDiameter Influence on Growth Rates” J. Am. Chem. Soc., 134(38), 15887-15896,
2012【学術関係の受賞など】 Qiu Shi Graduate Student Scholarship (2009)
Supported by the Scientific Research Foundation of Shandong University (2014)－ 31 －

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Ⅱ 博士研究員 (2013)【氏名】 Lung Wa Chung【職名】 JST Fellow (till July); Associate Researcher/Assistant Professor (tenure-track, since
end of October)【所属】 Fukui Kennichi Memorial Research Group 1, Fukui Institute For Fundamental
Chemistry; Department of Chemistry, South University of Science and Technology ofChina【直通電話】 075-711-7631; 0755-88018320【電子メールアドレス】 chung@fukui.kyoto-u.ac.jp; oscarchung@sustc.edu.cn【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. 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（過去 5 年以内）
Methylmalonyl-CoA Mutase. Stepwise or Concerted Mechanism?” J. Am. Chem.
Soc. 2009, 131, 5115.
2. 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
3. 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.
4. 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.
5. 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.
6. 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.
7. 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.
8. 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.
9. 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.
10. Ding, S.; Song, L.-J.; Chung, L. W.; Zhang, X.; Sun, J.; Wu, Y.-D. “LigandControlled Remarkable Regio- and Stereodivergence in Intermolecular
Hydrosilylation of Internal Alkynes: Experimental and Theoretical Studies”, J. Am.
Chem. Soc. 2013, 135, 13835.
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Ⅱ 博士研究員 (2013)【氏名】 Galina Petrova【職名】 Postdoctoral Scholar【所属】 Faculty of Chemistry and Pharmacy, University of Sofia【研究室】 Blvd. James Bourchier 1, Department of Organic Chemistry【直通電話】 (+ 359 2) 8161 433【FAX】 (+ 359 2) 9625 438【電子メールアドレス】 gppetrova@gmail.com【研究分野】 Computational Chemistry【現在の研究課題】 Hetero- and homogeneous catalysis【研究内容キーワード】 Asymmetric catalysis, Phase-transfer catalysts, DNA based catalysts, 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】 06/2013-02/2014, Postdoctoral Scholar at FIFC, Kyoto University, Kyoto, Japan
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. P. Petrova, H.-B. Li, K. Maruoka, K. Morokuma, “Asymmetric Phase-Transfer
Catalysis with Homo- and Heterochiral Quaternary Ammonium Salts: A Theoretical（過去 5 年以内）
Study”, J. Phys. Chem. B, 2014, 118 (19), pp 5154–5167.
2. G. P. Petrova, Z. Ke, S. Park, H. Sugiyama, K. Morokuma, “The origin ofenantioselectivity for intramolecular Friedel–Crafts reaction catalyzed bysupramolecular Cu/DNA catalyst complex”, Chem. Phys. Lett., 2014, 600, pp 87–
95.
3. 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
metal clusters: Insights from computational model studies”, Phys. Chem. Chem.
Phys., 2012, 14, pp 5879-5890.
4. 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”, Nat. Mater., 2011, 10, pp 310–315.
5. G. P. Petrova, G. N. Vayssilov, N. Rösch, “Interaction of ethene and ethyne withbare and hydrogenated Ir4 clusters. A density functional study”, Catal. Sci. Tech.
2011, 1, pp 958-970.
【学術関係の受賞など】 JSPS Research Fellowship, 2013-2014
Student award for high academic achievements of the Foundation for support of the
Bulgarian Higher Education named after Prof. Michael Klett (2003)－ 33 －

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Ⅱ 博士研究員 (2013)【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 transition metal homogeneous catalysis, and properties ofmetallocofactors and molecular magnets【研究内容キーワード】 Rh(I)-catalyzed hydroboration, DMRG, magnetic exchange coupling, [Fe-S] clusters【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.; Kurashige, Y.; Yanai, T.; Morokuma, K. Ab Initio Density Matrix
Renormalization Group Study of Magnetic Coupling in Dinuclear Iron and（過去 5 年以内）
Chromium Complexes. J. Chem. Phys. 2014, 140 (5), 054303.
2. Harris, T. V.; Szilagyi, R. K. Iron-Sulfur Bond Covalency from Electronic Structure
Calculations for Classical Iron-Sulfur Clusters. J. Comput. Chem. 2014, 35 (7), 540.
3. 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., 2013, 52(15), 8551.
4. Harris, T. V.; Szilagyi, R. K. Comparative Assessment of the Composition andCharge State of Nitrogenase FeMo-Cofactor. Inorg. Chem., 2011, 50 (11), 4811.
5. 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.
【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－ 34 －

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Ⅱ 博士研究員 (2013)【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】 諸熊グループ【電子メールアドレス】 Isegawa@fukui.kyoto-u.ac.jp【研究分野】 計算化学

【現在の研究課題】 励起状態を含む反応機構の解明【研究内容キーワード】 励起状態、反応経路、DFT、分子スイッチ【学歴】 京都大学理学部【学位】 理学（京都大学）【略歴】 2009- 博士号取得（理学、京都大学）
2010- 米国ミネソタ大学博士研究員
2013- 福井謙一記念研究センター研究員【学会活動】 (1) 分子科学討論会2013京都(2) 京都大学福井謙一記念センターシンポジウム2014【主な著書、学術論文】 1. 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.
（過去 5 年以内）
Chem. Phys. 135, 084107 (2011).
2. 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 (2012).
3. Electrostatically Embedded Molecular Tailoring Approach and Validation for
Peptide, M. Isegawa, B. Wang, and D. G. Truhlar, J. Chem. Theory Comput. 9,1381 (2013).
4. Predicting pathways for terpene from first principles-routes to known and newsesquiterpenes, M. Isegawa, S. Maeda, D. J. Tantillo, and K. Morokuma, Chemical
Science, 5, 1555 (2014).

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Ⅱ 博士研究員 (2013)【氏名】 W. M. C. Sameera【職名】 Postdoctoral Fellow【所属】 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】 sameera@fukui.kyoto-u.ac.jp【ホームページ】 http://www.wmcsameera.com【研究分野】 Computational Chemistry【現在の研究課題】 Hybrid methods, transition metal homogeneous catalysis, florescent probs.
【研究内容キーワード】 QM/MM and QM/QM methods, reaction mechanisms, excited states.
【学歴】 July 2005, BSc (Hons), University of Sri Jayewardenepura, Sri Lanka.
【学位】 PhD, University of Glasgow, United Kingdom.
【略歴】 Postdoctoral Fellow, University of Oxford (2010).
Posdoctoral Fellow, Institute of Chemical Research of Catalonia, Spain (2011).
【所属学会】 Marie Curie Fellowship, University of Gothenburg, Sweden (2013)【学会活動】 Member, Royal Society of Chemistry, United Kingdom.
Member, American Chemical Society.
【主な著書、学術論文】 1. J. Llaveria, Á. Beltrán, W. M. C. Sameera, A. Locati, M. M. Díaz-Requejo, M. I.
Matheu, S. Castillón, F. Maseras, P. J. Pérez, “Regio- and Stereoselective Silver（過去 5 年以内）
catalyzed aziridination of dienes: scope, mechanistic studies and ring-opening
reactions”, J. Am. Chem. Soc. 136, 14, 5342-5350.
2. L. Maestre, W. M. C. Sameera, M. M. Díaz-Requejo, F. Maseras, P. J. Pérez. “AGeneral Mechanism for the Copper- and Silver-Catalyzed olefin aziridination
reactions: concomitant involvement of the singlet and triplet pathways”, J. Am.
Chem. Soc. 2013, 135, 1338-1348.
3. W. M. C. Sameera, F. Maseras, “Transition metal catalysis by density functional
theory and density functional theory molecular mechanics”, WIREs Comput. Mol.
Sci., Wiley-VCH, 2012, 2, 375-380.
4. W. M. C. Sameera, D. A. Pantazis, “A hierarchy of methods for the energeticallyaccurate modelling of isomerism in aldohexoses”, J. Chem. Theory Comput., 2012,
8, 2630-2645.
5. W. M. C. Sameera, F. Maseras, “Quantum mechanics/molecular mechanics methods
can be more accurate than full quantum mechanics in system involving dispersion
correlations”, Phys. Chem. Chem. Phys., 2011, 13, 10520-10526.
【学術関係の受賞など】 Postdoctoral fellowship, Kyoto University. (2013)Marie Curie fellowship, University of Gothenburg, Sweden. (2012)
WATOC poster prize, WATOC conference, Santiago de Compostela. (2011)
Postdoctoral fellowship, ICIQ foundation, Spain. (2010)EPSRC postdoctoral fellowship, University of Oxford (2009)
CRC press award for the best poster, the seventh Canadian computational chemistry
meeting, Canada. (2009)
The Jim Gatheral Scholarship, University of Glasgow. (2008)
WestCHEM postgraduate scholarship, University of Glasgow. (2006)－ 36 －

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Ⅱ 博士研究員 (2013)【氏名】 Julong Jiang【職名】 Postdoctoral Fellow【所属】 The Morokuma Group, 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】 julong@fukui.kyoto-u.ac.jp【研究分野】 Computational Chemistry, Physical Organic Chemistry【現在の研究課題】 C-H activation in organic synthesis【研究内容キーワード】 Homogeneous Catalysis, Radical Reaction, Asymmetric Synthesis【学歴】 July, 2010, B.Sc (Hons), The University of Science & Technology of China
January, 2014, Ph.D, University of Sheffield, The United Kingdom【学位】 Ph.D, University of Sheffield, UK【略歴】 From March, 2014, Fukui Institute for Fundamental Chemistry【主な著書、学術論文】 1. Steven J. Edeson, Julong Jiang, Stephen Swanson, Panayiotis A. Procopiou,
Harry Adams, Anthony J. H. M. Meijer and Joseph P. A. Harrity, “Studies on the（過去 5 年以内）
stereochemical assignment of 3-acylidene 2-oxindoles”, Org. Biomol. Chem., 2014,12, 3201-3210.
2. Damien F.P. Crépin , Joseph P. A. Harrity , Julong Jiang , Anthony J. H. M. Meijer, Anne-Chloé M. A. Nassoy , and Piotr Raubo, “A Mechanistic Study of the Lewis
Base Directed Cycloaddition of 2-Pyrones and Alkynylboranes”, J. Am. Chem.
Soc., 2014, ASAP. (Authorship sequence in the alphabetical order with respect tothe surnames)【学術関係の受賞など】 Faculty of Science Scholarship, University of Sheffield, 2010-2013－ 37 －

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Ⅱ 博士研究員 (2013)【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
1974年3月末

京都大学
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。

【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. “Presence or absence of a novel charge-transfer complex in the base-catalyzedhydrolysis of N-ethylbenzamide or ethyl benzoate”, Shinichi Yamabe, Wei Guan
（過去 5 年以内）
and Shigeyoshi Sakaki, Beilstein J. Org. Chem. 2013, 9, 185-196.
2. “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
3. “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
4. “Substrate dependent reaction channels of the Wolff-Kishner reduction reaction: A
theoretical study”, Shinichi Yamabe, Guixiang Zeng, Wei Guan, Shigeyoshi Sakaki,
Beilstein Journal of Organic Chemistry 2014, 10, 259-270.
5. “SN1-SN2 and SN2-SN3 mechanistic changes revealed by transition states of thehydrolyses of benzyl chlorides and benzenesulfonyl chlorides”, Shinichi Yamabe,
Guixiang Zeng, Wei Guan and Shigeyoshi Sakaki, Journal of Computational
Chemistry, vol.35, issue 15, pages 1140-1148 (2014), DOI: 10.1002/jcc.23607.

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Ⅱ 博士研究員 (2013)【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】 hijikata@fukui.kyoto-u.ac.jp【ホームページ】 http://www.users.iimc.kyoto-u.ac.jp/~z59354/member_e/hijikata.html【研究分野】 Quantum Chemistry, Coordination Chemistry【現在の研究課題】 Gas Adsorption, Proton Conductivity【研究内容キーワード】 Porous Coordination Polymers【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 and Shigeyoshi SAKAKI, “Interaction of various gas moleculeswith paddle-wheel-type open metal sites of porous coordination polymers:（過去 5 年以内）
theoretical investigation”, Inorg. Chem., 53 2417-2426 (2014)
2. Hiroshi SATO, Wataru KOSAKA, Ryotaro MATSUDA, Akihiro HORI, Yuh
HIJIKATA, Shigeyoshi SAKAKI, Masaki TAKATA, and Susumu KITAGAWA,“Self-accelerating CO sorption in a soft nanoporous crystal”, Science, 343, 167-170(2014)
3. Yuh HIJIKATA, Satoshi HORIKE, Masayuki SUGIMOTO, Munehiro INUKAI,
Tomohiro FUKUSHIMA, and Susumu KITAGAWA, “Pore design of twodimensional coordination polymers toward selective adsorption”, Inorg. Chem., 52,3634-3642 (2013)
4. 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)
5. 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)【学術関係の受賞など】 JSPS Research Fellowships for Young Scientists (DC1) 2008-2011－ 39 －

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Ⅱ 博士研究員 (2013)【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】 溶液化学・計算化学・理論化学【現在の研究課題】 溶液中の遷移金属錯体の化学反応の理論的解析【研究内容キーワード】 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【学歴】 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【学位】 2010年9月 理学博士（京都大学）【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【所属学会】 日本分子化学会【主な著書、学術論文】 1. Aono S., Nakagaki M., Kurahashi T., Fujii H., and Sakaki S., “Theoretical Studyof One-Electron Oxidized Mn(III)− and Ni(II)−Salen Complexes: Localized vs（過去 5 年以内）
Delocalized Ground and Excited States in Solution”, J. Chem. Theory Comput. 101062 (2014).
2. 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
reaction of phenyl alpha- and beta-D-glucosides under basic conditions”, Phys.
Chem. Chem. Phys. 17 6368 (2013)
3. 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)
4. 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).
5. 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).
6. 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).
7. 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).
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Ⅱ 博士研究員 (2013)【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 Nov. 2013: Postdoctoral Research Fellow, Kyoto University, Japan【主な著書、学術論文】 1. Milind M. Deshmukh, Sakaki Shigeyoshi “Generation of Dihydrogen Moleculeand Hydrosiliylation of Carbon Dioxide Catalyzed by Zinc Hydride Complex:（過去 5 年以内）
Theoretical Understanding and Prediction, Inorg. Chem. (Under Revision 2014).
2. Milind M. Deshmukh, Masaaki Ohba, Susumu Kitagawa, and Shigeyoshi Sakaki“Absorption of CO2 and CS2 into the Hofmann-Type Porous Coordination Polymer:
Electrostatic versus Dispersion Interactions” J. Am. Chem. Soc. 135, 4840 (2013).
3. 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).
4. 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).
5. 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).
6. 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).
【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).

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Ⅱ 博士研究員 (2013)【氏名（ふりがな）】 Guixiang Zeng會

桂 香（そうけいか）【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. G. Zeng, Y. Guo, and S. Li, “H2 activation by a (PNP)Ir(C6H5) complex via the
dearomatization/aromatization process of the PNP ligand: A computational study”（過去 5 年以内）
Inorg. Chem., 48, 10257 (2009).
2. G. Zeng and S. Li, “Mechanistic insight on the hydrogenation of conjugated alkenes
with H2 catalyzed by early main-group metal catalysts” Inorg. Chem., 49, 3361
(2010).
3. G. Zeng and S. 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. G. Zeng, and S. 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. G. Zeng and S. Sakaki, “Theoretical Study on the Transition-Metal Oxoboryl
Complex: M−BO Bonding Nature, Mechanism of the Formation Reaction, andPrediction of a New Oxoboryl Complex” Inorg. Chem., 51, 4597 (2012).
6. G. Zeng and S. 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).
7. S. Yamabe, G. Zeng, W. Guan, and S. Sakaki, “An Aniline Di-cation like Transition
State in the Bamberger Rearrangement” Org. Biomol. Chem. 9, 1073-1082 (2013).
8. S. Yamabe, G. Zeng, W. Guan, and S. Sakaki, “Substrate Dependent Reaction
Channels of the Wolff-Kishner reduction reaction: A Theoretical Study” Beilstein J.
Org. Chem., 10, 259–270 (2014).
9. G. Zeng, S. Sakaki, K.-I. Fujita, H. Sano, and R. Yamaguchi, “Efficient Catalyst for
Acceptorless Alcohol Dehydrogenation: Interplay of Theoretical and Experimental
Studies” ACS Catal., 4, 1010−1020 (2014).
10. G. Zeng, S. Maeda, T. Taketsugu, and S. Sakaki, “Catalytic Transfer Hydrogenation
by a Trivalent Phosphorus Compound: Phosphorus-Ligand Cooperation Pathway
or PIII/PV Redox Pathway?” Angew. Chem. Int. Ed., 53, 4633–4637(2014).
11. S. Yamabe, G. Zeng, W. Guan, and S. Sakaki, “SN1-SN2 and SN2-SN3 Mechanistic
Changes Revealed by Transition States of the Hydrolyses of Benzyl Chlorides andBenzenesulfonyl Chlorides” J Comput. Chem., 35, 1140-1148(2014).
12. W. Guan, F. B. Sayyed, G. Zeng, and S. Sakaki, (common authors) “σ−BondActivation of Small Molecules and Reactions Catalyzed by Transition-Metal
Complexes: Theoretical Understanding of Electronic Processes” Inorg. Chem. DOI
10.1021/ic5003429.
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Ⅱ 博士研究員 (2013)【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

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【学位】 2002年 3月

理学博士（東京都立大学）【略歴】 2002年4月
2005年4月
2007年5月
2011年4月
2014年4月

日本学術振興会 特別研究員（PD）
自然科学研究機構・分子科学研究所 専門研究職員
ドイツ・フィリップス=マールブルク大学 博士研究員
京都大学・福井謙一記念研究センター 特定研究員
京都大学・触媒・電池元素戦略拠点ユニット 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., 135, 8955-8965 (2013).
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).
【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）－ 43 －

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Ⅱ 博士研究員 (2013)【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
The Chemical Society of Japan【主な著書、学術論文】 1. Masayuki Nakagaki and Shigeyoshi Sakaki “CASPT2 Study of Inverse SandwichType Dinuclear Cr(I) and Fe(I) Complexes of the Dinitrogen Molecule: Significant（過去 5 年以内）
Differences in Spin Multiplicity and Coordination Structure between These Two
Complexes” J. Phys. Chem. A, 118, 1247-1257 (2014)
2. Shinji Aono, Masayuki Nakagaki, Takuya Kurahashi, Hiroshi Fujii, and Shigeyoshi
Sakaki “Theoretical Study of One-Electron Oxidized Mn(III)– and Ni(II)–Salen
Complexes: Localized vs Delocalized Ground and Excited States in Solution” J.
Chem. Theory Comput., 10 1062-1073 (2014)－ 44 －

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Ⅱ 博士研究員 (2013)【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 Inert Bond Activation【研究内容キーワード】 C − C Bond Activation, Cooperative Catalysis, Lewis Acid, 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.; Sayyed, F. B.; Zeng, G. X.; Sakaki, S. Inorg. Chem. 2014, ic5003429.
（過去 5 年以内）
2. Guan, W.; Sakaki, S.; Kurahashi, T.; Matsubara, S. Organometallics 2013, 32, 7564
−7574.
3. Guan, W.; Yamabe, S.; Sakaki, S. Dalton Trans. 2013, 42, 8717−8728.

4. Yamabe, S.; Guan, W.; Sakaki, S. J. Org. Chem. 2013, 78, 2527−2533.

5. Yamabe, S.; Zeng, G. X.; Guan, W.; Sakaki, S. J. Comput. Chem. 2014, 35, 1140–
1148.

【学術関係の受賞など】 China Postdoctoral Science Special Foundation 2010-2011－ 45 －

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Ⅱ 博士研究員 (2013)【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】 Theoretical Study of Benzene formation from Alkyne catalyzed by Mo-Mo Quintuple
Bond.
【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; 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,
（過去 5 年以内）
10334-10338 (2010)
2. 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)
3. 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)
4. 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.” Inorg. Chem., 52,
13146-13159 (2013).
5. Yue Chen, Shigeyoshi Sakaki The important role of the Mo-Mo quintuple bondin catalytic synthesis of benzene from alkynes. A theoretical study. Dalton Trans.,
2014, Advance Article. DOI: 10.1039/C4DT00595C－ 46 －

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Ⅱ 博士研究員 (2013)【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, 117, 10455–10461.
（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.

－ 47 －

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Ⅱ 博士研究員 (2013)【氏名（ふりがな）】 山田 健太（やまだ けんた）
【職名】 特推研究フェロー (Special Promoted Research Post-doctoral Fellow)【所属】 京都大学 福井謙一記念研究センター【研究室】 303 号室【直通電話】 075-711-7907【電子メールアドレス】 ykenta@fukui.kyoto-u.ac.jp【研究分野】 計算化学、理論化学【現在の研究課題】 水素発生活性をもつ遷移金属錯体に関する理論研究【研究内容キーワード】 遷移金属錯体、分子構造、水素発生、触媒活性【最終学歴】 2011年 3月 名古屋大学大学院博士課程 単位取得済満期退学【学位】 2012年 4月 学位 博士(情報科学)（名古屋大学）【略歴】 2012年 5月 横浜市立大学 大学院生命ナノシステム科学研究科 特任助手
2012年 12月横浜市立大学 大学院生命ナノシステム科学研究科 特任助教
2013年 4月 京都大学福井謙一記念研究センター 特推研究フェロー【所属学会】 日本化学会【主な著書、学術論文】 1. Okamoto, T.; Yamada, K.; Koyano, Y.; Asada, T.; Koga, N.; Nagaoka, M. “A
Minimal Implementation of the AMBER–GAUSSIAN Interface for Ab Initio QM/（過去 5 年以内）
MM-MD Simulation” J. Comput. Chem. 32, 932–942, 2011.
2. Yamada, K.; Koyano, Y.; Okamoto, T.; Asada, T.; Koga, N.; Nagaoka, M. “Toward
a New Approach for Determination of Solute’s Charge Distribution to Analyze
Interatomic Electrostatic Interactions in QM/MM Simulations” J. Comput. Chem.
32, 3092–3104, 2011.
3. Yamada, K.; Koga, N. “Variationally determined electronic states for the theoreticalanalysis of intramolecular interaction: I. Resonance energy and rotational barrier of
the C–N bond in formamide and its analogs” Theor. Chem. Acc. 131, 1178–1195,
2012.
4. Yamada, K.; Koga, N. “Variationally Determined Electronic States for the
Theoretical Analysis of Intramolecular Interaction. II. Qualitative Nature of the
P–O Bond in Phosphine Oxides” J. Comput. Chem. 34, 149–161, 2012.
5. Yamada, K.; Kawashima, Y.; Tachikawa, M. “Muon-electron hyperfine coupling
constants of muoniated ethyl radical: a path integral simulations study withsemiempirical molecular orbital method” Chin. J. Phys. 52, 126–137, 2014.
6. Mashiko, T.; Yamada, K.; Kojima, T.; Nagashima, U.; Hiraoka, S.; Tachikawa,
M. “Molecular dynamics and principal component analysis for a self-assembled
nanocube in aqueous solution” Chem. Lett. 40, 366–368, 2014.
7. Hiyama, M.; Akiyama, H.; Mochizuki, T.; Yamada, K.; Koga, N. “Analysis
of Photoexcitation Energy Dependence in the Photo Luminescence of Firefly
Luciferin” Photochem. Photobio. Accepted. 2014
【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)－ 48 －

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Ⅲ 研究広報活動 (2013)

Ⅲ

研究広報活動Ϫ ◊✲ᗈሗάື
㸯㸬⚟஭ㅬ୍グᛕ◊✲ࢭࣥࢱ࣮ࢩ࣏ࣥࢪ࣒࢘
第 1１�京都大学福井謙一記念研究センターシンポ��ム
日時2014 年(平成 26 年) 1 月 23 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

谷口

正輝 (大阪大学産業科学研究所 教授)「１分子接合の物性」
10:15―11:15
永瀬茂（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）「高周期元素を骨格にもつ分子とフラーレン 」
11:30―12:30
宣博 (京都大学化学研究所 教授）

時任「高周期典型元素を含む新規なπ電子系の創出」
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）－ 49 －

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Ⅲ 研究広報活動 (2013)����������
第 11 �福井センターセ��ー
日時2013 年(平成 25 年) 7 月 24 日

場

所

京都大学福井謙一記念研究センター（1F 多目的室）

14:00～14:05

14:00－17:30

Opening by Professor Kazuyoshi Tanaka(Director, Fukui Institute for Fundamental Chemistry)

14:05～15:05

Professor Shin-ichi Yamabe(Fukui Institute for Fundamental Chemistry)“Proton transfers in some organic reaction pathways”

15:05 ～16:05

Professor Mitsutaka Okumura(Osaka University)“Theoretical study for the characteristics and catalytic reactions of Auclusters”
Break
16:20～17:30

Professor Odile Eisentein(Université Montpellier 2, France)“ Computational studies and chemical complexity: A half full/half empty glass story
illustrated by the computational studies of the olefin metathesis catalysis with the Schrock
alkylidene complexes ”��������������
高等学校������
(1) 畑中美穂 特定研究員
兵庫県立北摂三田高等学校〃
京都府立城南菱創高等学校

2013 年(平成 25 年) 9 月 12 日
2013 年(平成 25 年)12 月 18 日
2013 年(平成 25 年) 12 月 17 日

－ 50 －

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Ⅲ 研究広報活動 (2013)(2) 榊 茂好リサーチリーダー
京都府立洛北高等学校(3) 諸熊

2013 年(平成 25 年) 11 月 15 日

奎治シニアリサーチフェロー

京都府立南陽高等学校

2013 年(平成 25 年) 11 月 7 日

㸲㸬ࡑࡢ௚㸦ሗ࿌㸧  諸熊 奎治シニアリサーチフェローは、２０１３年ノーベル化学賞の受賞者の授賞研究の業績説明で、重要な貢献をした７人の中に含まれていることが判った。
（資料編６を参照）－ 51 －

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Ⅳ 研究業績 (2013)

Ⅳ

研究業績

１．専任教員

��
池田

��
昌司

総合研究部門�合研究��

准教授

����� �年度の研究の要�
ガラス転移・ジャミング転移の統計力学研究
���に� 液体を急冷すると、分子の運動が劇的にスローダウ
ンし、ついにはアモルファス状に凍結してしまう。これがガラス転移である。一方、このガラス転移とよく似た現象として、
ジャミング転移が知られている。ジャミング転移とは、泡や粉体などで見られる、流動相から非流動相への転移現象である。
ガラス転移とジャミング転移の違いは、後者の場合、粒子が十分大きく、その熱運動が無視できることである。しかしそれ以外では、共にアモルファス固体相への転移現象であり、非常に似通っていることから、その関係は近年のガラス研究のホットトピックとなっている。10 年程前に、現象論的に両転移を同一視する相図（図 1a）が提案され 1、当該分野で重要視されてきた。

私はここ数年、この両転移の関係解明に集中的に取り組んできた。昨年度には、シミュレーションを用いてガラス転移とジ
ャミング転移を分離することに成功した。具体的には、有限温度ではガラス転移を、ゼロ温度ではジャミング転移を起こすモデルに注目し、両者の統一的研究を行ったところ、両者を明確に分離することに成功した 2。
得た相図を図 1b に示す。
これは、図１ �� ガラス転移とジャミング転移

幅広い温度・応力・密度領域において、固体相と液体相のありに関する従来の現象論的相図。両かを示す相図である。図 1a と図 1b の違いは明らかだ。図 1aでは、ガラス転移とジャミング転移が混同されていたのだ。
本年度は、(1)この成果に基づいて多種多様な実験を説明する
試み、(2)この成果をモード結合理論で再現できるかを検討する

転移は区別されていない。 �� シミュレーションで決定した相図。両転移は明確に分離される。

試み、を行った。また付加的に、(3)これまで研究してきたガウスコア模型のガラス転移の研究を拡張する試み、を行った。以下でこれらを詳述する。
�レ��ジー��の��るガラス転移とジャミング転移�分離する� 以上のシミュレーションで得た知見をもとに、様々な分散系のレオロジー実験を解析した。まず、シミュレーションの結果と実験結果を整合的に記述する新しい現象論モデルを構築した。
分散系の粒子は、周りの液体分子に衝突されるために、熱運動しうる。一方で、粒子が別の粒子と接触するとき、粒子間には直接的な力が働く。つまり系は二つのエネルギースケールをもつ。一1－ 52 －

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Ⅳ 研究業績 (2013)

図２ PMMA コロイドの流動曲線（シンボル）を、開発し

図３ Oil in Water エマルジョンの流動曲線（シンボル）

たレオロジー模型（線）で解析した。

を、開発したレオロジー模型（線）で解析した。

つはブラウン運動の駆動力である「熱的なエネルギースケール kBT」であり、もう一つは粒子の硬さに対応する「非熱的なエネルギースケール(ここでは ε と置く)」である。そして、二つのエネル
ギースケールに付随して、二つの微視的時間スケールが現れる。散逸の時間スケール τ0 = ξa2/ε と、
ブラウン運動の時間スケール τT = ξa2/kBT である。ここで ξ を液体の粘性に由来する散逸として導入した。さらに，せん断流速 γ が，第三の時間スケールを与える．そこで重要な無次元量として，γτT を導入する．γτT << 1 は，粒子が，せん断流よりずっと速く，ブラウン運動している状態であり，γτT >>

1 は，ブラウン運動よりずっと速く，せん断流が粒子を押し流している状態である．

そして、応力についても、非熱的な応力スケール σ0 = ε/a3 と、熱的な応力スケール σT = kBT /a3 が現れる。
我々のシミュレーション研究は、ガラス転移は熱的な時間領域で見られる転移であり、そこで発生する応力は熱的なスケール σT にコントロールされており、ジャミング転移は非熱的な時間スケールで起こる転移であり応力は非熱的なスケール σ0 にコントロールされていることを示した。そこで、この効果を取り込んだ現象論的なレオロジー模型を導入する：

この模型の基本的な哲学は、ガラス転移とジャミング転移は別々であり、全応力は両者の寄与の和として表されるというものだ。Sg と Sj の具体形は、ガラス転移とジャミング転移の物理からそれぞれ別々に決まる。この模型を用いて、コロイド分散系、マイクロジェル、エマルション、泡、さらに調和粒子系のシミュレーションを解析した（図２、図３）。これらの実験系が、構築した現象論モデルで極めてうまく記述できることがわかった。この解析を用いると、これらの実験系のどの部分がガラス転移の物理にコントロールされており、どの部分がジャミング転移に対応しているかを解析することができる。その結果コロイド分散系は、完全にガラス転移の物理によりコントロールされていること、一方で泡はジャミング転移の物理によりコントロールされていることを示した。さらに、エマルションの理解には、ガラス転移とジャミング転移の両方の寄与をバランスよく取り込む必要があることが明らかとなった。最後にマイクロジェルの解析をしたところ、この系は2－ 53 －

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Ⅳ 研究業績 (2013)

しばしばジャミング転移のモデルとして研究されているにもかかわらず、ほぼガラス転移だけで解析できることが明らかとなった。上述の知見をまとめるために、図４に、様々な実験系のパラメータ領域を動的相図上にプロットした。各実験系が、ガラス転移を示すのか、ジャミング転移を示すのかは、極めて明確である。
�ガラス��・ジャミング��を�ー�����������
次に、これらのシミュレーションや実験の結果を、現在のガラス転移の微視的理論は説明できるかを検討した。具体的には、モード結合理論により、図１の相図が再現できるかに注目した。

図４ ガラス・ジャミング相図上に、様々な実験系のパラメータ領域をプロットした。

ここではシア流中に拡張されたモード結合理論に注目する。この理論は、ガラス的な系の応力を微視的に計算する理論である。この理論では、系の応力はと表される。ここで c(k)は直接相関関数であり、Ft(k,t)はシア流中での中間散乱関数、すなわち密度場の時間相関関数である。MCT に従って中間散乱関数を評価し、この表式を通じて系の応力を求めた。この計算を様々な密度と温度とシア流速の場合について繰り返し、モード結合理論による相図を得た。その結果をまとめると、(1)ガラス相において σT に比例する応力が発生する。(2)ジャミング相に向かい、応力が密度差の 4 乗で発散挙動を示す。(3)ジャミング相内部では、密度の増加とともに応力が減少する。このうち、(1)はシミュレーションの結果を正しく再現している。(2)は定性的には正しいが、定量的には大きく異なる。シミュレーションの場合、応力発散の指数は 1である。(3)はシミュレーションの結果を全く捕らえられていない。
従って、図１におけるガラス相の部分と、ガラス相からジャミング相への臨界的な挙動について
は、定性的にはモード結合理論で記述できることが分かった。一方でジャミング相の応力の再現には、さらなるガラス転移理論の深化が必要である。
�ガ�ス����に��に����の��� 柔らかいコロイド系のモデルとして、ガウスコア模型(GCM)が研究されてきた。ガウスコア模型は、系の粒子がガウス型の相互作用 v(r) = exp(-r2)をする
液体モデルである。我々の先行研究により、ガウスコア模型のガラス転移は、極度に平均場的になり、モード結合理論と極めて相性がよくなることがわかっている 3。一方で、ガウス関数の指数を２から４に変えた模型を一般化指数関数模型(n=4)と呼ぶ。近年、一般化指数関数模型(n=4)のガラ
ス転移が調べられ、その低温領域には、クラスターガラスという全く新しいガラス相があることが分かった 4。クラスターガラスとは、多数の粒子が一つのサイトに集まりクラスターを形成し、そしてそのサイトの空間分布がガラス状にアモルファスに分布する相である。

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では、この指数の変更は、系の統計力学をどのようにして変えているのだろうか？我々は、ガウス関数の指数を２から 2.01、2.02 と連続的に大きくし、まず、その結晶化挙動を詳しく解析した。
このような模型は、単なる理論家のおもちゃではない。実際に、両親媒性を有するデンドリマーの相互作用は、このような２よりわずかに大きいガウス関数でうまくモデル化できることが知られている。
我々はまず、HNC 理論と MSA 理論という液体の統計力学の手法を用いて、この系の相図の概略を検討した（図５）。すると、指数が２からわ

図５ 様々な指数での、一般化指数模型 v(r) =ずかに大きくなると、低密度での相図はほぼガウ

exp(-rn)の相図を HNC 理論と MSA 理論に基づいてスコア模型と同様であるが、高密度側で指数４の予測した。実線より下の部分が結晶相である。n=2 か場合と同種のクラスター相が現れることが分から大きくすると、ガウスコア模型の場合からのずれった。さらに指数を大きくすると、このクロスオ

が、高密度側で現れることが分かる。このリエントランーバ密度が徐々に低下し、最終的に、クラスター

ト的振る舞いを見せる結晶相こそ、クラスター相だ。

相が、結晶相全体を占めるようになることがわかった。さらにこの結果を、シミュレーションで確認し、その変化をポテンシャルエネルギー地形の観点からも解析した。すると、ポテンシャルエネ
ルギー地形そのものにおいても、クラスター状態が極めて安定に存在していることが分かった。
���� 1) A. J. Liu and S. R. Nagel, Nature (London), 39�, 21 (1998). 2) A. Ikeda, L. Berthier, P.

Sollich, Phys. Rev. Lett. 109, 018301 (2012). 3) A . Ikeda and K. Miyazaki, Phys. Rev. Lett., 10�,
015701 (2011). 4) D. Coslovich, M. Bernabei, A.J. Moreno, J. Chem. Phys. 137, 184904 (2012).

�� 論�(1) Daniele Coslovich and Atsushi Ikeda,“Cluster and reentrant anomalies of nearly Gaussian core particles”
Soft Matter 9, 6786-6795 (2013).
(2) Atsushi Ikeda, Ludovic Berthier and Peter Sollich“Disentangling glass and jamming physics in the rheology of soft materials”
Soft Matter (Highlight Article) 9, 7669-7683 (2013).
(3) 池田昌司“ガラス転移とジャミング転移を分離する”
日本物理学会誌 第 68 巻 第 7 号 464 頁 (2013 年 7 月号)(4) Atsushi Ikeda and Ludovic Berthier4－ 55 －

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Ⅳ 研究業績 (2013)“Yield stress in amorphous solids: A mode-coupling-theory analysis”
Physical Review E 88, 052305(1-14) (2013).

�� ����
(1) Atsushi Ikeda,“Unified study of glass and jamming rheology in soft particle systems”
Workshop: Bridging the Scales in Glasses II, 2013.10.22, Dresden, Germany. (Invited)(2) Atsushi Ikeda“Unified study of glass and jamming rheology in soft particle systems”
International Discussion Meeting on Relaxations in Complex Systems, 2013.7.25,
Barcelona, Spain. (Invited)(3) Atsushi Ikeda, Daniele Coslovich and Kunimasa Miyazaki,“Mean-field-like glass transition of the gaussian core model”
Nagoya Symposium on Depletion Forces: Celebrating the 60th Anniversary of the
Asakura-Oosawa Theory, 2014.3.15, Nagoya.

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２．シニアリサーチフェロー

ShigeruNAGASE
NagaseShigeru
Senior Research
Research Fellow
Fellow ofof FIFC
FIFC
Senior
1. Summary of the research of the year(a) Development of RI-MP2Auxiliary Basis Functions for 6-31G** and 6-311G** Basis Sets
Electron correlation plays an important role in the accurate description of energies, structures, andproperties of molecules. Density functional theory (DFT) is widely used to take account of electron
correlation because of its low computational cost. However, generally used DFT methods present several
shortcomings. For example, they fail to describe non-covalent interactions and reaction barriers.
Second-order Møller–Plesset perturbation (MP2) theory is the simplest method to include electron
correlation at an ab initio level, which is important for non-covalent interactions and reaction barriers.
However, the computational cost of MP2 calculations is considerably high and practical applications arelimited to molecules of moderate size. The resolution-of-identity (RI) approximation for MP2 is a promising
approach to reduce the computational cost and resources used for MP2 calculations without sacrificing
accuracy. The accuracy of RI-MP2 calculations, considering error from conventional MP2 calculations,depends on the quality of the auxiliary basis functions, while the computational cost of RI-MP2 calculations
depends on the size of auxiliary basis functions. Consequently, various RI-MP2 auxiliary basis functions aredeveloped to obtain appropriate accuracy with reasonable size.
Pople-type basis sets represented by 6-31G** and 6-311G** are widely used as standard basis sets forcalculations of large systems because of their reasonable accuracy and computational cost. However, theauxiliary basis functions are not developed up to date. Therefore, we have developed the auxiliary basis
functions that are suitable for RI-MP2/6-31G** and RI-MP2/6-311G** calculations in terms of accuracy andcomputational costs. In the development of the auxiliary basis functions, the strategy for adding g-type
auxiliary functions is proposed to improve the accuracy of the RI approximation with low computational cost.
The performance of the developed auxiliary basis functions is assessed for 114 small and 23 large molecules(Fig. 1). It is remarkable that the developed auxiliary basis functions shows much smaller RI errors thanother auxiliary basis functions used for 6-31G** and 6-311G** basis sets with similar computations costs.
This fact suggests that the developed 6-31G** and 6-311G* auxiliary basis functions are widely applicableto the RI-MP2 calculations of large molecules with high accuracy and low computational cost.

Fig. 1. Examples of large molecules tested for RI-MP2 calculations.
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Ⅳ 研究業績 (2013)(b) Carbide Cluster Metallofullertenes: Structures, Properties, and Possible Origin
Endohedral metallofullerenes (EMFs) are hybrid molecules with different metallic species encapsulated
inside hollow fullerene cages. In addition to conventional EMFs that contain merely metal ions, novelcompounds encapsulating a metallic cluster of, for instance, nitride, carbide, oxide, cyanide, and sulfide haveall been obtained. Among them, carbide cluster metallofullerenes(CCMFs) are quite unique because their synthetic processes require no
extra element except graphite and the metal sources, which results in
the intractable situation that the molecular structures of CCMFs are
particularly difficult to identify because exactly two carbon atoms areencapsulated inside the cage, but they do not participate in constructing
the cage framework. Because of recent achievements in the theoreticaland X-ray crystallographic studies of EMFs, several new CCMFs (e.g.
MxC2@C2n) have been assigned unambiguously, most of which werepreviously proposed as conventional EMFs Mx@C2n+2. Such species
are mainly scandium-containing compounds such as Sc3C2@Ih(7)-C80 [not Sc3@C3v(7)-C82] (see: Fig.2 ),Sc2C2@C2v(5)-C80 [not Sc2@C82], Sc2C2@Cs(6)-C82 [not Sc2@Cs(10)-C84], Sc2C2@C2v(9)-C82 [notSc2@C2v(17)-C84], Sc2C2@C3v(8)-C82 [not Sc2@D2d(23)-C84], and Sc2C2@D2d(23)-C84 [not Sc2@C86].
Additional examples of CCMFs include Gd2C2@D3(85)-C92, Sc2C2@C2v(6073)-C68, Ti2C2@D3h(5)-C78,
M2C2@C3v(8)-C82, M2C2@Cs(6)-C82 (M = Y, Er etc.), Y2C2@C84, Y2C2@D3(85)-C92, Y2C2@D5(450)-C100,
and Lu3C2@D2(35)-C88. We present a detailed summary of all aspects of CCMFs, including historicallyerroneous assignments and corrected structural characterizations, along with their intrinsic properties such as
electrochemical and chemical properties. Emphasis is given to the structural issues which are fundamental
aspects for understanding their intrinsic properties. Finally, discussion related to the formation mechanismand possible origin of cluster EMFs, not only related to CCMFs, is presented.

(c) Mechanistic Study of the Diels-Alder Reaction of La@C82
The Diels-Alder reaction is an extremely valuable type of cycloaddition in organic chemistry. In recent
year, much attention has been
focused on the Diels-Alder reactionof fullerenes because it can be ausefulmethodfor

introducing

functionality to fullerene cages. The
fact that fullerenes such as C60 and
C70 act as polyalkenes and possess
reactive

dienophilecharacterderived from their electron-deficient
properties

has

promptedthedevelopment of numerous efficient
Diels-Alder reactions of fullerenes.
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The reaction mechanism of the Diels-Alder reaction of paramagnetic endohedral metallofullertene, La@C82,
and 1,2,3,4,5-pentamethylcyclopentadiene (Cp*) was investigated theoretically and experimentally. Density
functional theory calculations reveal that the reaction proceeds via a concerted mechanism that includes
formation of a stable intermediate (Fig. 3). The activation energy of a retro-Diels-Alder reaction is also
investigated experimentally, which agrees well with the results of density functional theory calculations.

(d) Structural, Electronic, and Optical Properties of Bulk Graphdiyne
Graphdiyne is a newly discovered two-dimensional carbon allotrope with many special features. The
structural, electronic, and optical properties ofseveralbulk

graphdiyne

structures

wereinvestigated using density functional theory withvan der Waals correction (Fig. 4). It is found thatbulk graphdiyne can be either semiconductive or
metallic, depending on its stacking configuration.
The interlayer van der Waals force red-shifts the
optical absorption peaks of bulk graphdiyne
relative to those of monolayer; the spectra ofdifferent stacking structures display notabledifferences in the energy range below 1 eV. Finally, the structure of the recently synthesized graphdiyne film
is identified combining with previous electronic and optical experiments.

(e) Several Other Research Subjects(1) Unexpected Formation of Ru2Sn2 Bicyclic Four-Membered Ring Complexes with Butterfly andInverse-Sandwich Structures. (2) Density Functional Theory Study of Fullerene-Carbene Lewis Acid-Base
Adducts: Critical Role of Dispersion Interactions. (3) Hellicity-selective photoreaction of single-walledcarbon nanotubes with organosulfur compounds in the presence of oxygen. (4) Regiochemistry of
Nonclassical

C62

Fullerene:

Role

of

Tetragonal

Carbocyclic

Ring

in

Cycloadditions

andThermal/Photoinduced Interconversions of Fulleroid Derivatives. (5) Intramolecular versus IntermolecularElectronic Interactions between [5,6]-Open and [6,6]-Closed Adducts with exTTF. (6) Linear and Nonlinear
Two-Coordinate Vanadium Complexes: Synthesis, Characterization, and Magnetic Properties of V(II)Amides. (7) A Metallofullerene Electron Donor that Powers an Efficient Spin Flip in a Linear Electron
Donor- Acceptor Conjugate. (8) Enhanced Many-Body Effects in One-Dimensional Linear Atomic Chains.
(9) 1,3-Dipolar Cycloadditions of Stone-Wales Defective Single-Walled Carbon Nanotubes: A Theoretical
Study. (10) Dispersion Force Stabilized Two-Coordinate Transition Metal-Amido Complexes of the-N(SiMe3)Dipp (Dipp = C6H3-2,6-Pri2) Ligand: Structural, Spectroscopic, Magnetic, and Computational
Studies. (11) Cycloaddition of Benzyne to Armchair Single-Walled Carbon Nanotubes: [2+2] or [4+2]?
(12) Diversity of the Structures in a Distannene Complex and its Reduction to Generate a Six-Membered
Ti2Sn4 Ring Complex. (13) Regioselective Derivatization of C84 by Diels-Alder Reactions: Applications to
Photovoltaic Solar Cells and Fullerene Polymerization.
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Ⅳ 研究業績 (2013)

2. Original papers(1) 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).
(2) 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).
(3) Y. Maeda, J. Higo, Y. Amagai, J. Matsui, K. Ohkubo, Y. Yoshigoe, M. Hashimoto, K. Eguchi, M.
Yamada, T. Hasegawa, Y. Sato, J. Zhou, J. Lu, T. Miyashita, S. Fukuzumi, T. Murakami, K. Tohji, S.
Nagase, and T. Akasaka, "Helicity-Selective Photoreaction of Single-Walled Carbon Nanotubes with
Organosulfur Compounds in the Presence of Oxygen", J. Am. Chem. Soc., 135, 6356-6362 (2013).
(4) Y. Xie, M. Suzuki, W. Cai, N. Mizorogi, S. Nagase, T. Akasaka, and X. Lu, "Highly Regioselective
Addition of Admantylidene Carbene to Yb@C2v(3)-C80 to Afford the First Derivative of Divalent
Metallofullerenes", Angew. Chem. Int. Ed., 52, 5142-5145 (2013).
(5) T. Akasaka, T. Tsuchiya, L. Feng, Y. Takano, and S. Nagase, "New Vistas in Fullerene Chemistry:
Organosulfer Compounds Expand the Performance of Carbon Nanomaterials", Phosphorus, Sulfur
Silicon Relat. Elem., 188, 317-321 (2013).
(6) P. Jin and S. Nagase, "Density Functional Theory Study of Fullerene-Carbene Lewis Acid-Base
Adducts: Critical Role of Dispersion Interactions", RSC Adv., 3, 10177-10180 (2013).
(7) J. –S. Dang, W. –W. Wang, S. Nagase, and X. Zhao, "Regiochemistry of Nonclassical C62 Fullerene:
Role of Tetragonal Carbocyclic Ring in Cycloadditions and Thermal/Photoinduced Interconversions ofFulleroid Derivatives", J. Phys. Chem. C, 117, 12882-12889 (2013).
(8) G. Luo, Q. Zheng, W. –N. Mei, J. Lu, and S. Nagase, "Structural, Electronic, and Optical Properties of
Bulk Graphdiyne", J. Phys. Chem. C, 117, 13072-13079 (2013).
(9) Y. Takano, C. Schubert, N. Mizorogi, L. Feng, A. Iwano, M. Katayama, M. A. Herranz, D. M. Guldi, N.
Martion, S. Nagase, and T. Akasaka, "Intramolecular versus Intermolecular Electronic Interactions
between [5,6]-Open and [6,6]-Closed Adducts with exTTF", Chem. Sci., 4, 3166-3171 (2013).
(10) J. N. Boynton, J. –D. Guo, J. C. Fettinger, C. E. Melton, S. Nagase, and P. P. Power, "Linear andNonlinear Two-Coordinate Vanadium Complexes: Synthesis, Characterization, and Magnetic Propertiesof V(II) Amides", J. Am. Chem. Soc., 135, 10720-10728 (2013).
(11) M. Rudolf, L. Feng, Z. Slanina, T. Akasaka, S. Nagase, and D. M. Guldi, "A Metallofullerene Electron
Donor that Powers an Efficient Spin Flip in a Linear Electron Donor- Acceptor Conjugate", J. Am.
Chem. Soc., 135, 11165-11174 (2013).
(12) R. Fei, G. Luo, Y. Wang, Z. Gao, S. Nagase, D. Yu, and J. Lu, "Enhanced Many-Body Effects in
One-Dimensional Linear Atomic Chains", Phys. Status. Solidi B, 250, 1636-1643 (2013).
(13) W. Zhang, M. Suzuki, Y. Xie, L. Bao, W. Cai, Z. Slanina, S. Nagase, M. Xu, T. Akasaka, and X. Lu,"Molecular Structure and Chemical Property of a Divalent Metallofullerene Yb@C2(13)-C84", J. Am.
Chem. Soc., 135, 12730-12735 (2013).
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Ⅳ 研究業績 (2013)(14) T. Yang, X. Xhao, and S. Nagase, "1,3-Dipolar Cycloadditions of Stone-Wales Defective Single-Walled
Carbon Nanotubes: A Theoretical Study", J. Comput. Chem., 34, 2223-2232 (2013).
(15) T. Agou, T. Wasano, P. Jin, S. Nagase, and N. Tokitoh, "Synthesis and Structures of an Alumole and its
Dianion", Angew. Chem. Int. Ed., 52, 10031-10034 (2013).
(16) C. Schubert, M. Rudolf, D. M. Guldi, Y. Takano, N. Mizorogi, M. A. Herranz, N. Martín, S. Nagase,and T. Akasaka, "Rates and Energetics of Intramolecular Electron Transfer Processes in ConjugatedMetallofullerenes", Phil. Trans. R. Soc. A, 371, 20120490 (10 pages) (2013).
(17) M. Tanaka, M. Katouda, and S. Nagase, "Optimization of RI-MP2 Auxiliary Basis Functions for
6-31G** and 6-311G** Basis Sets for First-, Second-, and Third-Row Elements", J. Comput. Chem., 34,
2568-2575 (2013).
(18) H. Zheng, X. Zhao, W. –W, Wang, J. –S. Dang, and S. Nagase, "Quantum Chemical Insight into
Metallofullerenes M2C98: M2C2@C96 or M2@C98, Which Will Survive?", J. Phys. Chem. C, 117,
25195-25204 (2013).
(19) C. -Y. Lin, J. –D. Guo, J. C. Fettinger, S. Nagase, F. Grandjean, G. J. Long, N. F. Chilton, and P. P.
Power, "Dispersion Force Stabilized Two-Coordinate Transition Metal-Amido Complexes of the-N(SiMe3)Dipp (Dipp = C6H3-2,6-Pri2) Ligand: Structural, Spectroscopic, Magnetic, and Computational
Studies", Inorg. Chem., 52, 13584-13593 (2013).
(20) C. -Y. Lin, J. –D. Guo, J. C. Fettinger, S. Nagase, F. Grandjean, G. J. Long, N. F. Chilton, and P. P.
Power, "Cycloaddition of Benzyne to Armchair Single-Walled Carbon Nanotubes: [2+2] or [4+2]?", T.
Yang, X. Zhao, and S. Nagase, Org. Lett, 15, 5960-5963 (2013).
(21) M. Suzuki, N. Mizorogi, T. Yang, F. Uhlik, Z. Slanina, X. Zhao, M. Yamada, Y. Maeda, T. Hasegawa,S. Nagase, X. Lu, and T. Akasaka, "La2@Cs(17490)-C76: A New Non-IPR Dimetallic Metallofullerene
Featuring Unexpectedly Weak Metal-Pentalene Interactions", Chem. Eur. J., 19, 17125-17130 (2013).
(22) F. Uhlík, Z. Slanina, S. –L. Lee, T. Akasaka, and S. Nagase, "Predicting Stabilities of Endohedral
Metallofullerenes Yb@C84", Phys. Status Solidi B, 250, 2709-2712 (2013).
(23) J. N. Boynton, J. –D. Guo, F. Grandjean, J. C. Fettinger, S. Nagase, G. J. Long, P. P. Power, "Synthesis
and Characterization of the Titanium Bisamide Ti{N(H)AriPr6}2 (AriPr6 = C6H3-2,6-(C6H2-2,4,6-iPr3)2and its TiCl{N(H)AriPr6}2 Precursor: Ti(II)  Ti(IV) Cyclization", Inorg. Chem., 52, 14216-14223(2013).
(24) J. –S. Dang, W. –W. Wang, X. Zhao, and S. Nagase, "Regioselective Derivatization of C84 byDiels-Alder Reactions: Applications to Photovoltaic Solar Cells and Fullerene Polymerization", Org.
Lett., 16, 170-173 (2014).
(25) T. Kuwabara, J. D. Guo, S. Nagase, and M. Saito, "Diversity of the Structures in a Distannene Complex
and its Reduction to Generate a Six-Membered Ti2Sn4 Ring Complex", Angew. Chem. Int. Ed., 53,
434-438 (2014).
(26) J. Ruan, Y. Xie, W. Cai, Z. Slanina, N. Mizorogi, S. Nagase, T. Akasaka, and X. Lu, "Chemical
Properties of Divalent Metallofullerenes Yb@D3h(1)-C74 and Yb@C2(13)-C84", Fullerenes, Nanotubes,
Carbon Nanostruct., 22, 138-146 (2014).

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Ⅳ 研究業績 (2013)(27) Z. Slanina, F. Uhlík, S. –L. Lee, M. Suzuki, X. Lu, N. Mizorogi, S. Nagase, and T. Akasaka,"Calculated Temperature Development of the Relative Stabilities of Yb@C82 Isomers", Fullerenes,
Nanotubes, Carbon Nanostruct., 22, 147-154 (2014).
(28) Z. Slanina, F. Uhlík, S. –L. Lee, L. Adamowicz, H. Kurihara, H. Nikawa, X. Lu, M. Yamada, S. Nagase,and T. Akasaka, "Computations on Metallofullerenes Derivatized during Extraction: La@C80-C6H3Cl2and La@C82-C6H3Cl2", Fullerenes, Nanotubes, Carbon Nanostruct., 22, 173-181 (2014).
(29) Z. Slanina, F. Uhlík, S. –L. Lee, L. Adamowicz, L. Feng, M. O. Ishituka, T. Tsuchiya, X. Zhao, and S.
Nagase, "Sm@C74: Computed Relative Isomeric Populations", Fullerenes, Nanotubes, Carbon
Nanostruct., 22, 235-242 (2014).
(30) Z. Slanina, F. Uhlík, S. –L. Lee, B. C. Wang, L. Adamowicz, M. Suzuki, M. Haranaka, L. Feng, X. Lu,
S. Nagase, and T. Akasaka, "Towards Relative Populations of Non-Isometric Metallofullerenes:
La@C76 (Td) vs. La2@C76 (Cs, 17490)", Fullerenes, Nanotubes, Carbon Nanostruct., 22, 299-306(2014).

3. Review articles(1) X. Lu, T. Akasaka, and S. Nagase, "Carbide Cluster Metallofullerenes: Structure, Properties, andPossible Origin", Acc. Chem. Res., 46, 1627-1635 (2013).
(2) M. Yamada, T. Akasaka, and S. Nagase, "Carbene Additions to Fullerenes", Chem. Rev., 113,
7209-7264 (2013).
(3) S. Nagase, "Theory and Calculations of Molecules Containing Heavier Main Group Elements andFullerenes Encaging Transition Metals: Interplay with Experiment", Bull. Chem. Soc. Jpn. (Award
Accounts), 87, 167-195 (2014).

4. Books(1) M. Yamada, X. Lu, L. Feng, S. Sato, Y. Takano, S. Nagase, and T. Akasaka, "Fundamental and Applied
Aspects of Endohedral Metallofullerenes as Promissing Carbon Nanomaterials", In Organic
Nanomaterials: Synthesis, Chracterization, and Device Appilcations (Eds. T. Torres and G. Bottarti),
John Wiley & Sons, Chapter 12, pp. 241-258 (2013).
(2) 土屋敬広、溝呂木直美、永瀬 茂、赤阪 健、" 空間�����������の創�と機能"、

高次 空間の創発と機能開発、(赤阪 健、大須賀篤弘、福住俊一、神取秀樹 監修)、シーエム
シー出版、pp. 5-9 (2013).

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Keiji MOROKUMA
Keiji MOROKUMA
Senior Research Fellow, Kenichi Fukui Memorial Research Group 1
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. Of the FIFC teammembers who have contributed to the development of our program, five postdoctoral fellows (Fukui, JSPS and
CREST) from abroad left our group in FY 2013, and all of them found excellent faculty positions in theirrespective native countries. We have welcomed to our group one JSPS foreign postdoctoral fellow (from France)
and three postdoctoral fellows (from China, Sri Lanka and Japan) supported mainly by Kakenhi (grants from the
Minister of Education, Culture, Sports, Science and Technology) as well as one visiting research fellow (PhD
student from Thailand). We continued to have a strong team of theoretical/computational chemists at FIFC and at
Emory University working together toward a common goal. Since detailed description on individual projects at
FIFC can be found in the reports of postdoctoral fellows, here the areas of studies and titles of individual projects
are summarized.

I. Theoretical Studies of Reactions of Complex and Biomolecular Systems
In this area, in recent years we have studied structures and reactions of organic and organocatalytic systems,
and inorganic and homogenous metal catalytic systems as well as biomolecular systems. Our emphasis has beenon 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) tofind reaction pathways.
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 of potential
energy surfaces of multiple states of complex molecular systems.
IA. Organic and Organocatalytic Reaction Systems
a. The mechanism of the Ugi reaction, a four-component organic reaction (See research activities of R.
Ramozzi)b. Theoretical study of the Biginelli reaction, a three-component organic reaction (See research activities ofM. Puripat)
c. Heavy-atom tunneling in cyclobutadiene (See research activities of L. W. Chung)d. Asymmetric phase-transfer catalysis with homo- and heterochiral quaternary ammonium salts (Seeresearch activities of G. P. Petrova)e. Mechanistic study on the metal-free C-H activation by using a hypervalent iodine(III) reagent (Seeresearch activities of J. Jiang)－163 －

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Ⅳ 研究業績 (2013)f. aromaticity of hexa-group 16 atom-substituted benzene dications (See research activities of M. Hatanaka.
Paper 1)
g. Multiple pathways for primary step of spiropyran photochromic reaction: a CASPT2//CASSCF study(see paper 18)
h. Multireference ab initio density matrix renormalization group (DMRG)-CASSCF and -CASPT2 study
on the photochromic ring-opening of spiropyran (see paper 11).
IB. Inorganic and Organometallic Reaction Systems
a. Theoretical study of aqueous Mukaiyama-Aldol reaction catalyzed by lanthanide complexes (See research
activities of M. Hatanaka, Papers 12 and 22)
b. Asymmetric Mukaiyama-Aldol reaction of silicon enolates with aldehydes catalyzed by chiral Fe(II)complex (See research activities of W. M. C. Sameera)c. QM/MM structural and spectroscopic analysis of the di-iron(II) and di-iron(III) ferroxidase site in M
ferritin (Paper 15)
d. sp3–sp2 vs sp3–sp3 C–C activation in Rh-catalyzed ring opening of benzocyclobutenol: A DFT study (Seeresearch activities of L. Ding. Paper 6)
e. Mechanistic origin of chemo- and regioselectivity of nickel-catalyzed [3+2+2] cyclization reaction (Seepaper 9)f. Hydroboration mechanism revisited: alkene addition partner depends on ligand and substrate (Seeresearch activities of T. Harris)g. The origin of enantioselectivity for intramolecular Friedel-Crafts reaction catalyzed by supramolecular
Cu / DNA catalyst complex (See research activities of G. P. Petrova)
h. Theoretical investigation on the Pd-catalyzed C(sp3)-H activation in the synthesis of unnatural aminoacids (See research activities of J. Jiang)
i. Density matrix renormalization group (DMRG) calculations of magnetic exchange coupling in dinuclear
transition metal complexes (See research activities of T. Harris. Paper 4)
j. Application of ab initio density matrix renormalization group (DMRG) on the simplest Fe(IV)-oxo
complex. (See research activities of L. W. Chung)k. Excited-state proton transfer controls irreversibility of photoisomerization in mononuclear
ruthenium(II) monoaquo complexes: a DFT study (See research activities of L. Ding. Paper 3).
IC. Biomolecular Reaction Systems
a. A theoretical study on the UVR8 photoreceptor (See research activities of L. W. Chung)II. Simulation of Nanomaterials
In the area of simulation of nanomaterials, we continued our research efforts on quantum chemical molecular
dynamics (QM/MD) computations of carbon nanostructure formation based on density functional tight binding(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 addressed 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. The research activity in this area is slightly slowed down, as we
feel that we have accomplished what we can hope for using the present methodology and techniques.
a. Quantum chemical simulations reveal acetylene-based growth mechanisms in the chemical vapor－ 64
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Ⅳ 研究業績 (2013)

deposition synthesis of carbon nanotubes (See paper 5)b. Temperature dependence of catalyst-free chirality-controlled single-walled carbon nanotube growthfrom organic templates (See paper 10)
c. Revealing the dual role of hydrogen for defect healing and growth inhibition in polycyclic aromatichydrocarbon formation with QM/MD simulations (see paper 19)
d. Nucleation of graphene precursors on transition metal surfaces: insights from theoretical simulations(See paper 21)
e. Step-edge self-assembly during graphene nucleation on a Ni surface: QM/MD simulations (See paper 7)
f. Graphene nucleation on a surface-molten copper catalyst (See research activities of H.-B. Li)

III. Method Developments and Applications
In collaboration with Profs. Koichi Ohno and Satoshi Maeda, combining the two methods of potential energy
search, 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. Thesemethods allow determination of all the reaction pathways, including intermediates and transition states as well as
minimum 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 such as transition metal catalysts
and metal-free organocatalysts, for which the research area I above should also be referred to. The GRRM
strategy has been particularly powerful in finding reaction pathways of photo-activated molecules, in which
multiple pathways involving various electronically excited states and crossings between them can efficeintly belocated using the GRRM strategy.
IiIA. Development of the GRRM Strategy
a. Exploring pathways of photoaddition reactions by artificial force induced reaction (AFIR) method: A
case study on the Paternò-Büchi reaction (See paper 17)
b. Exploring transition state structures for intramolecular pathways by the artificial force induced reaction(AFIR) method (See paper 8)
c. Automated search for minimum energy conical intersection geometries between the lowest two singlet
states S0/S1-MECIs by the spin-flip TDDFT method (See paper 14)
IIB. Applications of the GRRM Strategy
a. Theoretical study on the photodissociation of methylamine involving S1, T1, and S0 states (See paper 20)
b. A CASPT2 study of photodissociation pathways of ketene (See paper 16)
c. Theoretical studies of photodissociation of nitromethane (See research activities of M. Isegawa)d. CASPT2 study of reaction paths starting from N(2D) + H2NO (See research activities of M. Isegawa)e. Mechanism of CnH� (n = 2, 4, 6) generation in the interstellar media (See research activities of M.
Hatanaka)f. Predicting pathways for terpene formation from first principles – routes to known and newsesquiterpenes (See research activities of M. Isegawa. Paper 2)
g. Development of a new class of azo-based fluorescence probes to detect different levels of hypoxia (Seepaper 13)h. Computational studies of fluorescent probes, Tokyo Green and Tokyo Magenta (See research activities ofW. M. C. Sameera)－365 －

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i. Ring opening-closing mechanism of diarylethene induced by UV-visible photon: potential energy surface
mapping by spin-flip time dependent DFT (See research activities of M. Isegawa)
IIIC. Othersa. Development of Gau_mopac2012 algorithm (See research activities of W. M. C. Sameera)

Original papers
1. M. Hatanaka, M. Saito, M. Fujita and K. Morokuma, �-Aromaticity in Hexa-Group 16 Atom-Substituted Benzenes
Dications. A Theoretical Study. J. Org. Chem. 79, 2640–2646 (2014).
2. M. Isegawa, S. Maeda, D. J. Tantillo and K. Morokuma, Predicting Pathways for Terpene Formation from First
Principles – Routes to Known and New Sesquiterpenes, Chem. Sci. 5, 1555-1560 (2014).
3. L. Ding, L. W. Chung, and K. Morokuma, Excited-State Proton Transfer Controls Irreversibility of
Photoisomerization in Mononuclear Ruthenium(II) Monoaquo Complexes: A DFT Study. J. Chem. Theory Comput.
10, 668–675 (2014).
4. T. V. Harris, Y. Kurashige, T. Yanai, and K. Morokuma, Ab Initio Density Matrix Renormalization Group Study ofMagnetic Coupling in Dinuclear Iron and Chromium Complexes, J. Chem. Phys. 140, 054303/1-10 (2014).
5. Y. Wang, X. Gao, H.-J. Qian, Y. Ohta, X. Wu, G. Eres, K. Morokuma, and S. Irle , Quantum Chemical Simulations
Reveal Acetylene-Based Growth Mechanisms in the Chemical Vapor Deposition Synthesis of Carbon Nanotubes.
Carbon 72, 22-37 (2014).
6. L. Ding, N. Ishida, M. Murakami, and K. Morokuma, sp3–sp2 vs sp3–sp3 C-C Site-Selectivity in Rh-Catalyzed Ring
Opening of Benzocyclobutenol: A DFT Study, J. Am. Chem. Soc. J. Am. Chem. Soc. 136, 169–178 (2014).
7. Y. Wang, A. J. Page, H.-B. Li, H.-J. Qian, M.-G, Jiao, Z.-J. Wu, K. Morokuma, and S. Irle, Step-Edge
Self-Assembly During Graphene Nucleation on a Ni Surface: QM/MD Simulations, Nanoscale 6, 140-144 (2014).
8. S. Maeda, T. Taketsugu, and K. Morokuma, Exploring Transition State Structures for Intramolecular Pathways by the
Artificial Force Induced Reaction (AFIR) Method. J. Comput. Chem. 35, 166-173 (2014).
9. S. Komagawa, C. Wang, K. Morokuma, S. Saito and M. Uchiyama, Mechanistic Origin of Chemo- andRegioselectivity of Nickel-Catalyzed [3+2+2] Cyclization Reaction. J. Am. Chem. Soc. 135, 14508–14511 (2013).
10. 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, J. Phys. Chem. Lett. 4. 3176-3180 (2013).
11. F. Liu, Y, Kurashige, T. Yanai, and K. Morokuma, Multireference Ab Initio Density Matrix Renormalization Group(DMRG)-CASSCF and -CASPT2 Study on the Photochromic Ring-Opening of Spiropyran, J. Chem. Theory
Comput. 9, 4462–4469 (2013).
12. M. Hatanaka and K. Morokuma, Theoretical Study of Mukaiyama-Aldol Reaction Catalyzed by Water-Tolerant
Lanthanide Lewis Acid, J. Am. Chem. Soc. 135, 13972–13979 (2013).
13. W. Piao, S. Tsuda, Y. Tanaka, S. Maeda, F. Liu, S. Takahashi, Y. Kushida, T. Komatsu, T. Ueno, T. Terai, T.
Nakazawa, M. Uchiyama, K. Morokuma, T. Nagano, and K. Hanaoka, Development of a New Class of Azo-based
Fluorescence Probes to Detect Different Levels of Hypoxia. Angew. Chem. Int. Ed. 52, 13028-13032 (2013).
14. Y. Harabuchi, S. Maeda, T. Taketsugu, N. Minezawa, and K. Morokuma, Automated search for minimum energy
conical intersection geometries between the lowest two singlet states S0/S1-MECIs by the spin-flip TDDFT method.
J. Chem. Theory Comput. 9, 4116–4123 (2013).
15 T. V. Harris and K. Morokuma, QM/MM Structural and Spectroscopic Analysis of the Di-iron(II) and Di-iron(III)
Ferroxidase Site in M Ferritin, Inorg. Chem. 52, 8551-8563 (2013).
16. H. Xiao, S. Maeda and K. Morokuma, A CASPT2 Study of Photodissociation Pathways of Ketene. J. Phys. Chem.
A, 117, 7001–7008 (2013).
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Ⅳ 研究業績 (2013)17. S. Maeda, T. Taketsugu, and K. Morokuma, Exploring Pathways of Photoaddition Reactions by Artificial Force
Induced Reaction Method: A Case Study on the Paternò-Büchi Reaction. Zeit. Phys. Chem. 227, 1421-1433 (2013).
18. F. Liu and K. Morokuma, Multiple Pathways for Primary Step of Spiropyran Photochromic Reaction: a
CASPT2//CASSCF Study, J. Am. Chem. Soc. 135, 10693–10702 (2013).
19. H.-B. Li, A. J. Page, S. Irle, and K. Morokuma, Revealing the Dual Role of Hydrogen for Defect Healing and
Growth Inhibition In Polycyclic Aromatic Hydrocarbon Formation with QM/MD Simulations, J. Phys. Chem. Lett.,
4, 2323–2327 (2013).
20. H. Xiao, S. Maeda and K. Morokuma, Theoretical Study on the Photodissociation of Methylamine Involving S1, T1,
and S0 States, J. Phys. Chem. A 117, 5757–5764 (2013).
21. A. J. Page, Y. Wang, H.-.B Li, K. Morokuma, and S. Irle, Nucleation of Graphene Precursors on Transition Metal
Surfaces: Insights from Theoretical Simulations. J. Phys. Chem. C, 117, 14858–14864 (2013).
22. 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.
9, 2882–2886 (2013).

4. Presentation at academic conferences and universities
1. Keiji Morokuma, Exploring potential energy surfaces with GRRM automatic search strategy, International
Symposium on Organic Reaction Mechanism, Shenzhen, China, May 8-9, 2013.
2. Keiji Morokuma, Development of Advanced Approaches to Potential Energy Landscaping for Fuel Cracking andOxidation, US AFOSR symposium on combustion, Arlington, VA, USA, June 3-6, 2013.
3. Keiji Morokuma, Exciting World of Theoretical Studies of Chemical Reactions -- From Gas Phase Reactions to
Catalysts, and Enzymatic Reactions, Asian Pacific Conference of Theoretical and Computational Chemistry(APCTCC6), Gyeonju, Korea, July 10-13, 2013.
4. Keiji Morokuma, Theory Can Provide Insights Unavailable from Experiments in Catalysis, A, The SixteenthInternational Symposium on Relations between Homogeneous and Heterogeneous Catalysis, Sapporo, Japan,
August 4-9, 2013.
5. Keiji Morokuma, Theory Provides Insights Unavailable from Experiments in Chemical Reactions, The CRC
symposium of post ISHHC-16 “Advanced Synthesis and Characterization Techniques for the Atomic-level
Understanding and Control of Chemical Reactions” and The 4th CSE Summer School. Jozankei, Sapporo, Japan,
August 10-11, 2013.
6. Keiji Morokuma, Theory Provides Insights Unavailable from Experiments in Chemical Reactions, Department ofChemistry, California Institute of Technology, Pasadena, CA, USA, August 26, 2013.
7. Keiji Morokuma, Automatic exploration of potential energy surfaces for catalysis and other complex chemical
reactions, DOE Symposium on New Theoretical Concepts and Directions in Catalysis, Santa Barbara, CA, USA,
August 27-30, 2013.
8. Keiji Morokuma, Automatic exploration of reaction pathways in complex environments, CAMM Forum, Tokyo,
October 3, 2013.
9. Keiji Morokuma, Exciting World of Theoretical/Computational Studies of Chemical Reactions of Complex
Chemical Systems, CMSI International Symposium “Extending the power of computational materials sciences with
K-computer”, Tokyo, October 21-22, 2013.
10. Keiji Morokuma, Automatic exploration of reaction pathways in complex environments, Symposium on"Electronic Structure in Complex Environments”, Southeast Regional Meeting of the American Chemical Society,
Atlanta, GA, USA, November 13-14, 2013.
11. Keiji Morokuma, Complex Chemical Reaction Pathways Explored by Automatic Search Strategy, 5th－567 －

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Japan-Czech-Slovakia International Symposium on Theoretical Chemistry, Nara, , December 2-6, 2013.
12. Keiji Morokuma, Chemical Theory of Complex Molecular Systems: Discovery and Insights from Computational
Studies of Chemical Reactions, CRC�EC Joint International Symposium on Chemical Theory for Complex
Systems, Atlanta, GA, USA, January 9-10, 2014.

5. Public talks
1. Let’s Explore the World of Chemical Reactions Using Computer (in Japanese), Career Orientation Forum, NanyoHigh School, Kyoto, November 7, 2013.
2. The Root of My Science (Chemistry): Izumisano, Presentation Ceremony of Honorary Citizenship, City of
Izumisano, Osaka, March 19, 2014.

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３．リサーチリーダー

Shigeyoshi SAKAKI
Shigeyoshi Sakaki

Research Leader, Kenichi Fukui Memorial Research Groups II
Research Leader, Kenichi Fukui Memorial Research Groups II

1. Summary of the research of 2013
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. This is because those molecules play important roles as metal enzymes, molecular catalysts, andmolecular devices such as photo-sensitizer, molecular switch, luminescence material etc. Also, they exhibit
a variety of geometry, molecular property, and bonding nature, which attract a lot of interest in theoreticaland computational chemistry. All these features deeply relate to their electronic structures. In this regard,
the theoretical knowledge of the electronic structure of the complex system including transition metalelement is indispensable in wide areas of chemistry.
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 targets even nowadays. Also, the post Hartree-Fock calculations of very big systems
like metal-organic-framework and molecular crystal are challenging. Our group is theoreticallyinvestigating those complex systems bearing complicated electronic structure.
This year, we theoretically investigated (i) gas absorption into the Hofmann-type metal-organic-framework(MOF), (ii) RASPT2 study of unusual Ni(I) and Co(I) dioxygen complexes, (iii) luminescentvapochromic compounds including an AuCu2(NHC)2 core, (iv) interest in new heterodinuclear
transition-metal/main-group-metal complexes: electronic structure and mechanism of fluoride sensing
function, and (v) 3D-RISM-SCF method with dual solvent boxes for a highly polarized system: application
to 1,6-anhydrosugar formation reaction of phenyl - and -D-glucosides under basic conditions, (vi)
Theoretical Study of Reactivity of Ge(II)-hydride Compound:Comparison with Rh(I)-Hydride Complex andPrediction of Full Catalytic Cycle by Ge(II)-hydride, (vii) Novel Ni(0)-Catalyzed [6 − 2 + 2] Cycloaddition
Reactions of Isatoic Anhydrides with Alkynes: Origin of Facile Decarboxylation and (viii) The crucial roleof a Ni(I) intermediate in Ni-catalyzed carboxylation of aryl chloride with CO2.
. We wish to report summary of them.
(i) Gas Absorption into the Hofmann-type Metal-Organic-Framework (MOF)
Porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) recently attract a lot of
attentions because of their potential application to gas storage,1,2 gas separation,2,3 catalysis,4 and nanospaceengineering.5 The flexibility in the use of a variety of organic linkers and/or metals leads to syntheses ofmany kinds of PCP with required properties. Among the desired properties, selective uptake6 and storage1,2
of gas molecule have been investigated well. However, theoretical understanding of the gas absorption andgas storage has been reported well. One reason is that the dispersion interaction plays important role in gas
absorption and gas storage but the evaluation of dispersion interaction in big system is not easy evennowadays. In this regard, we have started theoretical study of gas absorption and gas storage into MOF,
recently.
This year, absorption of CO2 and CS2 molecules into the Hofmann-type three-dimensional porous
coordination polymer (PCP) {Fe(Pz)[Pt(CN)4]}n (Pz = pyrazine) was theoretically explored with the ONIOM(MP2.5 or SCS-MP2:DFT) method, where the M06-2X functional was employed in the DFT calculation.
The binding energies of CS2 and CO2 are evaluated to be -17.3 kcal mol-1 and -5.2 kcal mol-1, respectively at－ 69 －

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the ONIOM(MP2.5:M06-2X) level and-16.9 kcal mol-1 and -4.4 kcal mol-1 at the
ONIOM(SCS-MP2:M06-2X) level. It is
concluded that CS2 is strongly absorbed inthis PCP but CO2 is weakly. The absorption
position is completely different between
these two molecules; CO2 exists between
two Pt atoms. To the contrary, one S atomof CS2 exists between two Pz ligands andthe other S atom is between two Pt atoms,
Figure 1. Absorption positions of CO2 and CS2 in theas shown in Figure 1. The optimized
Hofmann-type MOF
position of CS2 agrees with experimentally
reported X-ray structure. To elucidate thereasons of these differences, we performed the energy decomposition analysis and found that (i) both of thelarge binding energy and the absorption position of CS2 arise from a large dispersion interaction between CS2
and the PCP, (ii) the absorption position of CO2 is mainly determined by the electrostatic interaction between
CO2 and the Pt moiety, and (iii) the small binding energy of CO2 comes from the weak dispersion interaction
between CO2 and the PCP. Important molecular properties relating to the dispersion and electrostaticinteractions are discussed in detail, which are useful for understanding and predicting gas absorption into
PCP.
(ii) 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
Theoretical Study of Mononuclear Nickel(I), Nickel(0), Copper(I), and Cobalt(I) Dioxygen Complexes:
New Insight into Differences andActivation of dioxygen by such first row transition metals as Mn, Fe, Co, Ni, and Cu plays crucial
roles in biological oxidation. For instance, the importance of copper dioxygen complex is well recognized inbioinorganic chemistry. In this regard, a lot of efforts have been made to characterize the geometry, theelectronic structure, the physicochemical property, and the nature of metal-dioxygen interaction of those
dioxygen complexes. However, the nickel-dioxygen interaction and the role of the nickel center in therelevant dioxygen complexes have been much less investigated than those of copper-dioxygen complexes
despite the importance of the nickel-dioxygen species in superoxide dismutase. It is of considerable
importance to know how much and why the electronic structure and bonding interaction of the nickel
dioxygen complex are different from and/or similar to those of the copper dioxygen complex. Suchknowledge is indispensable for understanding the various metal dioxygen complexes in biological systems.
Geometries,
bonding
nature,andelectronic structures of (N^N)Ni(O2) (N^N =β-diketiminate), its cobalt(I) and copper(I)analogues, and (Ph3P)2Ni(O2) were investigatedby DFT and MS-RASPT2 methods. Only
(N^N)Ni(O2) takes a CS symmetrical structure
due to the pseudo-Jahn-Teller effect, while all Scheme 1. Ni(I), Co(I), and Cu(I) dioxygen
complexes investigated here.
other complexes take a C2V structure. The
symmetry lowering in (N^N)Ni(O2) is induced－ 70 －

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Ⅳ 研究業績 (2013)by the presence of the singly occupied
orbital. In all these complexes, significant superoxo (O2)character is found from the occupation numbers of natural orbitals and the O-O
bond order, which is
independent on the number of d electrons and the oxidation state of metal center. However, this is not atypical superoxo species because spin density is not found on the O2 moiety even in open-shell complexes,(N^N)Ni(O2) and (N^N)Co(O2). The M-O and O-O distances are considerably different from each other inspite of the similar superoxo character. The M-O distance and the interaction energy between the metal andorbital energy of the metal moiety taking the valence state. The
O2 moieties are determined by thebinding energy of the O2 moiety is understood in terms of theorbital energy in the valence state and thepromotion energy of the metal moiety from the ground state to the valence state. Because of theorbitalparticipations of various charge transfer (CT) interactions between the metal and O2 moieties, theenergy and the electron population of the O2 moiety both do not clearly relate to the O-O bond length. Here,the π bond order of the O2 moiety is proposed as a good measure for discussing the O-O bond length.
Because the d electron configuration is different among these complexes, the CT interactions are different,
leading to the differences in the  bond order and hence the O-O distance among these complexes. The
reactivity of dioxygen complex is discussed with theorbital energy.
(iii) A Theoretical Study of Luminescent Vapochromic Compounds Including an AuCu2(NHC)2 Core
Vapochromic complexes [Au(im(CH2py)2)2(Cu(MeCN)2)2]3+ 1, [Au(im(CH2py)2)2(Cu(MeOH))2]3+ 2
and [Au(im(CH2py)2)2(Cu(H2O))2]3+ 3 were theoretically investigated with DFT and MP2 methods. The
Au–Cu distances of 1 and 2 (4.631 Å and 2.767 Å, respectively) optimized by the SCS-MP2 method in thiswork agree with the literature experimental values (4.591 Å and 2.792 Å). Their structural features are
explained by computational
results: (i) in 1, two MeCN
molecules coordinate with
the Cu center, because of
the strong coordination
ability of MeCN, to afford afour-coordinate
Scheme 2. Vapochromic complexes including AuCu2 coretetrahedral-like Cu center.
This geometry needs a long Au–Cu distance. (ii) In 2 and 3, only one MeOH or H2O molecule coordinateswith the Cu center because of their weak coordination abilities, to afford a three-coordinate planar Cu center.
Because the threecoordinate Cu center is flexible, the Au–Cu distance becomes short due to the Au–Cu
metallophilic interaction, the strength of which is 5.3 kcal mol−1 at the SCS-MP2 level. The emission
energies of 1, 2 and 3 (2.62, 2.40 and 2.38 eV, respectively) calculated here by the B3PW91 agree with theirliterature experimental values (2.68, 2.47, and 2.39 eV). The lowest energy triplet excited state (T1) is
assigned as the excitation from the Cu d to the pyridine π* orbital in 1 and that from the Au–Cu 5d–3d
anti-bonding MO to the Au–Cu 6p–4sp bonding MO in 2 and 3. As a result, the emission energy from the T1
to the ground state is different between these compounds. The difference in Au–Cu distance is one of theimportant factors for the differences in emission energy and assignment between 1 and others (2 and 3). The
vapochromism of these compounds arises from the difference in Au–Cu distance which is determined by thebalance between the strengths of the coordination of a gas molecule and the Au–Cu metallophilic interaction;in other words, the Au–Cu heterometallophilic interaction is important for the vapochromic activity of thecomplex.
(iv) Interest in New Heterodinuclear Transition-metal/main-group-metal Complexes: Electronic－ 71 －

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Structure and Mechanism of Fluoride Sensing Function
Systematic DFT calculations were carried out
on a series of heterodinuclear complexes[(o-(Ph2P)C6H4)3M1M2Cl]+ (M1 = As, Sb, or Bi; M2= Pd or Pt) to investigate the mechanism ofcolorimetric sensing function for the fluoride anion.
The fluoride anion binds with the M1 center toafford a hypervalent M1 species with large
stabilization energy. For instance, the stabilizationenergy by the fluoride adduct formation is −15.5
kcal mol−1 for 3 (M1 = Sb; M2 = Pd) and −16.2
kcal mol−1 for 6 (M1 = Sb; M2 = Pt), where anegative value represents stabilization. Interestingly, Scheme 3. Transition metal/heavy main groupthe allosteric coordination of the third phosphine element hybrid complexes.
with the M2 center is induced by the fluoride adduct formation. For chloride, bromide, and thiocyanide
anions, the binding energies are positive (4.5 kcal mol−1), and the allosteric coordination does not occur.
The allosteric coordination plays a crucial role in the absorption spectrum change induced by the fluoride
adduct formation. For instance, the fluoride adduct formation quenches the absorption band of 3 around 400
nm and newly exhibits two absorption peaks at longer wavelength, 475 and 451 nm. These two peaks are
assigned to ligand-field transitions (dxy → dz2 and dx2−y2 → dz2) including metal-toligand charge transfer
character. We discussed the reasons why the allosteric coordination can occur only in the fluoride adduct andinduces these two absorptions in the longer wavelength region. In addition, the Bi–Pd combination is also
recommended for a fluoride sensing material, while the Sb–Pt combination is recommended for cyanide
sensing.
(v) A 3D-RISM-SCF method with dual solvent boxes for a highly polarized system: application to
1,6-anhydrosugar formation reaction of phenyl - and -D-glucosides under basic conditions
One of the difficulties in application of the usual reference interaction site model
self-consistent field (RISM-SCF) method to a highly polarized and bulky system arises from theapproximate evaluation of electrostatic potential (ESP) with pure point charges. To improve thisESP evaluation, the ESP near a solute is directly calculated with a solute electronic wavefunction,that distant from a solute is approximately calculated with solute point charges, and they areconnected with a switching function. To evaluate
the fine solvation structure near the solute byincorporatingthelong-range

solute–solvent

Coulombic interaction with low computational cost,
we introduced the dual solvent box protocol; one
small box with the fine spacing is employed for the
first and the second solvation shells and the otherlarge box with the normal spacing is employed forlong-range

solute–solvent

interaction.

The

levoglucosan

formationphenyl

and

from

a-

Scheme 4. Stereoelectronic effect in transition
states in the rate-determining step oflevoglucosan formation reaction

b-D-glucosides under basic conditions is successfully inspected by this 3D-RISM-SCF method at theMP2 and SCS-MP2 levels, though the 1D-RISM-SCF could not be applied to this reaction due to thepresence of highly polarized and bulky species. This 3D-RISMSCF calculation reproduces the－ 72 －

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experimentally reported higher reactivity of the b-anomer. The 3D-RISMSCF-calculated activation
free energy for the b-anomer is closer to the experimental value than the PCM-calculated one.
Interestingly, the solvation effect increases the difference in reactivity between these two anomers.
The reason is successfully elucidated with 3D-RISM-SCF-calculated microscopic solvation structureand decomposition analysis of solute–solvent interaction.

(vi) Theoretical Study of Reactivity of Ge(II)-hydride Compound:Comparison with Rh(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 density functional theory andspin-component-scaled secondorder Møller−Plesset methods. This reaction easily occurs with moderate
activation barrier and considerably large exothermicity, to afford a Ge(II) alkoxide 2 through afour-membered transition state. In the transition
state, the charge transfer from the Ge−H
σ-bonding molecular orbital (MO) to the C=O
π*-antibonding MO of CF3PhCO plays animportant role. Acetone ((CH3)2CO) andbenzophenone (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 catalytic hydrogenation of CF3PhCO
by 1 is difficult because the reaction of 2 with a Scheme 6. Theoretically proposed catalytic cycles
dihydrogen molecule needs a large activation by Ge-H compoundenergy. On the other hand, our calculations
clearly show that the catalytic hydrogenation of ketone by cis-RhH(PPh3)2 4 easily occurs, as expected. The
comparison of catalytic cycle between 1 and 4 suggests that the strong Ge−O bond of 2 is the reason of thevery large activation energy for the hydrogenation by 1. To overcome this defect, we investigated various
reagents and found that the catalytic cycle can be completed with the use of SiF3H. The product is silylether
CF3PhCHOSiF3, which is equivalent to alcohol because it easily undergoes hydrolysis to afford F3PhCHOH.
The similar catalytic cycles are also theoretically predicted for hydrosilylations of CO2 and imine. This is thefirst theoretical prediction of the full catalytic cycle with a heavier main-group element compound.
(vii) Novel Ni(0)-Catalyzed [6 − 2 + 2] Cycloaddition Reactions of Isatoic Anhydrides with Alkynes:
Origin of Facile Decarboxylation
A thorough theoreticalanalysis was carried out on
the
novel
Ni-catalyzed
decarboxylative [6 − 2 + 2]
cycloaddition reactions ofisatoic
anhydrides
withalkynes. This is the first
theoretical analysis of thisnew kind of decarboxylative
coupling reaction, which has
attracted recent attention. The
Figure 2. Gibbs energy changes in the [6-2+2] cycloaddition
reaction－ 73 －

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Ⅳ 研究業績 (2013)active species is a two-coordinate Ni0(phosphine)(alkyne) complex. The catalytic cycle consists of the four
elementary processes: oxidative addition, decarboxylation, alkyne insertion, and reductive elimination. The
oxidative addition of the C(=O)−O bond of isatoic anhydride to Ni(phosphine)(alkyne) proceeds with amoderate Gibbs activation energy (ΔG°‡) of 18.0 kcal/mol. In the transition state, the charge transfer fromthe Ni 3dπ orbital to the antibonding LUMO of isatoic anhydride plays an important role in the weakening of
the anhydride C(=O)−O bond, which determines the regioselectivity of the oxidative addition. Then, thedecarboxylation proceeds in a stepwise manner through Ni−N bond formation and CO2 elimination. In thisdecarboxylation, the Ni−N bond formation is crucial for a moderate ΔG°‡ value of 6.7 kcal/mol. After thisstep, alkyne and phosphine change their positions around the Ni center, followed by alkyne insertion into thenickel−acyl (Ni−C(=O)R) bond and reductive elimination. All of these steps occur easily with moderate
ΔG°‡ values. The facile decarboxylation is the origin of this successful catalytic reaction. This is because theN atom in isatoic anhydride plays an important role by coordinating with the Ni center to accelerate thedecarboxylation. The electronic processes of decarboxylation as well as other important elementary steps are
discussed in detail.
(viii) The crucial role of a Ni(I) intermediate in Ni-catalyzed carboxylation of aryl chloride with CO2
Over the past few years, significantly large growth has been achieved in CO2 conversion to useful chemicals
with catalysts.1,2 Transition metal complexes are promising catalysts for the CO2 conversion. Actually,
many catalysts have been developed for the syntheses of avariety of useful chemicals. In particular, syntheses ofcarboxylic acids and their derivatives from CO2 are ofrecent interest because they are important starting materials
of organic syntheses. However, the successful results
have been very limited. Recently, Tsuji and coworkers
reported interesting synthesis of benzoic acid fromchlorobenzene with CO2 using Ni(0) complex as a catalyst.
In this catalytic system, the Mn metal powder was
employed. We theoretically investigated this catalytic
reaction to elucidate the reason why Mn metal powder is Scheme 7. Ni(0)-catalyzed carboxylationindispensable in this catalytic reaction. DFT calculations of phenyl chloride
show the important features of this reaction; the active
species is Ni(0) complex and the first step is the oxidative addition of Ph-Cl to the Ni(0) complex to afford aNi(II) phenyl chloride species. The next step is one-electron reduction of the Ni(II) phenyl species to aNi(I)-phenyl species with the Mn metal powder. This one-electron reduction is indispensable to perform theCO2 insertion into the Ni(I)-Ph bond. This is because the CO2 insertion into the Ni(II)-Ph bond is difficult
but easy into the Ni(I)-Ph bond. The final is one-electron reduction of the Ni(I)-h2-benzoate species. It isclearly shown that the one-electron reduction of the Ni(II)-phenyl complex is necessary to perform the next
CO2 insertion. The reason was clearly elucidated by considering the charge-transfer from the Ni(I)-Ph
moiety to CO2.
Original Papers(1) Toru Matsui, Yasutake Kitagawa, Mitsutaka Okumura, Yasuteru Shigeta, Shigeyoshi Sakaki,“Consistent scheme for computing standard hydrogen electrode and redox potentials”
J. Comp. Chem., 34, 21-26 (2013).
(2) Shinji Aono, Takashi Hosoya, and Shigeyoshi Sakaki" A 3D-RISM-SCF method with dual solvent boxes for a highly polarized system: application to－ 74 －

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1,6-anhydrosugar formation reaction of phenyl - and -D-glucosides under basic conditions”
Phys. CHem. Chem. Phys., 15, 6368-6381 (2013).
(3) Milind Madhusudan Deshmukh, Masaaki Ohba, Susumu Kitagawa, and Shigeyoshi Sakaki“Absorption of CO2 and CS2 into the Hofmann-Type Porous Coordination Polymer: Electrostatic
versus Dispersion Interactions”
J. Am. Chem. Soc., 135, 4840−4849 (2013).
(4) Guixiang Zeng and 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, 2844−2853 (2013)..
(5) Shinya Tsukamoto and Shigeyoshi Sakaki,“A theoretical study of luminescent vapochromic compounds including an AuCu2(NHC)2 core”
Dalton Trans., 42, 4809-4821 (2013).
(6) Terutaka Yoshizawa, Shigeyoshi 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. Compt. Chem., 34, 1013-1023 (2013).
(7) Wei Guan, Shinichi Yamabe and Shigeyoshi Sakaki,“Interests in new heterodinuclear transition-metal/main-group-metal complexes: DFT study ofelectronic structure and mechanism of fluoride sensing function”
Dalton Trans., 42, 8717 – 8728 (2013).
(8) Nozomi Takagi and Shigeyoshi Sakaki,,“Theoretical Study of Reactivity of Ge(II)-hydride Compound: Comparison with Rh(I)- Hydride
Complex and Prediction of Full Catalytic Cycle by Ge(II)-hydride”
J. Am. Chem. Soc., 135, 8955−8965 (2013).
(9) Wakioka, M.; Nakamura, Y.; Hihara, Y.; Ozawa, F.; Sakaki, S. ,“Factors Controlling the Reactivity of Heteroarenes in Direct Arylation with Arylpalladium Acetate
Complexes”
Organometallics, 32, 4423 4430 (2013).
(10) Guan, W.; Sakaki, S.; Kurahashi, T.; Matsubara, S.
“Theoretical Mechanistic Study of Novel Ni(0)-Catalyzed [6-2+2] Cycloaddition Reactions ofIsatoic Anhydrides with Alkynes: Origin of Facile Decarboxylation,”
Organometallics, 32, 7564-7574 (2013).
(11) Yue Chen and 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”
Inorg. Chem., 52, 13146−13159 (2013).
(12) Fareed Bhasha Sayyed,a Yasushi Tsujib and Shigeyoshi Sakaki“Crucial Role of Ni(I) Intermediate in Ni-Catalyzed Direct Carboxylation of Aryl Chloride with CO2:
A Theoretical Study”
Chem. Comm., 49, 10715 – 10717 (2013).
(13) Takashi Hosoya and Shigeyoshi Sakaki,“Levoglucosan Formation from Crystalline Cellulose: Importance of a Hydrogen Bonding Networkin the Reaction”
ChemSusChem, 6, 2356 – 2368 (2013). .
3. Presentation at academic conferences(1) Shigeyoshi Sakaki,“Theoretical Study of Complex Systems From Small Transition Metal Complex to Big Systems
such as Metal Organic Framework and Infinite Molecular Crystal”, 6th APCTCC Asian PacificCongress for Theoretical and Computational Chemsitry, Gyeongju, Korea, July 10-13. (keynote)(2) Shigeyoshi Sakaki“Gas Absorption and Spin Transition of the Hofmann-type Porous Coordination Polymer
Theoretical Study”, UK-Japan Workshop on Organic-Inorganic Framework Materials, Kyoto, Japan,
Oct. 10-11. (Invited)－ 75 －

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Ⅳ 研究業績 (2013)(3) Shigeyoshi Sakaki“Gas Absorption and Spin Transition of the Hofman-type Metal Organic Framework: Theoretical
Study”, The 5th Japan-Checz-Slovaria Joint-Symposium for Theoretical and Computational
Chemistry, Nara, Japan, Dec. 2-6. (Invited)
4. Others(1) 榊 茂好“遷移金属元素を含む複合系の理論的研究: 反応の電子的過程に注目して”
反応経路探索のニューフロンテイア2013、2013年9月 京都（京大 福井謙一記念研セ）(2) 榊 茂好“二核金属錯体の構造と電子状態：理論的研究”
第３回分子アーキテクトシンポジウム 2013 年 10 月 大阪(大阪市中央公会堂)(3) 榊 茂好“ｄ電子複合系の構造と機能の理論化学” 産総研ナノシステム連携促進フォーラム 2014
年 2 月 東京（秋葉原ダイビル）(4) 榊 茂好
“理論化学・計算化学と触媒・電池元素戦略研究” 触媒・電池元素戦略研究拠点 第 4
回公開シンポジウム 2014 年 3 月 東京（東大武田先端知ビル）(5) 榊 茂好“遷移金属複合系の構造と反応の理論および計算化学研究” 日本化学会第９４回春季年会
2014 年 2
3 月 名古屋（名古屋大学）－ 76 －

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Ⅳ 研究業績 (2013)

４．博士研究員

Takafumi IWAKI
Takafumi Iwaki
FIFC Fellow
FIFC Fellow

1. Summary of the research of the year

Study of DNA Double Strand Breaking Produced by Ionizing Radiations
DNA double-strand breaks (DSBs) represent a serious source of damage for all living things and thus
there have been many quantitative studies of DSBs both in vivo and in vitro. Despite this fact, the processes
that lead to their production have not yet been clearly understood, and there is no established theory that canaccount for the statistics of their production, in particular, the number of DSBs per base pair per unit Gy, here
denoted by P1, which is the most important parameter for evaluating the degree of risk posed by DSBs.
Using the single-molecule observation method with giant DNA molecules (166 kbp), we evaluate the number
of DSBs caused by -ray irradiation. We found that, in the dependence of P1 to the DNA concentration, there
are two characteristic regions. 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 acertain threshold DNA concentration. We calculate the probability to occur double strand breaking on thebasis of a simple model, which well accounts for the marked profile of P1 over all measured region. Basedon this argument, we show that it is necessary to consider the characteristics of giant DNA molecules assemiflexible polymers to interpret the intrinsic mechanism of DSBs. This work was published in The Journalof Chemical Physics.

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.

－ 77 －

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Here,

we

performedanumerical

simulation of thermal fluid on an irregularlattice with a finite volume method. Several
causes were assumed for the above-mentioned
effect of SDS. For example, the difference inthe shape of the droplet might have induced adifferent flow mode inside the droplet.
Nonlinear effect of the hydrodynamics might
have promoted the appearance of the different
modes in similar experimental systems. These
expectations were, however, denied by asequence of simulations. We found that the
migration direction changes due to thetemperature coefficients of surface tensionschanged by the presence/absence of SDS. The
Marangoni effect on an oil droplet on an
air-water interface caused by local heating
induces two types of actions on the droplet.
One is the viscous friction force from anexternal flow induced by caterpillar-likeaction of the droplet surface. This force
always accelerates the droplet to approach aheating spot. The other is the Young force

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

arising from 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 themagnitude relation of the temperature coefficients between air-water interface and oil surfaces reverses, theYoung force changes its direction.
Thus, we simulated a thermal flow for two typical sets of temperature coefficients of surface tensions.
Consequently, we obtained flow patterns and temperature distributions very similar to experimentallyobtained ones in the presence/absence of SDS, respectively, which rationalize that the above-mentioned
mechanism is applicable to the interpretation of the experimentally observed effect of SDS. This work was
published in Physical Review E.

Study of the Dynamical Mechanism of the Self-Organization of the Tooth Germ
In the development process of the tooth germ, the enamel knot is formed simultaneously with theepithelial invagination. The epithelial invagination is considered as the buckling of the growing surface layerof the tooth germ. However, the mechanism of the formation of the enamel knot is not understood well interms of both physics and molecular biology. In order to solve this problem from the perspective of physics,－ 78 －

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we performed Brownian dynamics simulations of a coarse-grained toy model of cell population. In thesimulations, we found that according to the proliferation rates of the surface layer and the interior of thedental epithelial, the buckling formation undergoes several courses. In particular, when the proliferation rateof the surface layer is considerably larger than that of the interior, the bending is not uniform, and the pluralbuds are formed similarly to the actual development process. This fact suggests that the formation of theenamel 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 elastic 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 a growth of plural peaks is more favored. This wellcorresponds to the simulation result and also the actual development process. We are now writing themanuscript of these results, which is submitted to a scientific journal.
Study of the radius of gyration for circular and linear DNA
The radius of gyration for polymer material is a historical problem. While the radius of gyration itself
is frequently measured, its distribution (standard deviation etc.) has been not argued in experimental study indetail. In this study, we measured a time series of major-axis length of BAC DNA for linear and circulararchitectures by means of fluorescent microscopy. In the result, we found that both DNA chains exhibit
considerably small standard deviations for major-axis length. The standard deviation for a circular chain isparticularly inhibited. Moreover, we found that the major-axis lengths for two types of molecules take very
similar values rather than the expected. We considered the radius of gyration of interacting semiflexible
polymer, and compared it with the present experimental result. Though the radius of gyration and the
major-axis length is not identical, additional simulations illustrate that this two variables are highly
correlated, and they can be equated with each other as a matter of fact. In this argument, we found that thetraditional equation of end-to-end distance of a segment in a circular chain leads to a result totally dislocatedfrom experimental observations. Thus we proposed a new equation on the basis of the mean-field theory, andcompared it with experiments. They well agree with each other except for the standard deviation for acircular chain. For the standard deviation for a circular chain, we may need to consider other factors such as
an effect of twisting and a transient topological constraint. This work is now being summarized as amanuscript, which is to be submitted to a scientific journal.

Study of two-dimensional convectional flows in two-phase mixtures
Recently, it was found that a stable interfacial wave appears when one pours ethanol on hot
water in a thin cuboid container. This phenomenon seems to derive from the coupled convectionalflows in upper and lower fluids which lead to an oscillatory hydrodynamic pressure on the interface.
To testify this explanation with a simple model, we devise and examine several toy models. While
this process is still developing, this concept should be more rationalized with the further
experimental tests. It is planned to advance a theoretical consideration to lead to some－ 79 －

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phenomenological prediction, which will be examined by an actual experimental test.
2. Original papers(1) Shunsuke F. Shimobayashi1, 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”, The Journal of Chemical Physics 138, 174907 (2013).
(2) Masatoshi Ichikawa, Fumi Takabatake, Keitaro Miura, Takafumi Iwaki, Nobuyuki
Magome, and Kenichi Yoshikawa, “Controlling negative and positive photothermal
migration of centimeter-sized droplets”, Phys. Rev. E 88, 012403 (2013).
3. Presentation at academic conferences(1) 岩城 貴史、“非等方粘性系を用いた上皮細胞増殖による形態形成のモデル”、 日本物理学会
2013 年秋季大会、Tokushima, Sep. 28, 2013

(2) 岩城 貴史、“ライデンフロスト効果とベナール対流の協奏： 水-エタノール系の自発的界面振動”、 日本物理学会第 67 回年次大会、Kanagawa, March 30, 2014
4. Others
We cooperated with an online encyclopedia project developed by Springer. We provided thefollowing article to the Encyclopedia of Polymeric Nanomaterials edited by S. Kobayashi and K.
Muellen: “DNA as Polymer and Polyelectrolyte” by Takafumi Iwaki and Kenichi Yoshikawa(containing about 3400 words and 2 figures).

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嶺澤
��

範行
��

センターフェロー�ン�ー���ー�� 今年度の研究の要�
今年度は昨年度に引き続き、溶液内における光化学反応を自由エネルギーの観点から解析した。

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溶液における光化学反応を理解するためには、電子励起状態の詳細な記述と溶媒効果の適切な評価を取り入れる必要がある。過去の研究において、時間依存密度汎関数法 (TDDFT) と積分方程式を組み合わせた手法を導入した[1]。TDDFT 法は、動的電子相関の取り扱いに優れ、計算コストも小さい。さらに、解析的なエネルギー微分も得られるため、励起状態のポテンシャル面の構築には適当な方法である。溶媒効果は、溶媒和構造を分子論的に記述できる積分方程式 (RISM) で取り入れ、
電子状態計算と組み合わせた (RISM-SCF)。この方法は、溶媒分子の配置空間について統計サンプ
リングを必要とせず、溶液における自由エネルギーを効率よく決定できる。今年度は、電子励起状
態の自由エネルギー面をこの手法で構築し、光化学反応への応用を目指した。

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まず、TDDFT 法と RISM-SCF 法を組み合わせた計算手法[1]の精度について検証した。電子励起状態の平衡溶媒和自由エネルギー面を構築するためには、励起状態の電子密度と溶媒和構造が平衡でなければならない。しかしながら、TDDFT 法は多配置関数の方法とは異なり容易ではない。これは、線形応答を仮定しているためである。すなわち、電子基底状態を参照系として、時間依存の摂動を加えた時の分子の密度変化に着目している。励起エネルギーは参照系の情報のみで記述することができ、励起状態の情報を一切必要としない。これは、長所であると同時に短所でもある。

実際、RISM-TDDFT 法における自由エネルギーはˆ]ˆ ]   V   Tr[( X + Y)Q
A0   0  Tr[( X + Y)Q Q 
ここで、 A0 は基底状態の自由エネルギー、 0 は溶媒を凍結した時の励起エネルギー、 X  Y はA

transition amplitude、Q̂ は電荷生成演算子である。第 3 項から明らかなように、溶媒の再配向エネル
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ギーの寄与は、遷移に伴う電荷の変化とそれに伴う静電ポテンシャル V の変化の積であらわされる。電子励起状態の電子密度はあらわに含まれないため、基底状態と励起状態で電子密度が大きく変化する場合、再配向の効果が適切に表現される保証はない。

今回、励起状態の電子密度を反映させるため、非平衡自由エネルギーの表式 (LRFE) [2,3]を
図 1: PBN の自由エネルギープロファイル

TDDFT 法と組み合わせた。LRFE-TDDFT 法における自由エネルギーはA

1
A0  0  Q  V
2

ここで、Q  Q ex  Q gs は、基底状態と励起状態の電荷の差をあらわに含んでおり、励起状態の電子密度が自由エネルギーに反映されている。

この 2 つの溶媒和モデルの比較を分子内電荷移
動反応 (ICT) の記述で検証した。ICT 反応では

図 2: PBN の分子軌道 (左) HOMO (右) LUMO

基底状態 (DA) と励起状態 (D+A−) で電荷分布が大きく異なるため、適当な計算例である。(N-pyrrolo)benzonitrile (PBN) のアセトニトリル溶液を分子系として選択した。図 1 から明らかなように、反応座標に対して、線形応答溶媒和モデル(RISM-TDDFT) と状態依存溶媒和モデル (LRFE-TDDFT) では、定性的に異なる描像を与えた。これは、生成物が twisted-ICT であり、HOMO-LUMO 励起における、分子軌道間の重なりが小さい (図ˆ  の寄与も非常に小さい。したがって線形応答溶媒和モデル2)。その結果として Tr ( X  Y)Q

(RISM-TDDFT) では、緩和による安定化を過小評価してしまう。このような場合、あらわに励起状態の電子密度の溶媒和への寄与を考慮した LRFE-TDDFT 法を適用しなければならない。本研究の結果は近日中に公開予定である[4]。

���� ���������������
昨年度、溶液における円錐交差を決定する方法を開発した。それは、2 つの非平衡自由エネルギー2－ 82 －

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Ⅳ 研究業績 (2013)

面を定義し、その交差を求めることである[2,3]。非平衡自由エネルギーは、核座標だけでなく溶媒和座標にも依存するため、両方の座標について構造最適化を行う。アルゴリズムは非断熱カップリングの計算を必要としない分岐面更新法[5]を採用している。

本研究では、緑色蛍光タンパク質 (GFP) の発色団である
p-hydroxybenzylideneimidazolinone (HBI) (図 3) の水溶液について考察した。発色団分子はタンパク質に囲まれた状
態では、非常に良い蛍光物質である。一方、この分子だ
けを水に溶解させた場合、蛍光の量子収率が著しく減少
し、蛍光が消失する。これは、タンパク質残基の阻害を

図 3: HBI の分子構造受けない自由な分子内振動により無輻射遷移が優位になることを示唆している。そこで、励起状態の自由エネルギー面の解析により、その HBI 分子の水溶液における光化学を明らかにすることを目標とする。

その第一歩として、spin-flip TDDFT 法[6]を用いて円錐交差の構造を孤立分子と水溶液で決定した (図 4)。エチレン分子で見られた傾向と同様に、C9 における面外角が減少した。これは、溶質‐溶媒間の相互作用により、分子内の構造変化をそれほど必要としないことと対応する。現在、電子励起状

図 4: HBI の円錐交差 (黒) 気相 (グレー) 水溶液

態の自由エネルギー面の構築を進めており、詳細は発表予定である[7]。

䛆ᩥ⊩䛇㻌

1.

N. Minezawa, J. Chem. Phys. 138, 244101 (2013).

2.

S. Yamazaki and S. Kato, J. Chem. Phys. 123, 114510 (2005).

3.

T. Mori, K. Nakano, and S. Kato, J. Chem. Phys. 133, 064107 (2010).

4.

N. Minezawa, “State-specific solvation effect on the intramolecular charge transfer reaction in solution:
A linear-response free energy TDDFT method”, Chem. Phys. Lett., in press.

5.

S. Maeda, K. Ohno, and K. Morokuma, J. Chem. Theory Comput. 6, 1538 (2010).

6.

Y. Shao, M. Head-Gordon, and A. I. Krylov, J. Chem. Phys. 118, 4807 (2003).

7.

N. Minezawa, “Photoisomerization of green fluorescence protein chromophore in aqueous solution:3－ 83 －

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Linear-response free energy/spin-flip time-dependent density functional theory approach”, inpreparation.

�� 論�(1) 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. 138, article No. 244101 [8 pages] (2013).
(2) Y. Harabuchi, S. Maeda, T. Taketsugu, N. Minezawa, and K. Morokuma, “Automatedsearch for minimum energy conical intersection geometries between the lowest two singlet
states S0/S1-MECIs by the spin-flip TDDFT method”, J. Chem. Theory Comput. 9,4116-4123 (2013).
(3) N. De Silva, N. Minezawa, and M. S. Gordon, “Excited-state hydrogen atom transfer
reaction in solvated 7-hydroxy-4-methylcoumarin”, J. Phys. Chem. B 117, 15386-15394(2013).

�� 学会��

(1) 嶺澤 範行「SF-TDDFT法による溶液内分子の最小自由エネルギー交差点の探索」
第7回分子化学討論会

京都 09/25/2013 2P116

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RyuichiRyuichiOKAMOTO
OkamotoProjectAssistant
AssistantProfessor,
Professor,Tokyo
TokyoMetropolitan
Metropolitan University,
Project
University,TokyoTokyo
1. Summary of the research of the year (3-5 pages, includes appropriate figures and tables)
Attractive interaction and bridging transition between neutral colloidal particles due topreferential adsorption in a near-critical binary mixture
We study solvent mediated interaction between uncharged colloidal particles in a near-criticalbinary fluid mixture. The surface of the particles preferentially attracts one of the fluid
components, which results in composition gradient (adsorption layer) near the surface. The
overlap of the composition gradient around each particle induces attractive force between theparticles. Particularly, near the critical point of the mixture, the composition gradient becomes
long-ranged and exhibits universal behavior in the sense that it does not depend on the
microscopic details of the surface and the solvent molecules. Correspondingly, the solvent
mediated interaction becomes universal, strong and long-ranged near the critical point.
In order to investigate the universal, strong and long-ranged interaction, we take into account therenormalization effect due to the critical fluctuations using our local functional theory [Okamoto
and Onuki, J. Chem. Phys. 136, 114704 (2012)]. We find the interaction become strong when the
mixture is poor in the component preferred by the surface. Especially, in one phase state near thecoexistence curve below the critical temperature Tc, the adsorption layer bridges the particles
when the separation distance is smaller than a threshold value (Fig. 1). In the bridged state, theadsorption layer induces strong attractive force between the particles.

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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 due 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 adsorption 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.

2. Original papers(1) Ryuichi Okamoto and Akira Onuki“Attractive interaction and bridging transition between between neutral colloidal particles
due to preferential adsorption in a near-critical binary mixture”, Phys. Rev. E 88, 022309(2013)(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. 82, 084003 (2013)－ 86 －

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3. Presentation at academic conferences(1) Ryuichi Okamoto and Akira Onuki”Wetting on ionizable surfaces: Statics and dynamics”(powter)
International soft matter conference 2013, Rome, Italy, September 15-19, 2013
(2) Ryuichi Okamoto and Akira Onuki“Wetting on an ionizable surface: Statics and dynamics” (oral)
Physical society of Japan autumn meeting 2013, Tokushima, September 25-28, 2013－ 87 －

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TakuyaTakuyaSAITO
Saito
FIFC Fellow
1. Summary of the research of the year
Fluctuation in polymer stretching
Pulling of a polymeric chain is a basic operation tofinvestigate a physical characteristics. A linear
polymericchain is largely

stretched to an

inhomogeneous shape by pulling the one end. Thexdeformed shape is described by the relation of thex(t)tension with thermal agitation. The fluctuation ofeach monomer should have the information about

Fig.

the interaction among monomers such as the1

Schematic

representation

of

the

polymer stretching under steady state.

excluded volume effect as well as the string-likechain connectivity, but the better description of the

dynamical fluctuation on the large deformation still remains elusive.
We proposed the theoretical approach of the fluctuation in the polymer stretching. The stochastic dynamics
is described by the pre-averaged non-linear Langevin equation, in which the transversal monomer fluctuation
is casted on the pulling direction.
We furthermore apply the homogeneous approximation by the head spatial fluctuation. The Langevin eq.
then becomes linear so that it enables us to analytically handle the fluctuation on the stretching. On the basisof the approximated Langevin equation, we theoretically obtained the variance of the head monomer
position as well as the average under stretching steady state. We found two regimes; (i) the
relaxation of internal configuration; (ii) the translational diffusion. The former shows theanomalous (sub-) diffusion, while the latter is the normal diffusion.
To verify the theory, we carried out the molecular dynamics (MD) simulation. In the steady state,
the predicted scaling laws are in agreement with the MD results.

Effects of cis-/trans-sides in the driven polymer translocation
Polymer translocation is a polymer passage through the small pore and has been intensively
investigated for various purposes. Especially, in experiment, the electric potential difference across the porehas been used in the translocation of DNA or RNA and it allows us to measure the passage time, the scalinglaws of which has been experimentally reported. Establishing the scaling theory of the driven translocation isthen considered to be an attractive subject in single chain dynamics.
In translocation, a membrane or a thin plate separate the system and the polymer passes across cis- totrans-sides. In cis-side, polymer is pulled and the tension is transmitted along the polymeric chain. The
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moving domain, in which the tension is propagated, is stretched and grows with time. On the other hand, intrans-side, the polymer is pushed and compressed in the vicinity of the pore, and then the part isdecompressed outward. Previous studies can deal with each side, separately, but lacks the understanding of
the large deformations in cis- and trans-sides on even ground.
To evaluate both sides in the same framework, we describe the cis- and trans-side effect by fast andslow diffusion equations, respectively. Both are described by the same type of non-linear partial differential
equation, but physical characteristics is completely different. The lower line (the higher volume) density is,
the higher current is in cis-(trans-)sides. Moreover, to give the time evolution at the scaling levels, the cis
dynamics needs the global information (extension), but the trans-side only requires the local quantities
around pore.
On the basis of them, we established the scaling theory of the passage time. The scaling exponents aresuggested to be determined by the cis-side in the long chain limit.

Dynamical efficiency in template-directed polymer synthesis
Many of biopolymers like DNA, RNA have sequence information in one dimensional structure. In thesynthesis, a catalyst reads a sequence along the template and incorporates the substrates into the product.
However, mismatches between template and productelements sometimes occurs, since the synthesis takes
place in the presence of thermal random force.
The substrates serve as the energy sources as

0.020

well as the materials, which drive the catalyst. The

0.015

catalyst moving at the high effective speed achieves
the high production rate. However, we may imagine,

measured by different scales, and then the qualitative
discussion about a balance between the accuracy andspeed is difficult.
In this study, we propose a rate of the

0.08
0.06

Jx

0.04

0.010
0.005

br=0.26

in a lot of situations, the high speed is not compatible
with the accuracy. The accuracy and speed are usually

0.10

Jx
IJ

0.025

0.26

0.42

0.58

bw

0.74

IJ

0.02
0

0.90

Fig. 3 Numerical results of TDS rate and total
probability flow on the sequential switchingpotential model.

template-directed synthesis (TDS) to evaluate thebalance of the speed with the accuracy on the same scale. First we define the order of the correct sequences.
In our criterion, if the amount of the products is larger, the products are more correct. Developing thisarguments, we can define the TDS rate, which evaluates the TDS system. The TDS rate contains a function
form analogous to the Shannon entropy. The high speed basically increases the TDS rate, but, if thesequences of the products are diversified, the TDS rate decreases.
We discuss how the system conditions affects the TDS rate in two different models. Even if thesynthesis speed is enhanced, the TDS rate does not necessarily increases.
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2. Original papers(1) Takuya Saito, and Takahiro Sakaue,“Cis-trans dynamical asymmetry in driven polymer translocation”
Phys. Rev. E 88, 042606(2013).
3. Presentation at academic conferences(1) 齋藤拓也, 坂上貴洋,“Crumpled Globule における標識されたモノマーの異常拡散”
日本物理学会 2013 秋季大会, 徳島大学 常三島キャンパス, Sep 28, 2013
(2) 齋藤拓也、坂上貴洋“Crumpled Globule の異常拡散現象”
第３１回染色体ワークショップ, 第１２回核ダイナミクス研究会 足柄下郡箱根町
ホテルおかだ, Nov 26, 2013(3) 齋藤拓也、坂上貴洋“伸張される高分子鎖の過渡的過程における揺らぎ”
日本物理学会第６９回年次大会 東海大学 湘南キャンパス, Mar 27, 2014
4. Others(1) Takuya Saito and Takahiro Sakaue“Crumpled Globuleにおける標識されたモノマーの異常拡散現象”
The 11th symposium of Fukui Institute for Fundamental Chemistry, Kyoto, Jan. 23, 2014.

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Fu-Quan BAIFIFC Fellow
1. Summary of the research of the year
Excited States of a Significantly Ruffled Porphyrin: Computational Study on the
Structure-Induced Rapid Decay Mechanism via Intersystem Crossing
The out-of-plane macrocycle distortion in a series of sterically-crowded porphyrins results in
unusual optical properties. Their enhanced radiationless decay of the 1(π, π*) excited state iscomparable to those of the DNA bases. Not only ruffled metalloporphyrins but also ruffled
free-base porphyrins reduce excited-state life time by a factor of 200, which indicates that the originof the rapid decay is not only in the metal d-d deactivation but also in the excited state of the
distorted porphyrin ring. This raises the possibility that the excited-state properties of the porphyrin
are able to adjust step by step through introducing distortions into this tetrapyrroles skeleton. It is,therefore, important to understand how the structural distortion is linked with the photochemicaland photophysical consequences.
In the last decade, there have been significant progresses particularly in quantitative
computational study on the excited states of porphyrins. Concerning the excited state decay via
intersystem crossing (ISC), Marian and co-workers performed DFT/MRCI calculations forunsubstituted planer free-base porphin and found two possible decay pathways from S1 to T1 state.
Spin-orbit coupling (SOC) increases by out-of-plane vibrations of the porphyrin ring. Concerning
ruffled porphyrins, there was a controversy on the origin of the bathochromic shift of the Q band(the lowest-energy absorption) in the absorption spectrum; out-of-plane distortion of the ring versus
the electronic effect of substituents On the origin of the fast deactivation, however, we have foundno report on the excited-state potential surface to explain the course of the relaxation process.

Figure 1 (a) Chemical structures of free-base porphyrin (H2P) and meso-tetra-tert-butylporphyrin(H2T(t-Bu)P). (b) and (c) Ground-state optimized structures of H2P and H2T(t-Bu)P, respectively.
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The green area denotes the dihedral angles C4-C5-C6-N4 and C14-C15-C16-N2 (see (a) for atomic
indices). (d) and (e) The side view of (c) along C10-C20 axis and N1-N3 axis, respectively.

Figure 2. Potential energy profiles of the singlet and triplet excited states of (a) H2P and (b)H2T(t-Bu)P at equilibrium and intersystem crossing points. Calculations were performed at
B3LYP/6-31+G(d,p) level.

Figure 3. Potential energy curves of singlet and triplet states of H2T(t-Bu)P along theC4-C5-C6-N4 angles. Calculations were performed at the (a) SCC-RICC2/def-SV(P) and (b)CASSCF/ANO-RCC-VDZP levels. Structure was optimized for T1 state at each angle. Cross marks
denote potential energies at S0/T1 structure that was optimized at the B3LYP/6-31+G** level.
Spin-Orbit Coupling between the S0 and T1 states and between the S1 and T2 states were obtainedwith the CASSI method.
Ruffled porphyrins show by 100 times more rapid decay from electronic excited states. This
photophysical property is in contrast with the ordinary planer porphyrins that are often used forphotosensitization and transportation medium for excitation energy transfer in biology andphotochemistry. As nature shows, stabilization of the chemical system against photo irradiation isachieved by introducing a good quencher molecule that can release extra electronic energy to2－ 92 －

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thermal bath. In the present study, we study potential energy surface of a ruffled porphyrin,
H2T(t-Bu)P, to understand the rapid non-radiative decay mechanism.
On the basis of the SCS-RICC2 calculations, which is an approximated coupled-cluster
method, we investigated potential energy surfaces of H2T(t-Bu)P. We found that the S1 and T2
states lie close in energy from the S1 minima point to a wide range of structures with distortion
angles. There should be many chances for ISC to the T2 surface and then to the T1 surface (Kasharule). Regarding the S0/T1 ISC, we located MEISC point at the B3LYP/6-31+G(d,p) level. The
MEISC structure is similar to that of T1 minimum but with more distorted dihedral angles. We also
found that the T1 surface along the distortion is surprisingly flat. The reason of the flatness isinterpreted by the nodal structure of HSOMO in which the distortion helps to avoid destabilization
due to the anti-bonding interactions at the twisting bond. This result indicates that the trajectory caneasily reach to the ISC crossing point after relaxing into the T1 surface. We also performed
CASSCF(6e, 6o) calculations and obtained similar results. CASSI calculations were also performed
for calculating SOCs between S1-T2 states and between T1-S0 states. From these results, in addition
to the vibronic SOC mechanism as has been proposed for the planer porphyrin, ISC through the
T1-S0 intersection could also be a possible mechanism for the distorted porphyrin case. We also
investigated excited state potential surfaces of H2P and located two MEISC points. In contrast to
the H2T(t-Bu)P case, there are significant energy barrier in the T1 surface to reach the minimum
energy ISC points.
2. Original papers(1) Jie Chen, Jian Wang, Fu-Quan Bai, Li Hao, Qing-Jiang Pan*, Hong-Xing Zhang*,“Connection style and spectroscopic properties: Theoretical understanding of the interface
between N749 and TiO2 in DSSCs”.
Dyes and Pigments, 99(1), 201-208, (2013). DOI: 10.1016/j.dyepig.2013.04.008(2) Jie Chen, Jian Wang, Fu-Quan Bai, Qing-Jiang Pan, Hong-Xing Zhang*,"Theoretical Studies on Structural and Spectroscopic Properties of Photoelectrochemical
Cell Ruthenium Sensitizers, Derivatives of AR20".
International Journal of Quantum Chemistry, 113(7), 891-901, (2013).
(3) Juan Jin, Fu-Quan Bai, Ming-Jun Jia, Yan-Ning Wang, Hong-Li Jia, Jie-Hui Yu*, Ji-Qing
Xu*,“New Cd2+, Pb2+ complexes with acylhydrazidate molecules from in situ acylation
reactions”.
Dalton Transactions, 42(24), 8771-8780, (2013). DOI: 10.1039/c3dt50411e.
3. Presentation at academic conferences(1) Fu-Quan Bai, The 12th National Symposium of Computational Chemistry, Suzhou, China,
Oct. 21-24, 2013.
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Jing-Dong GUO
SPR Fellow

Jing-Dong Guo
SPR Fellow
1.

Summary of the research of the year
I.

Theoretical study of the Diels−Alder reaction of La@C82 with 1,2,3,4,5Pentamethylcyclopentadiene.

The Diels-Alder (DA) reaction is an extremely valuable type of cycloaddition in organic chemistry. The
DA reaction of pure C60 with CpH was explored and published. (Osuna, et.al, J. Phys. Chem. A, 2009,
113, 9721) In our paper, we investigated the mechanism and regioselectivity of the reaction ofparamagnetic metallofullerene (La@C82) with Cp*H by using density functional theory at spinunrestricted M06-2x level.

Figure 1a) Reaction profile for the DA reaction of La@C82 and Cp*. 1b) Singly linked
intermediate (III) for the stepwise cycloadditionreaction between La@C82 and Cp*H.
§1. It is shown in Figure 1a that the reaction proceeds via a concerted mechanism.

In the initial step for the cycloaddition reaction, a complex of La@C82 and Cp* (intermediate I) was
formed, which is more stable by 10.6 kcal/mol than the reactants (La@C82 + Cp*). The shortest carboncarbon distances between La@C82 and Cp* for I with addition carbon sites are 3.069 and 3.084 Å.
The slight differences of these two distances are derived from the asymmetric structure of I. The energy－ 94 －

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barrier from I to the final adduct via a transition state (II) is 12.2 kcal/mol. The geometry of II closely
resembles the reported transition structure for the DA reaction of C60 with CpH. The closest
carbon−carbon distances between La@C82 and Cp* are 2.318 and 2.181 Å, which are similar to the
distances reported for the transition states of C60−Cp and C60−quinodimethane reactions.
§2. The located singly linked intermediate exhibits that stepwise way is much less favorable thanthe concerted way.

For the case of the stepwise addition, the singly linked intermediate between La@C82 and Cp* ataddition carbon site C21 or C23 was searched in detail. As a result, the formation of one singly linked
intermediate shown in Figure 1b was found. It is notable that the Intermediate is 19.3 kcal/mol higher inenergy than reactants. This result suggests that the energy barrier for the stepwise path is considerablylarger than that for the concerted path in the reaction of La@C82 and Cp*H.

Figure 2. The α-HOMO, β-LUMO,α-LUMO, and β-LUMO+1 of I. Orange circles show the additionsite.
§3. Molecular orbitals analysis suggests that the DA reaction proceeds via a concerted mechanism.
According to the Woodward−Hoffmann rule and Frontier Molecular Orbital theory, the LUMO of
La@C82 is expected to play a key role in the interaction with the HOMO of Cp*H because the smaller
HOMO−LUMO gap between the HOMO of diene and the LUMO of dienophile results in the decreasingof the energy barrier. Furthermore, In the initial step for this reaction, we found that the α-LUMO and βLUMO+1 of La@C82 have large orbital coefficients on the addition site carbons (C21 and C23) (Figure2). This indicates that the α-LUMO and β-LUMO+1 of La@C82 can play a main role in interaction with－ 95 －

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the HOMO of Cp*H. The fact that the α-LUMO and β-LUMO+1 of La@C82 present a favorable orbitalat the addition site to react with Cp*H suggests that the DA reaction proceeds via a concerted mechanism.

Figure 3. Relative energies calculated for La@C82Cp* isomers.
§4. The relative stability of regioisomer confirms that isomer a with addition C21/23 sites isprobably the monoadduct.

Experimentally, the DA reaction between La@C82 and Cp* afforded only one isomer. To confirm theexperimental result, the addition site of 13 isomers in Figure 3 was selected by the orbital coefficients in
the LUMO of La@C82. It is noted that the most stable on is isomer a which is determined using X−ray
crystallographic analysis. These results confirm that isomer a is not only kinetically but also
thermodynamically the most conceivable monoadduct.
§5. The retro-DA reaction data verify that the utilized M06-2x functional is reliable.

The activation energy for the retro-DA reaction of La@C82Cp* was determined as 27.0 kcal/mol, whichis 3.1 kcal/mol higher in energy than the retro-DA reaction of La@C82Cp. This higher activation energy
is mainly attributable to the substituent effect of electron donation derived from five methyl groups of
Cp*H, increasing the stability of La@C82Cp* similarly in the case of C60Cp*. In addition, theexperimental value of 27.0 kcal/mol agrees reasonably well with the calculated values of 29.9 kcal/mol,suggesting that the M06-2x functional is suitable for the exploration of such DA reaction.
In conclusion, results of this study show that the DA cycloaddition reaction of Cp*H and paramagnetic－ 96 －

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La@C82 proceed via a concerted bond formation mechanism, through an intermediate formation of
La@C82 and Cp*H. The experimentally obtained results related to the retro-DA reaction of La@C82Cp*
exhibit the activation energy, which is in good agreement with the theoretical predicted one. Using theM06-2X method therefore enables the analysis of endohedral metallofullerene DA cycloaddition
reactions, in spite of the fact that La@C82 has a radical character. This approach is therefore also
promising for further investigation of the reaction mechanism of functionalization of endohedral
metallofullerenes.

1.

Original papers:(1) Satoru Sato, Yutaka Maeda, Jing-Dong Guo, Michio Yamada, Naomi Mizorogi,
Shigeru Nagase, 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).

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Wei-Wei WANG
Wei-Wei Wang

SPR Fellow
SPR Fellow

1. Summary of the research of the year
I.

Oxygen Reduction and Nitrogen Doping Mechanisms of Graphene Oxides

Ever since its isolation in 2004, graphene has attracted tremendous attention due to its
exceptional characteristics. To date, great achievements have been made on graphene-based
nanomaterials in the fields of chemistry, physics, and life science. Besides the pristinegraphene structure, both experimental and theoretical efforts were made to design andsynthesize heteroatom-doped graphene materials to tailor the physicochemical properties forextending applications. For example, because of the unique electronic properties,
nitrogen-doped graphene (NG), in which one or more carbon atoms are substituted bynitrogen atoms, is expected to utilize in fuel cells and other electrochemical devices.
Structurally, there are three types of bonding configurations for a doped nitrogen atom ingraphene, including graphitic N, pyridinic N, and pyrrolic N (Figure 1). The pyridinic N andpyrrolic N are formed at the edge or defective sites. The graphitic N, which bond with threecarbon atoms, is formed inside the continuous network of graphene.

Figure 1. Bonding types of nitrogen atoms in nitrogen-doped graphene
In 2009, Li et al reported a simple chemical method to obtain NG in bulk quantities. By
annealing the graphene oxides (GO) in NH3, they synthesized NG materials at evaluatedtemperatures. XPS spectra revealed that the nitrogen atoms were embedded into the carbon
skeleton and the graphitic N exhibited a more prevailing role than pyridinic N and pyrrolic N
over 900°. So far as we know that nearly all the theoretical studies of GO focus on the oxygen
reduction reactions and there is no explanation on the nitrogen-doping mechanisms. In thiscontext, our objectives is to elucidate the interactions between ammonia and various oxygengroups (epoxide, hydroxyl and carbonyl), and to uncover the formation mechanisms ofgraphitic N from NH3 and GO.
We modeled the structures of graphene oxides as finite fragmental carbon sheets withvarious oxygen groups (Figure 2). Such finite structures have been extensively used fortheoretical calculations. All computations were performed with the M06-2X density
functional in conjunction with the basis sets of 6-31G(d) by using the Gaussian 09 program.

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Figure 2. Structures of graphene oxides.
In general, our calculations suggest that chemically reduction on perfect carbon skeleton
of GO with ammonia is facilitated at evaluated temperature, but the following doping process
is kinetically impossible because of the high energy requirement. Accordingly, direct dopingfrom flawless graphene network seems unpractical. To put the nitrogen atom into carbon
network, graphene vacancies is indispensible and the reactions between NH3 and defective
GO with hydroxyl or carboxyl groups have been calculated. All possible mechanisms are
explored in detail. The formation of hexagonal graphitic N from NH3 and GO with vacancies
is proved to be a feasible process at high temperature and the interaction between NH3 andoxygen groups is found to play a fundamental role in assisting the nitrogen doping and theoxygen removal processes. The results provide insight into hetero-graphene formation andmay useful for the design of functionalized carbon-based hybrid materials in the future.
II. Theoretical Study of Atomic Carbon Participated Fullerene Growth Mechanisms
Ever since the discovery of fullerene C60, numerous hypothetical models were proposed
around its formation. Among various theoretical predictions, the “bottom-up” growth iswell-accepted because of experimental supports. As illustrated in the hypothesis, theenlargement of fullerenes is achieved by capturing and assembling the ambient small carbon
clusters (e.g. C2 dimer). The C2 addition was firstly proposed by Endo and Kroto in 1992 to
explain the fullerene growth (Figure 1). Subsequently, this Endo-Kroto model was proved as a
stepwise pathway and widely used to interpret the topological connection between carbon
cages.
However, in some cases, structural relations among special carbon cages (such as theformation of C70 from C68) indicate that direct C2 insertion cannot always accomplish thegrowth and structural reconstruction is unavoidable. For instance, the Stone-Walestransformation (SWT, Figure 1) is a common reaction to describe the rearrangement between
fullerene species, although the process needs to overcome a huge energy barrier (5-7 eV).

Figure 1. Endo-Kroto C2 addition (left) and Stone−Wales transformation (right)－ 99 －

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Figure 2. (a) Saito C2 addition model and (b) structural connection between #6290C68_C2
and #8149C70_D5h.
Besides the classical Endo-Kroto model, another C2 addition model (Figure 2 (a)) which
was proposed by Saito et al., has long been dismissed as “chemically unacceptable” becauseof the large energy requirements for the dissociation of the C2 dimer. Nevertheless, it isundeniable that the Saito model can accomplish special connections among fullerenes which
can not be constructed by the Endo-Kroto model. For example, existing theoreticalinvestigations have suggested that there is still no direct C2 growth route among stable C68 andC70 cages. However, based on our geometrical analysis, #6290C68_C2 and #8149C70_D5h, thelowest energy isomers of C68 and C70, can be topologically connected via the Saito C2 addition
model (see Figure 2 (b)). Therefore, if a reasonable mechanism can be offered to explain the
kinetic process, a direct growth channel toward the formation of C70 can be uncovered.
Energetically, the “Saito addition” is not approbated because the hypothesized
overlapping C2 insertion seems unrealistic. However, such a C2 addition which leaps over two
carbocyclic rings can be considered as stepwise atomic carbon additions on two respective
carbon segments, since it was proved that besides the C2 group, other addition reagents (suchas C1 or C3) can assist the growth of fullerenes as well. Moreover, since the odd-numberedfullerenes were reported recently in experiments, the atomic carbon addition can serve as
another significant fullerene growth route while using the odd-numbered cages asintermediates. Therefore, we proposed that the “Saito addition” can be chemically treated as
two sequential atomic carbon additions combining with the migration and reconstruction of
the unsaturated sp-hybridized carbon. Worthwhile to note that though the reconstruction is
unavoidable after the single atom injection, the rearrangement which occurs on the active
odd-numbered fullerene clusters can be assisted by the unsaturated carbon, and consequently,
a considerably lower energy barrier can be predicted.
In the present study, we proposed an atomic carbon growth mechanism to explicate the
SWT-involved growth procedure for some special fullerenes (e.g. #6290C68_C2 →#8149
C70_D5h). The DFT calculation results (at the level of B3LYP/6-311G(d)) suggest that theenergy barrier of single carbon addition mechanism (2-3 eV) is much lower than that of the
traditional Stone-Wales rearrangement (5-7 eV). Our work will supply a new interpretation on
fullerene formation mechanisms.

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2. Original papers(1) J. –S. Dang, W. –W. Wang, S. Nagase, and X. Zhao
“Regiochemistry of Nonclassical C62 Fullerene: Role of Tetragonal Carbocyclic Ringin Cycloadditions and Thermal/Photoinduced Interconversions of Fulleroid”
J. Phys. Chem. C 117, 12882-12889 (2013).

(2) H. Zheng, X. Zhao, W. –W, Wang, J. –S. Dang, and S. Nagase“Quantum Chemical Insight into Metallofullerenes M2C98: M2C2@C96 or
M2@C98, Which Will Survive?”
J. Phys. Chem. C 117, 25195-25204 (2013).
(3) J. –S. Dang, W. –W. Wang, X. Zhao, and S. Nagase“Regioselective Derivatization of C84 by Diels-Alder Reactions: Applications to
Photovoltaic Solar Cells and Fullerene Polymerization”
Org. Lett. 16, 170-173 (2014).
(4) W. –W. Wang, and S. Nagase“Oxygen Reduction and Nitrogen Doping Mechanisms of Graphene Oxides”
Manuscript in preparation(5) W. –W. Wang, S. Nagase, J. –S. Dang, and X. Zhao
“Theoretical Study of Atomic Carbon Participated Fullerene Growth Mechanisms”
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Miho HATANAKA
Miho Hatanaka
FIFC Fellow

FIFC Fellow
1. Summary of the research of the year
1.1. Theoretical study of aqueous Mukaiyama-Aldol reaction catalyzed bylanthanide complexes
Highly stereoselective reactions have been achieved by using chiral catalysts, and thecomputational chemistry contributed to better understanding of the mechanism of such reactions.
Conventional chiral catalysts usually have rigid structures, and only a few transition states ofstereo-determining step need to be computed to elucidate the origin of stereoselectivity.
Recently, many catalytic systems having flexible structures have been reported for highly
stereoselective C-C bond formations in aqueous media. These catalysts are quite different fromconventional rigid chiral catalysts which were used for various reactions in organic solvent.
Here, three questions arise in the following way; [1] How do the flexible chiral catalysts control
the stereoselectivities? [2] Is it an appropriate way to compute one or few transition states forstudying the stereo-selectivity of flexible reaction systems? [3] What role does water play, justsolvent or an important key for the reactions?
To discuss the stereoselectivity of such flexible catalytic systems, it might not be enough tocompare only few TSs of stereo- determining step because there should be a number of TSs
whose structures are slightly different because of the structural fluctuation. To overcome thisproblem, an automated explore method, called the Global Reaction Root Mapping (GRRM)
strategy was applied to predicting the ratios of stereoisomers quantitatively. In this study, I focus
on two flexible reaction systems, such as the Kobayashi-modification of Mukaiyama-Aldol
reactions catalyzed by two kinds of lanthanide (Ln) Lewis acid catalysts in aqueous solution anddiscuss their stereoselectivity.
【Topic 1】Ln3+ catalysts are drawing attention because they are active as Lewis acid catalysts
even in aqueous media. Though the first report about the aqueous Mukaiyama-Aldol reaction
catalyzed by Ln3+ (Scheme 1) was published 20 years before by Kobayashi, there are still
unsolved questions concerning the role of water. One question is why the product yield of thisreaction catalyzed by Ln(OTf)3 in organic solvent dramatically increased upon addition of water.
Another is why the diastereoselectivity of this aqueous reaction shows syn-preference.

Scheme 1. Aqueous Mukaiyama-Aldol reaction catalyzed by Eu(OTf)3.

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To answer these questions, we applied one of the GRRM strategy, the artificial force induced
reaction (AFIR) method with the B3LYP-D3 theory and clarified the most favorable reaction
pathway. This reaction proceeds via a stepwise mechanism, first C-C bond formation, followedby proton transfer from water to benzaldehyde and then trimethylsilyl (TMS) dissociation
caused by nucleophilic attack by bulk water molecules. The answer of the first question can befound by the nature of the Gibbs free energy surface of this reaction. Without water, thisreaction should stop after the first C-C bond formation step because the remaining steps needwater molecules. Focusing on the first step, the rate of backward reaction is much faster thanthat of the forward one, which results in low yield under anhydrous condition. Next, to discuss
the diastereoselectivity, the structural sampling of TSs of stereo-determining C-C bondformation step was obtained exhaustively. We used the AFIR method and found 91 syn-TSs and73 anti-TSs whose coordination structures around Eu3+ and orientation between two substrates
are slightly different. Among them 17 TSs contributed greatly to the diastereomeric ratio and I
succeeded in reproducing the ratio
quantitatively by considering all theobtained TSs. The second question
was explained by the comparison of
the lowest syn- and anti-TSs. The
anti-TS for C−C bond formation inwater is entropically less favored
relative to the syn-TS because of theexistence of a rigid hydrogen bondFigure 1. Obtained TSs for C-C bond formation
step producing the syn-structures

between the TMS part and coordination water around Eu3+ in the former. As shown above,
considering only a few TSs for the rate-determining step is not enough to reproduce theexperimental ratio, the exhaustive sampling of TSs can be obtained by the AFIR method, andwater was not just a solvent but contributed to promote the reaction.
【Topic 2】One may think that Ln3+ complex seems to be unsuitable for highly stereoselective
reactions because of its flexible coordination structure. However, this problem can be solved byremoving coordination water molecules around Ln3+ by using a ligand. For example, Allen et al.
reported the highly enantio- and diastereo-selective aqueous Mukaiyama-Aldol reaction
catalyzed by chiral Eu-DOTA derivative (Scheme 2). However, Ln-DOTA and its derivatives
are known to have a number of conformers and flexible structures. How does this flexible
catalyst control the stereoselectivity? To answer this question, thepossible conformations of the catalyst were explored by using theanharmonic downward distortion following (ADDF) method whichis the second method in the GRRM strategy and it was found that

Scheme 2. Chiral
Eu-DOTA derivative－ 103 －

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three conformers (A, B, and C shown in Figure 2) coexisted in the reaction system.

Figure 2. Four stable conformers of the chiral Eu-DOTA derivative. Gibbs free energies at -25oC
are in kcal/mol. Numbers in parentheses are the existing probabilities.
Next, to discuss the stereoselectivity, the AFIR calculations were performed for gathering theTSs of C-C bond formation step. By considering all the obtained TSs, both diastereomeric ratio
and enantio excess were evaluated very quantitatively. The most stable TS which produced the
major (R,R) product had Conf. B structure, that was not the most stable conformer, for thecatalyst part. The structure of catalyst part of the most stable TS producing the enantiomer (S,S)
was not Confs. A and B but Conf. C. What we can say from here is that if Conf. C does not exist
in the reaction system, the enantioselectivity should be higher. Therefore, to improve theenentio-selectivity, we need to control the stability of each conformer to reduce the amount ofConf. C. The easiest way to change the stability of each conformer is changing the lanthanide
cations. Figure 3 shows the existing probabilities of four conformers in each Ln-DOTA
derivative. By using lighter Ln, the existing probability of Confs. A and C can be reduced
dramatically. This result is consistent with theexperimental

study

that

the

highestenantioselectivity was shown in Nd catalyst
and the second in Pr catalyst. Therefore, we
can say that for flexible catalytic systems, themostimportant

point

to

improve

thestereoselectivity is not to use bulky catalysts
but to reduce the conformers which produce
the minor products.

Figure 3. Existing probabilities of Ln-DOTA
derivatives at -25oC condition

1.2. Mechanism of CnH (n = 2, 4, 6) generation in the interstellar media
In the past few decades, a number of cations and neutral molecules were detected in theinterstellar media (ISM) and the mechanism of generation and reactivity of these molecules
have been investigated by experimental and computational methods. However, there are still
remaining questions. One of them is the generation mechanism of anions. Until now, only six
anions, such as CnH (n = 4, 6, 8) and CnN (n = 1, 3, 5) have been detected and the existence
probability of CnH increases as the number of carbon (n) increases. However, the reason of the－ 104 －

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low abundance of anions and the abundance dependency on carbon chain have not clarified. In
this study, to clarify the reason of the questions above, three reaction systems CnH + e →CnH (n = 2, 4, 6) were focused on and the critical points on potential energy surfaces (PESs) of
CnH and CnH were explored by using the ADDF method.
Although the numbers of carbons are different, there were many similarities for CnH/CnH (n =2, 4, 6) systems. The GMs on neutral doublet ground states (D0) and anionic singlet groundstates (S0) had linear structures for n = 2, 4, 6. To form anions from neutral CnH, their PESs
must have crossing points. However, the difference between PESs of D0 and S0 were too large
and they did not cross each other. Therefore, the formation of anions from neutral CnH should
proceed through excited states of anions. Crossing points between D0 and anionic excited states
were found nearby the GM structures. However, the characters of anionic excited states
depended on the number of carbon atoms.
For n = 2, the closest anionic state from D0 was the lowest triplet state. However, the MSX
between D0 and the triplet state was 17 kcal/mol higher than the GM on D0, and so the electron
attachment process cannot occur in the ISM. For n = 4, the closest anionic state from D0 was
also the triplet state and the energy of their MSX was close to the GM on D0. Though thereaction barrier for electron attachment is enough small, the following radiative stabilization toreach the S0 state rarely proceeds because of the spin-forbidden transition. For n = 6, on theother hand, the closest anionic state from D0 was not triplet but singlet excited state. Therefore
the radiative stabilization after the electron attachment can proceed easier than that for n = 4.
The singlet excited state had the Rydberg state character where 2s orbital of H atom was singly
occupied. Therefore, the electron attachment process for n = 6 is the same as those for typicalmolecules where electrons aretrapped on Rydberg states first
and then relaxed to the groundstates. As shown above, thereason of anion abundance
dependency on the number ofcarbon can be explained.

Figure 4. Schematic explanation about the reaction
pathways for the CnH (n = 2, 4, 6) formations.

�����-aromaticity of hexa-Group 16 atom-substituted benzene dications
Nowadays many systems that show aromaticity caused by σ, δ, and ϕ electrons have beenreported, though the typical aromaticity is shown in π-electron delocalized systems. One of thewell-known candidates that show -aromaticity is C6I62+ in which removal of two 
anti-bonding electrons localized on I6 from neutral C6I6 results in fulfilling the Hückel (4n+2)
rules for I62+ as well as C6 parts. Such -aromaticity is not shown in C6Br62+ and C6Cl62+ because－ 105 －

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smaller overlaps of in-plane valence p orbitals of halogens cause smaller destabilization of 
anti-bonding orbital and result in removal of two electrons not from the anti-bonding  orbital
but from a delocalized  orbital. Hexa-group 16 atom-substituted benzene dications can be also
candidates because of the similarity of electronic states between halogens and group 16 atoms
capped by hydrogens or substituents. One of the advantages of hexa-group 16 atom-substituted
benzenes is that geometries and electronic structures can be controlled by modifying
substituents on the group 16 atoms. If the magnitude of overlap of valence p orbitals, which
determines the stability of the  anti-bonding orbital, can be controlled by changing geometry
and electronic structures with different substituents, hexa-group 16 atom-substituted benzene
derivatives can have strong -aromatic character.
To investigate the aromaticity of dicationic benzene derivatives, the isotropic nucleus
independent chemical shift (NICSiso) and its zz component (NICSzz) were evaluated by B3LYP
theory. NICS is a magnetic index of aromaticity and negative NICS values indicate aromaticity,whereas positive NICS values indicate anti-aromaticity. Figure 5 shows the Kohn-Sham orbitals
and NICSzz(1) values of dicationic benzene derivatives. (b) and (c) in Figure 5 are different
conformers of C6(SH)62+ and the directions of H atoms
are perpendicular to the C6 plane for (b) and four ofthem are in-plane and two are perpendicular for (c).
Only the conformer with D3d symmetry (b) has a similar
LUMO to C6I62+ which results in fulfilling Hückel
(4n+2) rules for S62+ and C6 parts and having aromaticcharacter. The other conformer with C2h symmetry (c)hasadelocalized

LUMO

and

anti-aromaticity.

Therefore, to find a molecule that shows -aromaticity,
we should find a molecule whose most stable conformer
has the singlet state and the geometry where all of the

Figure 5. Molecular orbitals and
NICSzz values of singlet dications

substituents are directed perpendicular to the C6 plane.
To find such molecules, a number of derivatives were examined and several candidates were
found, such as C6(SeH)62+, C6(TeH)62+, and their derivatives, which have larger aromaticcharacters than neutral benzene. To clarify the origin of larger aromatic characters, the NICS
values were dissected into contributions from canonical molecular orbitals and from localized
natural bonding orbitals. Both analyses showed the existence of contributions to aromaticity
from  orbitals of C6 and in-plane  orbitals of Se6 and Te6. To clarify the substituent
dependency on aromaticity, their derivatives were examined. However, the NICS values were
almost independent of the substituents, because the charge transfer between group 16 atoms andsubstituents takes place only through pz orbitals that are orthogonal to the in-plane  orbitals. In
addition, the aromaticity of hexa-groups 14 and 15 atom-substituted benzene dications were

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examined and it was found that only C6(SbH2)62+ had a large negative NICS value.

2. Original papers(1) M. Hatanaka, M. Saito, M. Fujita, K. Morokuma, “-Aromaticity in Hexa-Group 16 Atom
Substituted Benzene Dications. A Theoretical Study”, J. Org. Chem. 79, pp 2640-2646(2014).
(2) M. Hatanaka, K. Morokuma, “Role of Water in Mukaiyama-Aldol Reaction Catalyzed by
Lanthanide Lewis Acid: A Computational Study” J. Am. Chem. Soc. 135, pp 13972-13979(2013).
※Spotlights on Recent JACS Publications, 135, pp. 13999-13999 (2013)(3) M. Hatanaka, S. Maeda, K. Morokuma, “Sampling of Transition States for Predicting
Diastereoselectivity Using Automated Search Method —Aqueous Lanthanide-Catalyzed
Mukaiyama Aldol Reaction” J. Chem. Theory. Comput. 9, pp 2882-2886 (2013).
(4) 前田 理, 畑中 美穂, 植松 遼平, 武次 徹也, 諸熊 奎治, “人工力誘起反応法による化学反応経路の自動探索：有機合成化学への応用と展望”, 有機合成化学協会誌 72,
pp567-579 (2014).

(総説:査読なし)

3. Presentations at academic conferences(1) ○M. Hatanaka, “Theoretical study of highly stereoselective Mukaiyama-Aldol reaction inaqueous

media”,

AsianInternational

Symposium –Chemo-informatics, Computational Chemistry – in The 94

th

Theoretical

Chemistry,

Annual Meeting of the

Chemical Society of Japan, Nagoya, Japan, March, 2014 (Invited Talk)(2) ○M. Hatanaka, K. Morokuma, “Theoretical study on Aqueous Lanthanide-Catalyzed
Mukaiyama-Aldol Reaction”, 5th JCS Intermational Symposium on Theoretical Chemistry,
Nara, Japan, December, 2013. (Invited Poster)(3) ○畑中美穂, 諸熊奎治, “ランタノイドキレート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の理論的研究”,第 7 回分子科学討論会 2013, 京都, 2013 年 9月. (優秀講演賞受賞)(4) ○畑中美穂, 前田理, 諸熊奎治, “ランタノイド触媒を用いる水中向山アルドール反応の機構と立体選択性”, 第 16 回理論化学討論会 2013, 福岡, 2013 年 5 月. (口頭)
(5) ○M. Hatanaka, S. Maeda, K. Morokuma, “The role of water in aqueous Mukaiyama-Aldol
reaction catalyzed by lanthanide Lewis acid”, The 6th Asia Pacific Conference ofTheoretical and Computational Chemistry, Gyeongju, Korea, June, 2013. (Best poster
award)

4. Others
4.1. Presentations at symposiums(1) ○ M. Hatanaka, K. Morokuma, “Theoretical Study of Highly Stereoselective－ 107 －

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Mukaiyama-Aldol Reaction in Aqueous Media”, the 11th symposium of FIFC, Kyoto,
January, 2014 (Poster).
(2) ○畑中美穂, 諸熊奎治, “ランタノイド DOTA 誘導体の構造揺らぎ－キラル触媒・
MRI コントラスト剤を例に－”, 化学反応経路探索のニューフロンティア 2013, 京
都, 2013 年 9 月. (Poster)(3) ○M. Hatanaka, “Mechanism of Mukaiyama Aldol Reaction Catalyzed by Water-Tolerant
Lanthanide Lewis Acid – An Artificial Force Induced Reaction Study”, The 10th Fukui
Center Seminar, Kyoto, Japan, March 2013. (Invited Talk)
4.2. Lectures for high school students(1) 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, 兵庫県立北摂三田高等学校, 2013 年 12 月. (高校 1 年生(約 30人)対象)(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, 京都府立城南菱創高等学校, 2013 年 12 月. (高校 1 年生(約 160 人)対象)(3) 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, 兵庫
県立北摂三田高等学校, 2013 年 9 月. (高校 2 年生(理系限定約 120 人)対象)－ 108 －

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Fengyi LIU
Fengyi LIU
Postdoctoral Fellow
Postdoctoral Fellow
1. Summary of the research of the year
Exploring the Deactivation Path of Fluorescent Dyes by SF-TDDFTThe quantum yields for fluorescent dyes are critical, while theoretical predictions of radiationless decay
channel are often difficult due to the known issues. 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. We employed the GRRM MSX searching algorithm, in
combination with spin-flipping (SF) TDDFT, to locate the minimal-energy crossing points (MECP) between
the excited and ground states of the fluorescent dyes. Taking the open-shell, triplet ground state as reference,
the SF-TDDFT can describe the S1 and S0 state balancedly, therefore is capable of describing the conicalintersection region. The influences of the reference function, i.e., unrestricted or restricted open-shell DFT,
different Kohn-Sham wave functions, etc., have been systematically evaluated. The results are useful inexplaining experimental findings as well as designing new high-yield fluorescent materials.

Figure 1. Schematic radiationless decay channel for a fluorescent dye.

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. In this project, CASSCF and CASPT2 studies on the reaction
mechanismofthephotochromic

ring-opening

processofaspiropyran(SP)(1′,3′,3′-trimethylspiro-[2H-1-benzopyran-2,2′-indoline], also known as BIPS) have been performed and－ 109 －

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possible excited-state C–O (and C–N) bond cleavage pathways and S1-to-S0 nonadiabatic transition channels
have been explored. (1) The C–O bond dissociation in SP does not follow a conical-intersection mechanismthat has been proposed in a model study with a simplified benzopyran. The CASSCF-optimized crossing
points are actually avoided crossings with a 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 (cis–cis–cis
with respect to the configuration around α, β, γ) and TCC (trans–cis–cis) intermediates of merocyanine (MC)are barrierless, in line with the experimentally observed ultrafast formation of MC. (3) An unexpected
low-energy hydrogen-out-of-plane (HOOP) valley on the (π→σ*) surface was located not far from the 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 make a transition to theS0 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 high internalconversion yields of SP. These findings shedding light on the complex mechanism of SP–MC
interconversion provide fundamental information for design spiropyran-based photochromic devices.

Figure 2. Multiple pathways for the primary step of the spiropyran photochromic reaction.

The photochromic ring-opening reaction of spiropyran has been revisited at the multireference CASSCF
and CASPT2 level with a CAS(22e,20o) active space, in combination with density matrix renormalizationgroup (DMRG) methods. The accuracy of the DMRG-CASSCF and DMRG-CASPT2 calculations, withrespect to the number of renormalized states, the number of roots in state-averaged wave functions, and thenumber basis functions, was examined. For the current system, chemically accurate results can be obtainedwith a relatively small number of renormalized states. The nature and vertical excitation energies of theexcited (S1 and S2) states are consistent with conventional CAS(or RAS)PT2 with medium active spaces. The
capability of the DMRG-CASSCF method in the optimization of molecular geometry is demonstrated for the
first time. The computation costs (several hours per optimization cycle) are comparable with that of theconventional CASSCF geometry optimization with small active space. Finally, the DMRG-PT2 computed－ 110 －

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S1-MEP for the C–O and C–N bond-cleavage processes show good agreement with our previous calculations
with a CAS(12e,10o) active space [Liu, F.; Morokuma, K. J. Am. Chem. Soc. 2013, 135, 10693–10702].
Especially, the role of the HOOP valleys in the S1 → S0 nonadiabatic decay has been confirmed.

Figure 3. Multireference Ab initio DMRG-CASSCF and DMRG-CASPT2 study on the photochromic
ring opening of Spiropyran.

2. Original papers(1) Fengyi Liu and Keiji Morokuma
Multiple Pathways for the Primary Step of the Spiropyran Photochromic Reaction: A
CASPT2//CASSCF Study
J. Am. Chem. Soc., 2013, 135 (29), pp 10693–10702.
(2) Fengyi Liu, Yuki Kurashige, Takeshi Yanai, and Keiji Morokuma
Multireference Ab Initio Density Matrix Renormalization Group (DMRG)-CASSCF and
DMRG-CASPT2 Study on the Photochromic Ring Opening of Spiropyran
J. Chem. Theory Comput., 2013, 9 (10), pp 4462–4469.
(3) Piao, W., Tsuda, S., Tanaka, Y., Maeda, S., Liu, F., Takahashi, S., Kushida, Y., Komatsu, T., Ueno,
T., Terai, T., Nakazawa, T., Uchiyama, M., Morokuma, K., Nagano, T. and Hanaoka, K.
Development of Azo-Based Fluorescent Probes to Detect Different Levels of Hypoxia. Angew.
Chem. Int. Ed., 2013, 52: 13028–13032.

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Lina DING
Name:
Lina
Ding
Research
Fellow
Research Fellow
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

The detailed DFT investigation clears the working mechanism of the irreversible
photoisomerizationoftrans-[Ru(tpy)(pynp)(OH2)]2+

(TA)

and

cis-[Ru(tpy)(pynp)(OH2)]2+ (CA) complexes. Both TA and CA complexes present two
types of low lying triplet states, one resulting from a triplet metal–ligand
charge-transfer (TMLCT) and the other from a triplet metal-centered d–d transition(TMC). The vertical excitation of the singlet ground state of the complexes leads to asinglet excited state, which undergoes ultrafast decay to the corresponding TMLCT. For
TA, this TMLCT transforms with a low barrier to a TMC state. The dissociative nature of
the TMC state leads to easy water removal to produce a five-coordinate intermediatethat can isomerize via rotation of a pynp ligand and proceed towards the CA product.
For CA, however, during this excitation and intersystem crossing process, an
excited-state proton transfer (ESPT) occurs and the resultant TMLCT is very muchstabilized with a very strong Ru(II)–OH bond; the high barrier from this TMLCT blocks
conversion to a TMC state and thus prevents isomerization from the cis to the transisomer. This high barrier also prevents the possibility of the isomerization process－ 112 －

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from TA to CA solely on the adiabatic triplet pathway. Instead, crossing points(XMC-CB, XMC-CA) near the minimum of the triplet metal-centered state of the cis
isomer provide nonadiabatic decay channels to the ground-state S0--CA, which
completes the photoisomerization pathway from TA to CA.

P2. sp3–sp2 vs sp3–sp3 C–C Activation in Rh-Catalyzed Ring Opening of
Benzocyclobutenol: A DFT Study

The Csp3–Csp2 vs Csp3–Csp3 site selectivity in the C–C bond activation in
Rh-catalyzed ring opening of benzocyclobutenol was systematically investigatedusing density functional theory (DFT). The catalytic cycle includes threeelementary steps: the proton transfer from the substrate to a rhodium hydroxide,
the C–C cleavage, and the proton transfer from water onto a carbon forming thefinal product with regeneration of the rhodium hydroxide. The site selectivity isdetermined by the C–C cleavage step; the Csp3–Csp2 cleavage is favored over the
Csp3–Csp3 cleavage because the former transition state is stabilized by aninteraction between the benzene ring of the substrate and Rh. DMSO, a morepolar solvent, reduces the site selectivity as the more polar Csp3–Csp3 transition
state (TS) is stabilized more than the Csp3–Csp2 TS and decreases the advantage ofthe latter TS. DPPF ligand is bulky, and the steric repulsion on the tighter
Csp3–Csp2 TS causes the loss of the site selectivity. For the even more crowded
Rh(P(t-Bu)3)2 catalyst, one phosphine has to dissociate before the C–C cleavage
reaction takes place, and the advantage of the Csp3–Csp2 TS is regained for the lesscrowded RhP(t-Bu)3 active catalyst.

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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, J. Chem. Theory
Comput., 2014, 10 (2), 668–675.
(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, J. Am. Chem. Soc., 2014, 136 (1), 169–178.
(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.

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Hai-Bei LI
Hai-Bei Li

Postdoctoral Fellow, Fukui Kenichi Memorial Research Group 1
Postdoctoral Fellow, Fukui Kenichi Memorial Research Group 1
1. Summary of the Research of the Year
Graphene Nucleation on a Surface-Molten Copper Catalyst
CVD has been the most preferred method of producing graphene, due to its
ability to produce graphene films with large-domains and high-quality. Of particularimportance in this respect are Ni and more recently Cu catalysts, which are the mostwidely used for graphene formation. One limitation of Ni catalysts for CVD graphene
growth is their propensity to form multi-layered graphene sheets, as opposed to single
layer graphene, and this presumably arises from a metastable Ni-carbide phase at
CVD-relevant temperatures. Ni exhibits both high carbon solubility and bulk carbon
diffusivity. Cu, as opposed to Ni, predominantly forms single-layer graphene
exclusively via surface catalytic reactions and processes, and this can be explained byits ultralow carbon solubility. This, combined with the lower market price of copper,
have made it perhaps the most preferred catalyst for CVD graphene production.
Large-size, spatially self-aligned, and single-crystalline hexagonal graphene flakes
have been produced on liquid Cu surfaces, implicating remarkable surface atom
mobility in the formation of high-quality graphene. However, the role of surface
morphology on graphene formation with Cu catalysts therefore remains an importantquestion.
In this work, we present quantum chemical simulations towards this end. We
provide the first comprehensive atomistic picture of nucleation and growth ofgraphene on the Cu(111) surface. We demonstrate here that the physical state of theCu surface region plays a key role on graphene growth. In particular, we reveal a
potential mechanism that explains copper’s intrinsic ability to form higher quality
graphene structures compared with Ni and Fe catalysts, and attribute this phenomenon
to the healing role provided by highly mobile Cu surface atoms.

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Figure 1. (a) Evolution of trajectory 6, depicting graphene nucleation and defect rings healing on
Cu(111). Defect healing mechanisms discussed in the text (white circle) are included in supporting
information. (b) Formation statistics polygonal carbon rings as a function of simulation time fortrajectory 6.

Snapshots depicted in Figure 1(a) typify the dynamics of graphene nucleation
observed on the surface-molten Cu(111) surface. As predicted, the basic chemical
reaction observed here is similar to that observed on Ni(111). The formation ofextended polyyne chains and Y-junction precursors were common and immediate
following the deposition of a high density of C2 fragments. Following the formationof these polyyne chains, subsequent ring condensation and the formation of
sp2-hybridized islands is rapid. This simulation provides the first evidence of defecthealing during graphene growth, which potentially underpins the high structuralquality observed in graphene grown on Cu catalysts. Figure 1(a) shows a structure(1.4 ps) consisting of approximately 50% structural defects i.e. pentagonal andheptagonal rings. Following a further 50 ps, this highly defective structure –reminiscent of Haeckelite – was transformed into an essentially pristine graphene－ 116 －

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structure, i.e. one composed almost completely from carbon hexagons. This isconfirmed in Figure 1(b), which quantifies the population of different polygonalcarbon rings in the structure during the course of the trajectory. The transformation ofthis originally defective structure took place via a number of chemical pathways, yet
in all cases was driven by the mobility of the Cu atoms in the underlying catalyst
surface. For example, the pentagon-heptagon defect (indicated by the circle in Figure1(a)) observed at 1.4 ps was healed by 2.67 ps. This process is driven by the diffusionof a single Cu atom in the surface layer which opens a vacancy in the Cu(111) surface,and consequently forces the cleavage of a C-C bond in the heptagon. The terminal
carbon in the polyyne chain thus formed then resides in the surface vacancy, due toattractive forces between it and the Cu surface, and this facilitates the formation of thehexagon in place of the original heptagon defect. The attraction between this terminal
carbon atom and the Cu surface is sufficiently strong so that it is cleaved from thehexagon and diffuses into the subsurface region of the catalyst. The neighboring
pentagon defect was subsequently healed into a hexagon via a comparable chemicalroute – first C-C bond cleavage and then ring closure, both being driven by the
dynamics of the underlying substrate.
The formation of polygonal carbon rings on the molten Cu(111) is remarkably
different compared to that observed using Ni(111). Ring formation in the latter case isessentially instantaneous (due to the artificial nature of the initial conditions
employed), with the final structure obtained essentially within ca. 2.5 ps (Figure 2).
Conversely, using Cu(111), the ring formation statistics evolve over a much longer
period. Initially increasing sharply (ca 5 ps), it takes a further 30 ps for the ultimate
populations of pentagons, hexagons and heptagons to be obtained on Cu(111). This isbecause the nucleating graphene structure is constantly being reorganized by theunderlying catalyst atoms towards the most thermodynamically favorable
configuration (one consisting entirely of hexagons). Consequently, the population ofhexagons observed using graphene becomes maximized compared to heptagons and,more importantly, pentagons. This is not the case on Ni(111), for whichapproximately equal populations of pentagons and hexagons are formed.
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Figure 2. Average polygonal carbon ring populations observed during graphene nucleation on (a)Cu(111) and (b) Ni(111) surfaces. The final graphene structures observed on Cu(111) take an orderof magnitude longer to be achieved than for Ni(111), as the atomic configuration of the structure isconstantly rearranged by defect healing mechanisms. By contrast, the final graphene structure onNi(111) is obtained almost immediately, within ca. 5 ps. All data averaged over 10 trajectories.

2. Original papers(1) H-B. Li, A. J. Page, A. M. Mebel, S. Irle, and K. Morokuma, “Graphene Nucleation on

a Surface-Molten Copper Catalyst: Quantum Chemical Molecular Dynamics
Simulations”, Chem. Sci. accepted, 2014.
3. Oral Presentations at Academic Conferences(1) H-B. Li, A. J. Page, S. Irle and K. Morokuma, “SWCNT Growth from Organic Precursors
without a Catalyst: Possibility and Limitations Revealed by Theoretical Simulations”, NT14,
USC, University of Sourthern California ( June. 1, 2014)(2) H-B. Li, A. J. Page, S. Irle and K. Morokuma, “Graphene Nucleation on a
Surface-Molten Copper Catalyst: QM/MD Simulations”, NT14, University ofSourthern California, USA ( June. 7, 2014)－ 118 －

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Lung
WaWa
CHUNG
Name
Lung
CHUNG
Postdoctoral
Fellow
Title
Postdoctoral
Fellow
1. Summary of the research of the year
1. Application of Ab Initio Density Matrix Renormalization Group (DMRG) on the Simplest
Fe(IV)-Oxo Complex. Iron-containing oxygenases catalyze many important biochemical oxidations.
High-valent Fe(IV)-oxo species has been observed or proposed as an active oxidant in many of these
oxygenases. Previous studies on Fe(IV)-oxo species were mostly based on single-reference DFT method.
Recent rapid development of ab initio density matrix renormalization group (DMRG), e.g. DMRG-CASSCF
and DMRG-CASPT2, allows us to use a much larger active space than the conventional CASSCF method.
Through collaboration with Drs. Kurashige and Yanai, I studied the state order of the simplest Fe(IV)-oxo
complex and its reactivity towards CH4 by using various QM methods (e.g. DFT, DMRG-CASSCF,
DMRG-CASPT2, RASSCF, RASPT2) (Figure 1). PES computed by DMRG-CASPT2 is qualitatively
similar to that evaluated by the B3LYP method, esp. significant dynamic correlation observed in the productside.

Figure 1.
2. Heavy-atom Tunneling in Cyclobutadiene: Quantum mechanical tunneling plays an important role inenhanced reactivity of some organic and enzymatic reactions. Generally, tunneling probability increases withsmaller masses of atoms involved, as well as a lower reaction height and narrow barrier width. Thus,
tunneling involving electron or hydrogen was commonly observed. Besides, more reactions mediated byheavy-atom tunneling have been suggested or observed by experimental and computational means. For
instance, Carpenter proposed that automerization of cyclobutadiene (CBD) involves dominant heavy-atomtunneling below 0 oC. I carried out high-level QM (QM = CASSCF, CASPT2 and MRCI) calculations andvariational transition state theory (VTST) with multidimensional tunneling simulations to elucidate realisticand detailed heavy-atom tunneling of cyclobutadiene (Figure 2). These semi-classical results suggest that theheavy-atom tunneling dominates the reaction rate, even around the room temperature.

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Figure 2.
3. A Theoretical Study on the UVR8 Photoreceptor: By the irradiation of ultraviolet-B (UV-B) light,
UVR8 photoreceptor can undergo dissociation of the protein homodimer and regulate gene expression inplants. We have carried out high-level quantum mechanics (QM) and ONIOM(QM:MM) calculations tostudy spectra of key tryptophan residues in UVR8 homodimer. Benchmark calculations on the absorption
and emission of 3-methylindole in the gas phase have been performed by different QM methods (TD-DFT,CASSCF, MS-CASPT2, and SAC-CI). Twenty different DFT functionals, including double hybrid andMinnesota functionals, were tested, but all these functionals failed to give satisfactory description of two key
transitions. In comparison, SAC-CI and CASPT2 methods can give reliable transition energies and a correct
order of 1La and 1Lb excited states. Furthermore, the vertical absorption and emission energies oftryptophan in UVR8 have been investigated by the ONIOM method (Figure 3). Our results supported that
W285 is the major chromophore of UVR8, while W233 can also sense the UV-B light. Geometrical effects
as well as electrostatic and polarization interactions with the protein matrix were found to influence opticalproperties of these tryptophan residues in UVR8.

Figure 3. Histograms of distribution of the ONIOM computed (a) 1La→S0 emission, (b) S0→1La
absorption and (c) S0→1Lb absorption for W285 and W233 in UVR8.
2. Original papers(1) 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.

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Ⅳ 研究業績 (2013)(2) Ding, L.; Chung, L. W.; Morokuma, K.* “Excited-State Proton Transfer Controls
Irreversibility of Photoisomerization in Mononuclear Ruthenium(II) Monoaquo
Complexes: A DFT Study”, J. Chem. Theory Comput. 2014, 10, 668.
(3) Li, X.;* Chung, L. W.; Morokuma, K.;* Li, G. “A Theoretical Study on the UVR8Photoreceptor: Sensing Ultraviolet-B by Tryptophan and Dissociation of Homodimer”, J.
Chem. Theory Comput. 2014, DOI: 10.1021/ct5003362.
(4) Chung, L. W.; Hrovat, D. A.; Morokuma, K.; Borden, W. T. “Dominant Heavy-Atom Tunnelingfrom the Vibrational Ground State in Automerization of Cyclobutadiene Below Room
Temperature”, Manuscript in preparation.
(5) Chung, L. W.; Kurashige, Y.; Yanai, T.; Morokuma, K.; “Ab Initio Density Matrix Renormalization
Group Study of Hydrogen Atom Transfer with an Iron(IV)-Oxo Complex”, Manuscript in
preparation.

3. Presentation at academic conferences(1) Lung Wa Chung, Xin Li, Keiji Morokuma, “A Recent Mechanistic Insight andComparative Reactivity of Fe(III)-Superoxo and Fe(IV)-Oxo: DFT, QM/MM andMulti-Reference Methods”, The 4th Asian Conference on Coordination Chemistry(ACCC4), Jeju, November 5, 2013 (“invited lecture”).

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GalinaPETROVA
GalinaPetrova
Petrova
JST
Fellow, Fukui
Fukui Kenichi
Kenichi Memorial
Memorial Research
Research Group
Group IIJST Fellow,
1. Summary of the research of the year
Our research in the last year was concentrated on the theoretical modeling of experimentally studied
asymmetric organic reactions catalyzed by different homogeneous catalysts: a Cu/DNA supramolecular catalyst[Sugiyama et al. Chem. Commun. 2012], phase-transfer catalysts [Maruoka, Tetrahedron 2006], or asymmetriccounteranion directed catalysis [List et al. Angew. Chem. Int. Ed. 2013; Chem. Eur. J. 2012]. The aim of thetheoretical investigations was to gain better knowledge on the reaction mechanisms and the nature of theenantio(stereo) selectivity which may allow further modifications of the catalysts and the experimental conditions.
In modeling the reaction mechanisms we applied the artificial force induced reaction (AFIR) method [Maeda,
Ohno, Morokuma, Phys. Chem. Chem. Phys. 2013], in order to find all possible conformations of the transition
state (TS) structures without prejudice.

The

originofenantioselectivity

for intramolecular Friedel-Crafts

reaction

catalyzedbysupramolecular Cu / DNA catalyst complex
As a first stage of our investigation, we performed a combined MD and QM/MM theoretical study on
the binding of L-Cu(II)-R complex to d(CAAAAATTTTTG)2 dodecamer. The L-Cu(II)-R complex consistedof bipyridine (L) and the reactant (R) that undergoes the unimolecular FC reaction. The main goal was tofind the preferred conformation of the L-Cu(II)-R / DNA reactant complex and to explain the influence ofDNA micro-environment on the enantioselectivity of the reaction. We modeled 28 structures of the Cu /DNA supramolecular catalyst with different initial conformation of L-Cu(II)-R, two pro-S and two pro-R,and different intercalation position in the DNA strand considering all symmetrically unique base pairs layers(BP layers). In the comparison of different Cu / DNA complexes, several important features were taken into
account: energetic characteristics of the system as binding energy and energy of deformation, deformation of
the DNA strand, and deformation of the metal complex.
Intercalation of the metal complex at the edge of the DNA strand, BP layers C1/A2, was found least
favorable and hardly induced any distortion of the DNA structure from the standard B type DNA. Structureswith intercalation of L-Cu(II)-R in the central part of the DNA dodecamer (BP layers A4/A5, A5/A6, A6/T7)
showed higher binding energy BEMD as well as higher energy of interaction EintQM/MM. These complexes
showed slight DNA distortion towards A type DNA and more pronounced axis bending. As a result of theinteraction with the DNA strand, the metal complex itself was also deformed as loss of the indole-imidazol
π-π stacking of the reactant and the electrostatic interaction between the π-electrons and the Cu(II) center
was observed. Some of the complexes exhibited conformation with the indole moiety enveloped in the DNA
minor groove.
On the base of the obtained results and energetic and structural analyses, the preferred formation of the
S product in the experimental studies could be explained on the base of several characteristics of the system:(i) Stability of the supramolecular complexes: pro-S structures showed higher binding energy to the1－ 122 －

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DNA strand, and the formation of pro-S Cu / DNA complexes should be preferred to the formation of pro-R
reactant complexes (Fig. 1a).
(ii) Short C3-C2' distance in the supramolecular complexes: the C3-C2' distances in the pro-S
complexes are shorter in comparison to the pro-R structures and closer to the expected TS structures (Fig. 1b).
This feature also suggests the reaction to occur more easily for the pro-S structure. The pro-S structures areusually only shallowly intercalated in the DNA strand, which would also facilitate TS formation decreasing
the energy required for conformational changes.

Figure 1. (a) Binding energy of L-Cu(II)-R to DNA1, BEMD, estimated at MD level; (b) C3-C2' distances in the
supramolecular L-Cu(II)-R / DNA1 structures optimized at level M. Red triangles represent pro-R (R1 & R2)
structures, blue circles are used for pro-S (S1 & S2) structures.
The next stage of our study was focused on modeling the mechanism of the intramolecular Friedel-Crafts
reaction. The simulations were performed with 12 initial L-Cu(II)-R / DNA supramolecular complexes, featuring
the 4 conformations of the L-Cu(II)-R complex and 3 intercalating positions, DNA_56, DNA_67, andDNA_67maj with L-Cu(II)-R intercalated between BP layers 56 (AT-AT) and 67 (AT-TA) with R on the minor
groove side and 67 (AT-TA) but with reactant on the major groove side of DNA. All initial L-Cu(II)-R / DNA
supramolecular complexes were subjected to C3-C2' bond formation TS search within the AFIR approach.
The first C3-C2’ bond formation stage of the reaction involving L-Cu(II)-R / DNA_56 complex with pro-S
conformation of the reactant was the most favorable within the whole set of data. It was characterized by a very
low C3-C2' bond formation TSII32' (DNA_56_S2_TSII32', 2.6 kcal.mol-1) leading to formation of a very stableintermediate (i.e. reverse reaction would not be favored or expected to occur). The following hydrogen transfer
stage was found somewhat high in energy even through a water molecule (Fig. 2). If two water molecules wereconsidered to take part in this stage, the barrier for proton abstraction from C2' (through TS
DNA_56_S2_TSIV32'ww, 25.3 kcal.mol-1) was decreased by 10.1 kcal.mol-1. This TS, however, was found toconnect to the relatively unstable intermediate structure DNA_56_S2_V32'ww (24.5 kcal.mol-1) in which theabstracted proton remained in the H3O+ moiety instead of being transferred to C2. Our attempts to locate the TS
for the next HT (from H3O+ to C2 or the carbonyl O) failed which may mean that the process was spontaneous orclose to barrierless.
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Figure 2. Energy diagram and intermediate and TS structures for the intramolecular Friedel-Crafts reaction in thecase of the pro-S L-Cu(II)-R(S2) / DNA_56 supramolecular complex: L = bipyridine, L1 =5,6-dimethylphenantroline. Important interatomic distances (in Å) are provided; blue color is used for the C-C
bond formation distances, red color for H-bonds. Solvating water molecules and charge compensating Na+ are notshown for simplicity.

Asymmetric phase-transfer catalysis with homo- and heterochiral quaternary ammonium salts
We also performed a thorough theoretical study of phase transfer quaternary ammonium catalysts designed
in Maruoka group in attempt to gain better understanding in the properties and catalytic behavior of the homo- andheterochiral forms of these systems. For this pupose, we modeled the interconversion of the homo / heterochiralforms of conformationally flexible catalysts, simulated and analyzed the 1H NMR spectra of chiral forms ofseveral different quaternary ammonium salts as well as their performance in asymmetric catalysis for theinteraction of the imine ester of glycine ester and benzyl bromide. Considering the complexity of the system andits flexibility as well as the fact that the catalyst does not participate actively in the catalyzed process but only
provides the local asymmetric environment via electrostatic and short-range interactions, we used AFIR method
for automated TSs search.
The conformationally flexible analog was found to easily undergo interconversion from the homo- to theheterochiral form driven by the higher thermodynamic stability of the heterochiral isomer and resulting inalternation in catalytic behavior. Theoretical calculations of 1H NMR spectra of the two isomers for different
model systems are in good agreement with the experimental data, allowing us to conclude that the up-field shift of3－ 124 －

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signals for the benzylic protons in the heterochiral form could be explained by increase in the shielding effect of
the aromatic parts of the system around these protons due to the conformational changes.

Figure 3. Summary of the experimental and theoretical results for asymmetric alkylation of glycine Schiff baseunder phase-transfer catalytic conditions.
By applying the automated TS search procedure for the alkylation of glycine derivatives catalyzed by thehomo- / heterochiral form of a conformationally rigid analog (Fig. 3), we were able to locate more than 40
configurations of possible TS structures. The homochiral form was theoretically confirmed to catalyze theformation of predominantly R-product of the reaction, while for the heterochiral form the catalytic activity was
found to depend on two factors: (i) formation of a tight ion pair between the catalyst and the glycine derivative,
which resulted in decrease in the reaction rate, in agreement with the experimental data, and formation of only the
R-product; and (ii) the possibility that the reaction occured without the initial formation of the ion pair or after its
dissociation, in which case the formation of S-product was predominant. The combined effects of both factors
could explain the lower reaction rate and the poor enantioselectivity observed experimentally for the heterochiralform.

2. Original papers(1) G. P. Petrova, H.-B. Li, K. Maruoka, K. Morokuma, “Asymmetric Phase-Transfer Catalysis with
Homo- and Heterochiral Quaternary Ammonium Salts: A Theoretical Study”
J. Phys. Chem. B, 2014, 118 (19), pp 5154–5167(2) G. P. Petrova, Z. Ke, S. Park, H. Sugiyama, K. Morokuma, “The origin of enantioselectivity for
intramolecular Friedel–Crafts reaction catalyzed by supramolecular Cu/DNA catalyst complex”
Chem. Phys. Lett., 2014, 600, pp 87–95.

3. Presentation at academic conferences
4. Others4－ 125 －

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Travis HARRIS
Travis HARRIS
Research Fellow, Fukui Kenichi Memorial Research Group 1
Research Fellow, Fukui Kenichi Memorial Research Group 1
1. Summary of the research of the year
I. Density Matrix Renormalization Group Calculations of Magnetic Exchange Coupling in
Dinuclear Transition Metal Complexes
The applicability of ab initio multireference wavefunction-based methods to the study ofmagnetic complexes has been restricted by the quickly rising active-space requirements ofoligonuclear systems and dinuclear complexes with S > 1 spin centers. Ab initio density matrix
renormalization group (DMRG) methods built upon an efficient parameterization of the correlation
network enable the use of much larger active spaces, and therefore may offer a way forward. In thisresearch, we applied DMRG-CASSCF to the dinuclear complexes [Fe2OCl6]2- and [Cr2O(NH3)10]4+.
After developing the methodology through systematic basis set and DMRG M testing, we exploredthe effects of extended active spaces that are beyond the limit of conventional methods. The
calculated exchange coupling constants (J of the Heisenberg spin-Hamiltonian H = -2JSASB) for[Fe2OCl6]2- from various methods with a triple-ζ ANO-RCC basis set are shown in Table 1. The J
values were derived from the lowest spin states, S = 0 and 1,
2Table 1. J values for [Fe2OCl6]
because the higher spin states were not significantly populated
from various methods
in the temperature-dependent magnetic susceptibility-1methodJ (cm )
experiments from which the J value was derived. We find that
CAS(10,10)SCF-39.7
CASSCF with the minimal active space, (10,10), gives theCAS(16,13)SCF-58.6
weakest magnetic coupling of −39.7 cm−1, just 34% of the
MRCI(10,10)-61.3
experimental value (-117 cm-1). Including O(2p) orbitals in
MRCI(16,13)-96.3(16,13) considerably strengthens the interaction to −58.6 cm−1.
MRCI+Q(10,10)-75.6
Further inclusion of the virtual double shell orbitals for Fe(d)MRCI+Q(16,13)-115.3and O(p) in DMRG(16,26) captures a major portion of theDMRG(16,16)[1000] -57.7
dynamic correlation effects, leading to an accurate reproduction
DMRG(10,20)[256]-49.0of the experimental value. The analogous active space for
DMRG(16,26)[∞]-117.4[Cr2O(NH3)10]4+ (12,32) also considerably improves upon theexp-117
small active space results. For comparison, we performedaM values are given in brackets, butconventional MRCI+Q calculations and the J values arethey can all be considered as consistent with those from DMRG-CASSCF. We also
saturated for the respective active
examined the full Heisenberg spin ladder and found that, inspaces; thus they are not responsible contrast to previous studies, the two studied complexes behave
for the differences in the listed similarly, with weaker magnetic coupling at higher spin states,
DMRG J values.
regardless of the computational method.

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II. Hydroboration Mechanism Revisited: Alkene Addition Partner Depends on Ligand andSubstrate
This investigation of Rh(I)-catalyzed hydroboration with pinacolborane (HBPin) was
prompted by an experimental finding that norbornene reacts faster than 1-octene, both yielding
alkyl boranes. The catalytic cycle is shown in Figure 1. Addition of the alkene can occur througheither an H migration or a B migration path followed by reductive elimination with C-B or C-H
bond formation, respectively. The alkene addition partner (the migrating species) is typicallyconsidered to be the hydride, which leads to C-B reductive elimination. This reductive elimination
step is expected to be rate limiting, and to have a lower barrier for the primary alkyl (octyl) than thesecondary alkyl (norbornyl); thus, the hydroboration of norbornene may proceed through a different
mechanistic pathway.

Figure 1. Catalytic cycle for Rh(I)-catalyzed hydroboration.
To determine why the hydroboration reaction is faster for norbornene than 1-octene, thecatalytic cycles for RhCl(DiPPE) (DiPPE = 1,2-bis(diisopropylphosphino)ethane) were calculated－ 127 －

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Ⅳ 研究業績 (2013)at the B3LYP/6-31G(d) level. 1-octene was modeled as propene, whereas norbornene was nottruncated. For propene, H migration was rate limiting with a 20.2 kcal/mol barrier. The alternative
pathway was less favorable with a B migration barrier of 23.3 kcal/mol followed by a rate-limiting
reductive elimination step (23.6 kcal/mol). For norbornene, B migration had a lower barrier (18.4
kcal/mol) than H migration (25.1 kcal/mol), and both were the rate limiting steps in their respective
paths. Thus, the addition partner is the hydride for propene, and BPin for norbornene. These two
mechanisms are compared in Figure 2, which shows that norbornene has a lower rate-limiting
barrier (18.4 kcal/mol) than propene (20.2 kcal/mol), as expected based on the experimental
reaction rates.
In addition to the substrate dependence, the mechanisms are significantly affected byvarying the ligand. Calculations with 1,2-bis(dimethylphosphino)ethane (dmpe) showed that theadditionpartneristhehydridefor
bothsubstrates,
whereaswith
1,2-bis(ditertbutylphosphino)ethane (dtbpe) the addition partner is BPin for both. In summary,bulky ligands and norbornene both favor pathways in which BPin is the addition partner.

Figure 2. Free energy profiles of Rh-catalyzed hydroboration of propene and norbornene.

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III. AFIR Study of [2Fe-2S] Cluster Degradation by NO[Fe-S] clusters are biological targets of NO that disassemble, producing dinitrosyl ironcomplexes (DNICs), which are known to affect vasodilation, enzymatic activity, and otherbiological processes. To investigate the mechanism of [2Fe-2S] cluster degradation by NO,
TPSSh/TZVP calculations for all possible reactions after addition of each NO molecule werecarried out. The AFIR method was employed for a thorough assessment of the initial NO binding.
Figure 3 shows the free energy profile for this initial binding process. The most favorable pathway
involves NO insertion into an Fe-S bond, producing the intermediate EQ2. From here, a second NO
can bind, resulting in cleavage of the Fe-S(NO) bond, followed by loss of SNO. The formation of
two equivalents of DNIC products [FeCl2(NO)2]- thus requires 6NO, as two NO are involved information and dissociation of SNO. The full, detailed mechanism is currently in progress.

Figure 3. Free energy profile of NO binding to [Fe2S2Cl4]2-.
2. Original papers(1) Harris, T. V.; Kurashige, Y.; Yanai, T.; Morokuma, K.
“Ab Initio Density Matrix Renormalization Group Study of Magnetic Coupling in
Dinuclear Iron and Chromium Complexes”
J. Chem. Phys. 2014, 140 (5), 054303 (10 pages)(2) Harris, T. V.; Szilagyi, R. K.
“Iron-Sulfur Bond Covalency from Electronic Structure Calculations for ClassicalIron-Sulfur Clusters.”
J. Comput. Chem. 2014, 35 (7), 540-552－ 129 －

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Ⅳ 研究業績 (2013)(3) 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. 2013, 52 (15), 8551-8563
5. Others(1) Harris, T. V.; Kurashige, Y.; Yanai, T.; Morokuma, K.
“Ab Initio Density Matrix Renormalization Group Study of Magnetic Coupling in
Dinuclear Iron and Chromium Complexes” (Poster)
11th FIFC Symposium (2014).

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Miho
MihoISEGAWA
Isegawa
Research
Fellow
Research Fellow
1. Photodissociation of nitromethane
Photodissociation pathways of nitromethane following π  π* electronic excitation areinvestigated. The potential energy surfaces for four lowest singlet states are explored, and structures ofmany intermediates, dissociation limits, transition states and minimum energy conical intersections were
determined using the automated searching algorism called the global reaction route mapping (GRRM)
strategy. Geometries are finally optimized at CASSCF(14e, 11o) level and energies are computed at
CAS(14o,11e)PT2 level. The calculated preferable pathways and important products qualitatively
explain experimental observations. The major photodissociation product CH3 and NO2 (2B2) is formed bydirect dissociation from the S1 state. Important pathways involving S1 and S0 states for production ofvarious dissociation products CH3NO + O (1D), CH3O(X2E) + NO (X2Π), CH2NO + OH and CH2O +HNO, as well as various isomerization pathways have been identified. Three roaming processes also
have been identified: the O atom roaming in O dissociation from CH3NO2, the OH radical roaming in
OH dissociation from CH2N(O)(OH), and the NO roaming in NO dissociation from CH3ONO.

Fig. 1 S3 (black), S2 (green), S1(red), and S0 (blue) potential energy profiles (in kcal/mol) calculated at the
MS-CAS(14e,11o)PT2/6-311++G**//CASSCF(14e,11o)/6-31G* level. There are one S3/S2 (ocher), one S2/S1(cyan) and five S1/S0 (purple) minimum energy conical intersections (MECIs). Two energy values are given foreach CI; one for the upper state and the other for the lower state. Label of transition state (TS) is given by red andlabel of minimum (MIN) is given by black. The horizontal bar in side of S3/S2-I1 means S3 minimum is the samestructure as S3/S2-I1. The grey lines in the middle show energy of 193nm photon, 148.1 kcal/mol, and calculated
vertical excitation energy S3//S0-I1. IRC paths given by dotted line are above the energy of 193 nm photon.

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2. CASPT2 study of reaction paths starting from N(2D) + H2NO
We investigated reaction paths staring from N(2D) + H2O for doublet spin states, D0 and D1. The
potential energy surfaces are explored in an automated fashion using global reaction root mapping method(GRRM). The energy paths are confirmed by intrinsic reaction coordinate at the CASPT2 level taking fullvalence electrons in the active space. Three roaming processes, two roaming dissociation and one roamingisomerization; (1) H2NO  NOH--H  NO + H2, (2) cis-HNOH  HNO--H  H--HNO  H2 + NO, (3)H2NO  H--HNO  HNO--H  cis-HNOH, are confirmed at the CASPT2 level. Some analogies with
H2CO system are observed for the structure in the roaming. The two roaming dissociations (1) and (2) shouldplay important role to understand the reaction products, NO(2Π) + H2.

Fig. 2 Potential energy diagram of D1 and D0 for reactions starting from N(2D) + H2O on D1 and D0 PESs. Both ofstructure and energy are determined at MS-CAS(13e,10o)PT2/cc-pVTZ level. This diagram includes four D1/D0
conical intersections, D1/D0-MX1, MX2, MX3 and MX4. Label of transition state (TS) is given by red and labelof minimum (MIN) and conical intersection (MECI) is given by black. Critical points which relate to roaming
process are marked with shadow circle.

3. Predicting pathways for terpene formation from first principles – routes to known and newsesquiterpenes
The Artificial Force Induced Reaction (AFIR) method is applied to predict cyclization/rearrangement
pathways for carbocation precursors to sesquiterpenes. This method captures many of the features revealed inprevious studies as well as new ones, including a pathway to a sesquiterpene not yet isolated in nature that wesuspect will be in time.

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Figure 1. Reaction network arising from A1 computed by mpW91PW91/6-31+G(d, p). Relative energies are shown inkcal/mol including zero point energy corrections. All of structures shown are newly found in this paper by quantum
chemistry method, except for A1 and B, given in italic, that are known previously. The pathways particularly focused inthis paper are marked with stars.

h of

D0

bel

4. Ring opening-closing mechanism of diarylethene induced by UV-visible photon: potential energy
surface aapping by spin-flip time dependent density functional theory
Reaction mechanisms of laser induced ring opening and closing transformation are investigated fordiarylethene (DAE) which works as a molecular switch and photo device. Spin-flip time dependent density
functional theory is employed to reveal the reaction mechanism of the model system for three isomers,
normal, inverse, and mixed types. The reaction mechanisms we proposed based on potential energy mapping
and the intrinsic reaction coordinate (IRC) qualitatively explain the different quantum yields (QYs) for eachtype reported by Feringa’s group.

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Fig 6 Contour map of S0(root1) and S1(root3) for (a) normal, (b) mixed, and (c) inverse type.
Root1(mainly S0), root2(mainly T2) , and root3 (mainly S1) from left to right.

5. Original paper
Miho Isegawa, Satoshi Maeda, Dean J. Tantillo, and Keiji Morokuma, “Predicting pathways for
terpene formation from first principles – routes to known and new sesquiterpenes”, Chemical Science,
5, 1555 (2014).

6. Presentation at academic conferences(1) Miho Isegawa, Fengyi Liu, Satoshi Maeda, Keiji Morokuma,“Ab initio reaction paths of nitromethane”,
The 7th Annual Meeting of Japan Society for Molecular Science, 2013
(2) Miho Isegawa, Satoshi Maeda, Dean J. Tantillo,“Predicting pathways for terpene formation from first principles -routes to known and new sesquiterpenes”,
The 11th FIFC Symposium, 2014

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Ⅳ 研究業績 (2013)

W. M. C. SAMEERA
W. M. C. Sameera
Research
Fellow,
Fukui Kenichi
Memorial
Group 1
Research Fellow, Fukui
KenichiMemorial
Research
GroupResearch1
1. Summary of the research
Computational studies of fluorescent probes
Fluorescent compounds are powerful tools to visualize biological events in living cells andorganisms. Small fluorescent compounds can be used as fluorescent probes, and they show a changeof fluorescence properties in the presence of their target molecule (Figure 1a). There is a significant
interest to design fluorescent probes for biological research, diagnosis, and treatment of diseases.
Our focus in this study is two fluorescent compounds, TokyoMagenta (2-Me TM) and TokyoGreen(2-Me TG) (Figure 1b). The 2-Me TM system exhibits a large red-shift of the absorption spectrum
upon deprotonation at basic conditions. Fluorescence intensity of the anion form of 2-Me TM issignificantly larger than that of the neutral form. Therefore, 2-Me TM can be used as a fluorescenceprobe. In this study, we use computational methods to understand photophysical behaviours of
2-Me TM and 2-Me TG.

f)

b
)
R

ta
r
g
e
tm
o
le
c
u
le
Targetmolecule

X

flu
o
r
e
s
c
e
n
tp
r
o
b
e
(
s
ig
n
a
lO
ffs
ta
te
)
Fluorescent
probe(signal “off” state)

flu
o
r
e
s
c
e
n
tp
r
o
b
e
(
s
ig
n
a
lO
n
s
ta
te
)
Fluorescent
probe(signal “on” state)

H
O

O

2-Me TG (R = Me)

O
OH

S
i

O

2-Me TM (R = Me)(a)(b)
Figure 1. (a) Schematic representation of fluorescent probes. (b) Molecular structures ofTokyoGreen (TG) and TokyoMagenta (TM).
In photochemical reactions, nonadiabatic transitions occur through the conical intersections (CIs).
A CI is an f-2 dimensional intersection hyperspace between two or more potential energy surfacesof the same spin and space symmetry (f = the number of degrees of freedom). In the absence of
low-energy a CI(s), nonradiative decay pathway becomes slower, and exhibits a high fluorescencequantum yield. In this project, I calculate S0/S1 minimum energy conical intersections (MECIs) of
TM and TG with the spin-flip time-dependent density functional theory (SF-TDDFT) method in
combination with the anharmonic downward distortion following (ADDF) method. I havesystematically analysed possible S0/S1 MECIs of TokyoGreen and TokyoMagenta (model
systems), and identified the lowest energy MECIs (Figure 2). Calculated potential energy surfaces
are qualitatively similar for the both systems. The most striking difference is the barrier for goingfrom S1 equilibrium structure to S0/S1 MECI. In the case of 2-Me TG model system, S1
equilibrium structure is 68.6 kcal mol-l higher in energy, and S0/S1 MECI is further 19 kcal mol-lhigher in energy. This barrier becomes 23.4 kcal mol-1 for 2-Me TM model system, and therefore－ 135 －

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the nonradiative decay pathway is relatively difficult. This is in an agreement with theexperimental observations. My future studies of this project will be focused on more complex
fluorescent compounds. Our ultimate goal is to design fluorescent probes with very highfluorescence quantum yield.
Lowest&energy&MECI&

Rela‐ vely&high2energy&MECIs&(+87.6) S0 /S1 MECI

+96.1((+19.0)(+68.6) S1+102.7((+73.2) S0 /T1 MECI+110.8(

+46.0

+71.1

(+44.1) T1

-O

O

O

+117.0(Model&system&+117.3(

Energies(are(in(kcal(mol/1((0.0) S0(a)
Lowest&energy&MECI&

Rela‐ vely&high2energy&MECIs&(+86.3) S0 /S1 MECI

+99.5(+23.4(+23.9)(+62.9) S1+101.3((+61.1) S0 /T1 MECI+112.0(

+37.8

+64.0

(+36.3) T1
-O

Si

O

Model&system&(0.0) S0

Energies(are(in(kcal(mol/1(+115.5((b)
Figure 2. Calculated S0/S1 MECIs of (a) TokyoGreen, and (b) TokyoMagenta (model systems). The
BHandH functional was used in all calculations.
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Computational studies of transition metal homogeneous catalysis
Transition metal homogeneous catalysis is an efficient way to perform catalytic reactions in a
selective fashion. Quantitative mechanistic and selectivity details are very important to develop
more efficient catalysis. The emergence of computational methods over the past two decades meansthat these properties can now be computed within the vicinity of chemical accuracy.

Figure 3. (a) Asymmetric Mukaiyama aldol reaction of silicon enolates with aldehydes catalysed bychiral Fe(II) complex, (b) electronic structure of [FeII(L1)(DME)(H2O)]2+ complex, (c) computed
catalytic cycle [AFIR calculations: ONIOM(B3LYP-D3/LanL2DZ:PM6-D3). Structure
optimizations: B3LYP-D3 functional, SDD for Fe, 6-31+G for O and N, 6-31G(d) for other atoms].
I study the asymmetric Mukaiyama aldol reactions of Kobayashi and co-workers. In their approach,reaction of silicon enolates and aldehydes is catalysed by a chiral a Fe(II) complex to afford thedesired aldol product in a high yield and high diastereo- and enantioselectivity (Figure 3a). This
reaction proceeds in the presence of water at 0 0C. They have used Brønsted acids and bases as
efficient additives to increase the enantioselectivity of the reaction. My objective in this project is todevelop a full catalytic cycle for the reaction, and explain the diastereo- and enantioselectivities.
Electronic structural analysis of the [FeII(L1)(DME)(H2O)]2+ complex rationalized three important
ligand field states (Figure 3b). Of these, thermodynamically stable electronic state is the quintet,
while the triplet and single electronic states are significantly higher in energy. Similar trend can beobserved for all seven-coordination Fe(II)-based complexes in this study, which suggests the－3－－ 137 －

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single-state reactivity. I have analysed the possible intermediates in the solution, and identified alow-energy pathway leading to the product (Figure 3c). According to the calculated catalytic cycle,
selectivity-determining step of the mechanism is the carbon-carbon bond formation step (TS3-4).

Development of Gau_mopac2012 algorithm
In this project, I have been implementing the Gau_mopac2012 algorithm to perform
ONIOM(QM:QM) calculations in combination with the Gaussian09 and Mopac2012 programmes.
The ONIOM(QM:QM) implementation in Gau_mopac2012 supports for various semi-empiricalmethods available in the mopac2012 program. The Gau_mopac2012 package has three modules,
namely ext_mopac, make_inp, and make_out to automate the overall mechanism shown in Figure 4.

Gau_mopac2012!

Start!

ext_mopac!

Gaussian 09!

EIn le!

!

Keywords:!
!

External=“ext_mopac” !
Opt = NoMicro !
EOu le!

End!

!

File management!
Call make_inp and make_out
modules!
Call Mopac2012!
make_out!
module!

make_inp!
module!

Energy! Mopac2012!
Gradients!
!
Hessian!
Methods:!

input!
le!

PM7
PM6
PM3
MNDO
AM1
RM1
etc.

(“-D3” is available)

Figure 4. ONIOM(QM:QM) implementation in the Gau_mopac2012 algorithm.
The Gau_mopac2012 algorithm can be activated by using the external="ext_mopac" keyword in
the Gaussian09 input file. Then the Gaussian09 programme provides text files with the EIn
extension, and these files contain Cartesian coordinates and connectivity details of the atoms (bothreal and model systems). After that, make_inp module refers the information in EIn files to setup
input files for the Mopac2012 and run Mopac2012 program. Finally, the make_out module reports
energy and derivatives into a standard text file with the EOu extension, which can be recovered by
the Gaussian09 programme.
2. List of original papers
1. W. M. C. Sameera, F. Lui, S. Maeda, K. Morokuma, “Spin-flip time-dependent density
functional theory (SF-TDDFT) study of TokyoMagenta (2-Me TM) and TokyoGreen (2-MeTG)”. (In preparation)
2. J. Llaveria, Á. Beltrán, W. M. C. Sameera, A. Locati, M. M. Díaz-Requejo, M. I. Matheu, S.
Castillón, F. Maseras, P. J. Pérez, “Regio- and Stereoselective Silver-catalyzed aziridinationof dienes: scope, mechanistic studies and ring-opening reactions”, J. Am. Chem. Soc. 2014,－4－－ 138 －

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Ⅳ 研究業績 (2013)

136, 14, 5342-5350.
3. E. M. Zueva, R. Herchel, S. Borshch, E. V. Govor, W. M. C. Sameera, R. McDonald, J.
Singleton, Y. Sanakis, J. Krzystek, J. E. McGrady, and R. G. Raptis. Double exchange in amixed-valent octanuclear iron cluster, [Fe8(μ4-O)4(μ-4-Cl-pz)12Cl4]−, Dalton Trans. 2014 (Inpress) [This article is part of themed collection: Synergy between Experiment and Theory]
4. L. Maestre, W. M. C. Sameera, M. M. Díaz-Requejo, F. Maseras, P. J. Pérez. “A General
Mechanism for the Copper- and Silver-Catalyzed olefin aziridination reactions: concomitant
involvement of the singlet and triplet pathways”, J. Am. Chem. Soc. 2013, 135, 1338-1348.
5. I. Rivilla, W. M. C. Sameera, E. Alvarez, M. M. Díaz-Requejo, F. Maseras, P. J. Pérez,Catalytic cross-coupling of diazo compounds with coinage metal-based catalysts: anexperimental and theoretical study. Dalton Trans. 42, 4132-4138, 2013. [This article is part ofthemed collection: Mechanistic Organometallic Chemistry]
3. List of presentations at meetings.
1. W. M. C. Sameera, F. Maseras, DFT and DFT/MM methods for mechanistic and selectivity
studies of transition metal homogeneous catalysis. The 10th FIFC Symposium, Kyoto University.
(Poster, 2014)
2. Development of hybrid methods for the study of photon-driven processes of interstellar ices. The
chemical cosmos annual meeting, Windsor, United Kingdom. (Talk, 2013)
3. Density functional theory and density functional theory/molecular mechanics methods formodern homogeneous catalysis, University of Gothenburg. (Talk, 2013)－5－－ 139 －

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Julong JIANG
Julong JIANGSPR Fellow
SPR Fellow(From 1st, March, 2014)
Research Topics
1. Theoretical investigation on the Pd-catalyzed C(sp3)-H activation in the synthesis of
unnatural amino acids
In the past several decades, the dominant strategy in the organic synthesis to form a C-C bondwas through the transition metal catalyzed C-C coupling reactions. However, in most cases, aspecial starting material is required for the coupling reaction, for example, the boronic ester
employed in the Suzuki reaction. It is not straightforward to synthesize those precursors andthose reactions suffer from the decomposing of the reaction precursors. In recent years, people
turned the focus to the direct C-H activation, which has the potential to be a general andpowerful tool in the future’s organic chemistry. The Yu’s group in the Scripps research
institute has reported a series of direct C-H activation reactions. Among them, a recent paper,
which was published on Science, has the most exciting result as a direct C-H activation on sp3
carbons. (Yu et al., Science, 2014, 343, 1216).

Scheme 1 The Pd-catalyzed direct C(sp3)-H activation
Not only for the primary C(sp3)-H bond, by carefully choosing a ligand, a secondary C(sp3)-H
bond can also be activated for further C-C bond formation in a stereo-selective manner.

Scheme 2 Asymmetric C-C coupling reaction on the secondary sp3-carbon atom
However, as a pure synthetic publication, no details was given to discuss the mechanism.
Thus, we decide to carry out a theoretical investigation on this reaction, in order to reveal the－ 140 －

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Ⅳ 研究業績 (2013)mechanism for a general improvement of this reaction. Once the mechanism is unveiled, it
will helpful to make the reaction as a general and effective strategy to functionalize a
sp3-carbon atom, which is pursued by most of organic chemists.
We have already proposed a mechanism as the model for our calculations. It seems that thepalladium in this reaction goes through a Pd(II)-Pd(IV)-Pd(II) catalytic cycle, which is
uncommon.

Scheme 3 Proposed mechanism forPd(II)-Pd(IV)-Pd(II) cycle is involvedtheC(sp3)-H

activation

in

which

a

2. Mechanistic study on the metal-free C-H activation by using a hyper-valent iodine(III)reagent
Despite the transition metal catalyzed C-H activation, the organic chemists also started to seek
alternative methods to facilitate the C-H bond cleavage in a more economical way. The
Maruoka group in Kyoto university recently discovered a metal-free C-H activation which isvalidated by the using of hyper-valent iodine(III) reagent in a site-selective manner (Angew.
Chem. Int. Ed., 2013, 52, 8657). The hyper-valent iodine reagent has been employed inorganic synthesis for a long period as an oxidant, which is related to the Dess-Martin reaction.
However, it is novel to use the hyper-valent iodine reagent for the C-H activation purpose.

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Ⅳ 研究業績 (2013)

I(III) Reagent (1.5 equiv)tBu-OOH (1.5equiv)
tBu

O

O

+

tBu

MeCN
0 oC, 30 min

tBu

ketone_3

ketone_4

Major

Minor

Good Site-Selectivity,
Ratio of ketone_3 to ketone_4 up to 4.6:1
Various iodine(III) reagents were tested.
HO

AcO

I O

I

Me3SiO

OAc

I

O

CF3

Me3SiO

I

OTf

O

O
1

3a

2

8%

36%
AcO

I

OTf

TfO

I

OTf

O
Ph P O
OTf
I
Ph

3d

3c
40%

3b

29%

18%

11%

BEST
51% yield
3e (3.9:1)

51%

Scheme 4 The activation and oxidation of C-H by hyper-valent iodine (III) reagent
Not only for the oxidation of alkane, the hyper-valent iodine reagent is also reported as areactive catalyst to promote the formation of acyl radicals without decarbonylation (Nature
Chem., 2014, submitted manuscript).

Scheme 5 The hyper-valent iodine (III) promoted formation of acyl radical and thefurther addition to an alkene
A hypothetical hyper-valent iodine has been proposed by the Maruoka group to rationalize theexperimental observations. Therefore, our research will be focus on theoretically testing the
proposed mechanism in which a hypothetical iodine radical is involved, and propose
alternative mechanism if necessary.

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Ⅳ 研究業績 (2013)

Shinichi YAMABE
Shinichi

Yamabe

FIFC Fellow,
KenichiMemorial
Research
2
FIFC Fellow,
KenichiFukuiFukui
Memorial
Researchgroupgroup2
1. Summary of the research of the year
(1-1)

Proton Transfers in the Strecker Reaction Revealed by DFT Calculations

The Strecker reaction of acetaldehyde, NH3, and HCN to afford alanine was studied by DFT
calculations for the first time, which involves two reaction stages.

In the first reaction stage, theamino-nitrile was formed. The rate-determining step is the deprotonation of the NH3+ group in
MeCH(OH)-NH3+ to form 1-amino-ethanol, which occurs with an activation energy barrier (E≠) of
9.58 kcal/mol. The stereochemistry (R or S) of the product amino-nitrile is determined at the NH3
addition to the carbonyl carbon of the aldehyde.

While the addition of CN¯ to the carbon atom of

the protonated imine (7) appears to scramble the stereochemistry, the water cluster above the imine
plane reinforces the CN¯ to attack the imine group below the plane. The reforcement hinders thescrambling. In the second stage, the amino-nitrile transforms to alanine, where an amide
Me-CH(NH2)-C(=O)-NH2 is the key intermediate. The rate-determining step is the hydrolysis of the
cyano group of N(amino)-protonated amino-nitrile which occurs with an E≠ value of 34.72
kcal/mol. In the Strecker reaction, the proton transfer along hydrogen bonds plays a crucial role.

(1-2) Substrate dependent reaction channels of the Wolff-Kishner reaction; A theoretical
study
Wolff-Kishner reduction reactions were investigated by DFT calculations for the first time.
B3LYP/6-311+G(d,p) SCRF=(PCM, solvent=1,2-ethanediol) optimizations were carried out. To checkthe role of the base catalyst
hydrazine(H2N-NH2)

andthe base-free reaction was examined by the use of acetone,(H2O)8.

A

readyreactionchannelofacetone->

acetonehydrazone(Me2C=N-NH2) was obtained. The channelinvolves two likely proton-transfer routes.
However, the base-free reaction was found to be unlikey at the N2 extrusion step from the isopropyl－ 143 －

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Ⅳ 研究業績 (2013)

diimine intermediate(Me2C(H)-N=H-H).
Two base-catalyzed reactions were investigated by models of the ketone, H2N-NH2 and OH-(H2O)7.
Here, ketones are acetone and acetophenone.

While routes of the ketone -> hydrazone -> diimine

aresimilar, those from the diimines are different. From the iso-propyl diimine,the N2 extrusion and theC-H bond formation takes place concomitantly.The concomitance leads to the propane productconcertedly.

From the(1-phenyl)ethyl substituted diimine, a carbanion intermediate is formed.

Thepara carbon of the phenyl ring of the anion is subject to the protonation, which leads to the a3-ethylidene-1,4-cyclohexadiene intermediate. Its[1,5]hydrogen migration gives the ethylbenzene
product.

For both ketonesubstrates, the diimines undergoing E2 reactions were found to be key

intermediates.

(1-3) A DFT computational study of SN1-SN2 and SN2-SN3 mechanisticchanges in hydrolyses of benzyl chlorides and benzenesulfonyl chlorides
B3LYP/6-311(+)G(d,p) calculations of hydrolysis reactions of benzyl chlorides and benzenesulfonyl
chlorides were performed. A reaction of methyl chloride was also examined as a standard of a neutral SN2
reaction. Transition states (TSs) of Ph-CH2Cl + (H2O)n with n= 6, 9, 11, 17, 23 and 29 were obtained
under the SCRF=(PCM, solvent=acetone). The variation of n corresponds nearly to that of molar fractions in
the water-acetone binary solvent.
structures was examined with n=17.

For benzyl chlorides,

the effect of para-substituents (Zs) on those

For Z = O2N, Cl, H and H3C, paths of concerted bond interchanges

leading to the benzyl alcohols were obtained. In contrast, for Z=MeO, a stepwise path invloving a carbocation(MeO-C6H4-CH2+) or "solvent separated ion pair" was calculated.
Although the central carbons of benzyl chlorides are primary, the mechanistic change ("SN2-SN1") suggested
experimentallywasobtained.

Sameanalyses

were

made

for

benzenesulfonyl

chlorides(para-Z-C6H4-SO2-Cl). For all substituents (Zs) and the number of water molecules (n), concerted paths
were found. For the combination of the small n value and the electron-withdrawing group, the general basecatalysis by the second H2O molecule is enhanced. The enhancement would correspond to the SN2-SN3
Mechanistic change.
.

2

Original Papers(1) "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.
(2) "Three Competitive Transition States at the Glycosidic Bond of Sucrose in Its
Acid-Catalyzed Hydrolysis",
Shinichi Yamabe, Wei Guan and Shigeyoshi Sakaki－ 144 －

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Ⅳ 研究業績 (2013)

J. Org. Chem., 2013, 78 (6),(3)

2527-2533.

"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.

(4)"Interest in new heterodinuclear transition-metal/main-group-metal
complexes: DFT study of electronic structure and mechanism offluoride sensing function",
Wei Guan, Shinichi Yamabe and Shigeyoshi Sakaki,
Dalton Trans., 2013, 42, 8717-8728, DOI: 10.1039/C3DT50597A(5)"Substrate dependent reaction channels of the Wolff-Kishner
reduction reaction: A theoretical study",
Shinichi Yamabe, Guixiang Zeng, Wei Guan, Shigeyoshi Sakaki
Beilstein Journal of Organic Chemistry 2014, 10, 259-270.

(5)"A DFT Study of the Triplet Excited States of Iridium(III)Complexes with Terpyridine Ligands",
Naokazu Y., Shinichi Y.,*, Shigeyoshi S., Nobuko K.,
Tsuyoshi I., and Hiroshi T.,
Canadian Chemical Transactions, 2014, vol.2, issue 2, 134-148.

(6)"SN1-SN2 and SN2-SN3 mechanistic changes revealed by transition
states of the hydrolyses of benzyl chlorides and benzenesulfonyl chlorides",Shinichi Yamabe, Guixiang Zeng, Wei Guan and Shigeyoshi Sakaki,
Journal of Computational Chemistry,
pages 1140-1148 (2014),

vol.35, issue 15,

DOI: 10.1002/jcc.23607.

2. Presentation at academic conference“Proton transfers in some organic reaction pathways”,
July 24, 2013, The 11-th Fukui Center seminar
At Fukui Institute for Fundamental Chemistry, Kyoto University.

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土方
�方

優
�

FIFC フェロー

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、配位不飽和サイトと呼ばれる金属部位とガス分子の吸着相互作用に関する研究、およびその相互作用と構造から生み出されるガス分子の選択的吸着機構の解明に関する研究を行った。
䛆ጞ䜑䛻䛇㻌
多孔性配位高分子（PCPs: Porous coordination polymers）は金属イオンを有機配位子が架橋した無限構造を有した結晶性の物質群であり、生み出される骨格中には規則正しく並んだ空孔が存在している。その骨格や空孔を利用し、ガス貯蔵、ガス分離、触媒、光応答や磁性など様々な機能に関する研究が行われている。貯蔵に関してはガス分子の貯蔵可能な空隙が多く、捕捉されるガス分子と骨格との相互作用が強ければより有望な材料となりうる。一方で分離においては、あるガスに対して骨格からの相互作用が強い場合は、その他のガスに対してもその相互作用は強く働くことが多く、特定のガス分子に対してのみ強い相互作用を発現するような設計は容易ではない。本研究では PCPs の設計性の高さと構造の柔軟性を利用した self-accelerating という新しい分離機構を提案
し、さらに PCPs 中における相互作用部位とガス分子が相互作用した際に受ける影響を明らかにすることを目的とし理論計算によるアプローチを試みた。
䛆ィ⟬䚸⤖ᯝ䚸⪃ᐹ䛇
図 １ に 示 し た
kagomé 型層状骨格の[Cu(aip)]n （ aip=5-azidoisophthalate）
は、相互作用サイトとして paddle-wheel 型の潜在的な銅配位不飽
和サイト（Cu-OMS）を有している。この[Cu(aip)]n は分子物性（図１）対象とした PCP とその計算モデルの似通った CO と N2 に対し CO の高い選択性を有している事が実験によって見出された。一般にCO と N2 は分子サイズ、電子数、沸点、臨界温度、臨界圧など多くの性質が似ており、CO/N2 の分離は容易ではない。結晶構造解析によって CO の Cu-OMS への配位が確認されており、図１に示すようなモデルで CO と N2 の Cu-OMS への相互作用エネルギーの評価を行ったところ、
SCS-MP2/TZ//M06L/TZ レベルでそれぞれ-20.4 kJmol-1 と-13.0 kJmol-1 であった。同様の Cu-OMS
ユニットを有する HKUST-1 など他の PCPs では、このような CO/N2 における CO の選択性が見られないことから、この選択性は相互作用エネルギーの違いによるものではないことが示唆された。

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Ⅳ 研究業績 (2013)

この選択性の原因の一つは、ガス分子吸着前の Cu-OMS には隣接層のカルボキシレートの酸素が配位しており、N2 ではこの Cu-O 結合を切断することができない一方で、配位可能な CO の場合にのみ結合開裂を伴った吸着が起きるためと考えられる。CO が配位した後に注目すると、細孔内へのガス分子の拡散における障壁は理論計算から、100kJmol-1 以上の障壁であることが明らかとなった。つまり、CO, N2 どちらも拡散が困難である。仮に、非配位 N2 が配位 CO と交換した場合、上に示した相互作用のエネルギー差から不安定化するため、非配位 N2 と配位 CO の交換はやはり困難である。一方で、非配位 CO が配位 CO と交換した場合、エネルギー的損失は無くこの障壁を回避して細孔内への拡散が可能となり、CO のみの選択的な拡散が進行すると考えられる。相互作
用 部 位 を 骨 格 中 に 構 築 し 、 PCPs の 持 つ 柔 軟 性 と い う 特 徴 を 組 み 合 わ せ た PCP に お け る
self-accelerating という新しい分離機構を理論計算と組み合わせることで提案した。
さらに、上記の機構において重要となるのは CO が Cu-OMS と穏和な相互作用をするということである。一般に CO が金属に配位したカルボニル錯体では金属–CO 間の相互作用は強いことが知られている。これは Dewar–Chatt–Duncanson モデルおけるσ–donation とπ–back donation に
よって説明されており、CO の lone pair のσ–donation による金属への配位と同時にπ–backdonation によって CO の反結合性π*軌道への電子の流入が起き、金属–CO 間の結合が補強されるためである。このとき、CO の反結合性π*軌道への電子の流入によって C–O の結合は弱くなり、
低波数シフトする事も知られている。しかし、 [Cu(aip)]n では CO 伸縮の高波数シフトが観測され、モデル計算でも同様に高波数シフトを示した。Cu–CO におけるσ–donation とπ–back donationの量はそれぞれ 0.320 e と 0.034e であり、ほとんどπ–back donation が起きず適度な結合力によって Cu–OMS は CO を捕捉し CO 同士の交換を可能としていることを明らかにした。
しかし、π–back donation
はあくまでも CO の反結合性
π*軌道への電子の流入であり、観測される CO 伸縮は低波数シフトを示すはずである。一方で観測されたのは高波数シフトであり、その高波数シフトの原因を明らかにするため、Cu–OMS によって形成される静電場に注目（図 2）電荷が存在する時の CO の各軌道の電子密度の変化

した。図 2 に示したように、Cu-OMS の Cu の正電荷+q によって CO の電子密度の変化が誘起され、CO の結合領域の電子密度（t）が増加していることがわかる。この CO 結合領域の電子密度の増加によって高波数シフトが誘起されていることを明らかにした。さらに、各軌道の電子密度の増減をみると、CO のπ軌道の電子密度の変化を示す(5, 6)からπ電子が正電荷側に引き寄せられていることがわかる。一方、σ軌道の変化の和、lp+σは減少しており、π軌道の電子の結合領域への偏りによって CO の高波数シフトが誘起されているという事を明らかにした。一般に、PCPs の吸着測定では前処理として加熱するため単結晶性を保持するのは難しい。そのため、このような OMSs とガス分子の相互作用に関して、分光スペクトルの解釈において、細孔が形成する場の重要性を示すものと言える。

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2. ��(1) Shin-ichiro Noro, Katsuo Fukuhara, Yuh Hijikata, Kazuya Kubo and Takayoshi
Nakamura“Rational synthesis of a porous copper (II) coordination polymer bridged byweak Lewis-base inorganic monoanions using an anion-mixing method”
Inorg. Chem., 52, 5630-5632 (2013)(2) Hiroyuki Nakashima, Yuh Hijikata, and Hiroshi Nakatsuji“Solving the non-Born-Oppenheimer Schrödinger equation for the hydrogenmolecular ion with the free complement method II. Highly accurate electronic,
vibrational and rotational excited states”
Astrophys. J., 770, 144-1-9 (2013)(3) Yasuko Mito-oka, Satoshi Horike, Yusuke Nishitani, Tadao Masumori, Munehiro
Inukai, Yuh Hijikata, and Susumu Kitagawa“Siloxane D4 capture by hydrophobic microporous materials”
J. Mater. Chem. A, 1, 7885-7888 (2013)(4) Shin-ichiro Noro, Katsuo Fukuhara, Kunihisa Sugimoto, Yuh Hijikata, Kazuya
Kubo, and Takayoshi Nakamura“Anion-dependent host-guest properties of porous assemblies of coordination
complexes (PACs), [Cu(A)2(py)4] (A = PF6, BF4, CF3SO3, and CH3SO3; py = pyridine),
based on Werner-type copper (II) complexes in the solid state”
Dalton Trans., 42, 11100-11110 (2013)(5) Hiroshi Sato, Wataru Kosaka, Ryotaro Matsuda, Akihiro Hori, Yuh Hijiakta,
Shigeyoshi Sakaki, Masaki Takata, and Susumu Kitagawa“Self-accelerating CO sorption in a soft nanoporous crystal”
Science, 2014, 343, 167-170 (Science Express, 2013)(6) Yuh Hijikata and Shigeyoshi Sakaki“Interaction of various gas molecules with paddle-wheel-type open metalsites of porous coordination polymers: theoretical investigation”
Inorg. Chem., 53, 2417-2426 (2014)
3. ����
(1) Yuh Hijikata，Shigeyoshi Sakaki“Theoretical studies on proton conductive coordination polymer to reveal a
conductive pathway”－ 148 －

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The international symposia on advancing the chemical science 10 (ISACS 10),
Kyoto, 2013/6/19(2) Yuh Hijikata，Shigeyoshi Sakaki“Theoretical investigation for the interaction of various gas molecules withpaddle-wheel type open metal site of porous coordination polymers”
UK-Japan Workshop on Organic-Inorganic Framework Materials, Kyoto,
2013/10/10-11(3) 土方 優，榊 茂好「フッ化物アニオンを骨格に持つ PCP の二酸化炭素吸着に関する理論的研究」
錯体化学会第 63 回討論会 沖縄 2013/11/2-4(4) 野呂真一郎，水谷純也，土方 優，久保和也，中村貴義「電荷分極型中性配位子を用いた多孔性軽金属錯体の合成と吸着・分離機能」
日本化学会第 94 春季年会 愛知 2014/3/27-30(5) 土方 優，榊 茂好「フッ化物アニオンからなる多孔性配位高分子の二酸化炭素吸着に関する理論的研究」
日本化学会第 94 春季年会 愛知 2014/3/27-30－ 149 －

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Ⅳ 研究業績 (2013)

青野 信治
�野 ��
特定研究員

特定研究�
�� �年度の研究の��
本年度は遷移金属錯体に対する溶媒和効果を中心に研究を行った。
【序】 Mn(III)-および Ni(II)-salen 錯体は一電子酸化状態において、金属および salen 配位子の種類によりラジカル中心が salen 配位子内に局在化もしくは非局在化した原子価異性状態を示し、混合原子価電子状態の観点からも興味深い(Scheme 1)。これらの錯体の吸収スペクトルが実験で測定されており、Mn(III)-salen 錯体の一電子酸化体では強度が弱くブロードなスペクトルが、Ni(II)-salen 錯体では対称的な salen 配位子(R1 = R2)の場合に強度が強くシャープなスペクトルが観測されている。

Scheme 1: 金属 salen 錯体
これらの特徴的な違いに対し、実験分野では Mn(III)-salen 錯体のスペクトルは salen ラジカ
ルが一方の phenolate に局在した状態から他方の phenolate へ電荷移動遷移した一種の原子
価間電荷移動吸収(class II に対応)に、Ni(II)-salen 錯体のスペクトルは salen 配位子内の非局在な状態間の電子励起(class III に対応)に帰属し、解釈されている(Scheme 2) [1]。

Scheme 2: 局在的・非局在的な電子励起の違い
本研究では、salen 配位子の(R1, R2)が(Me, Me)、(OMe, OMe)、(OMe, Cl)の場合の Mn(III)および Ni(II)-salen 錯体の 3D-RISM-SCF 研究を行い、金属および配位子による電子状態と1－ 150 －

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溶媒効果の違いを検討した。また Mn(III)と同じ d4 金属である Tc(III)-salen 錯体、Ni(II)と同
じ d8 金属である Pd(II)-salen 錯体についても同様の計算を行い、d 軌道の広がりの違いが原子価異性にどう影響するのかを比較・検討した。
【方法】 CH2Cl2 溶媒中における錯体構造と溶媒和構造は 3D-RISM-DFT/M06 法により求めた。3D-RISM-SCF 計算では、溶質の電子密度から溶媒平衡分布 gs(x)を定める際に、溶質
周囲の静電ポテンシャルを求める必要があるが、本研究では式(1)のように溶質周囲の領域
では波動関数から静電ポテンシャルを計算し、溶質から遠く離れた領域では点電荷近似計
算を行い、この２つを swithing 関数 Sw(x)によって滑らかに接続する方法を採用した[2]。
a * (r )  (r )Q 1  Sw x 
Ves (x)   P Sw x  dr ,r  x ,a Ra  x 



(1)

これにより得られた電子基底状態に対する溶媒和構造 g gr,s(x)を一電子ハミルトニアン項に平均場近似として含める事で、２状態に対して状態平均を課した 3D-RISM-GMC-QDPT計算を行い、式(2)と(3)のように溶質の電子エネルギー変化と溶質-溶媒間相互作用の変化からなる励起エネルギー E、それに対応する振動子強度 f gr,ex を見積もった。
E   ex Hˆ gas  Vˆint (r; R , g gr )  ex   gr Hˆ gas  Vˆint (r; R , g gr )  gr ,2m
f gr,ex  2e E  gr  rˆi  ex3i  electron

2

,

(2)
(3)

但し、 Vˆint は式(4)で定義された演算子である。
Vˆint (r; R, g gr )  Qˆ a 
1
q s  dx g gr s (x) Sw (x)  1  Sw ( x) ,ˆi  xs  solvent sitei  electron ra Ra  x 




(4)

構造最適化および GMC-QDPT 計算では Mn、Ni には(311111/22111/411/1)基底を、Tc、Pdには(311111/22111/411)基底を用い、内殻電子は Stuttgart ECP に置き換えた。それ以外の原子には cc-pVDZ 基底を用い、O、N、Cl に diffuse 関数を加えた。また Mn、Tc では 22、Ni、Pd では 18 の軌道を active 空間に選び、主に基底状態と励起状態の各々に対応する２つの主配置から二電子励起までを許容する計算を行った。
【結果】 3D-RISM-UDFT(M06)による構造最適化の結果、対称的な salen 配位子(R1 = R2)の場合に Mn(III)-と Ni(II)-salen 錯体の違いが見られた。気相中では双方とも C2 対称構造を持つのに対して、溶媒効果を考慮すると Mn(III)-salen 錯体では対称性が低下し、salen ラジカルが片方の phenolate に局在化した電子状態を持つようになる。一方、Ni(II)-salen 錯体では溶媒効果による対称性の低下が起こらず、ラジカルが salen 配位子内で非局在化したままである（表 1）。
2
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表 1: Mn(III)-および Ni(II)-salen 錯体の最適化構造と溶媒効果
結合長 [Å]
C=O1
C=O2
M-O1
Mn(III)-salen
1.30
1.30
1.84
1.32
1.27
1.80
1.30
1.30
1.84
1.32
1.28
1.81
1.32
1.28
1.80
1.32
1.28
1.81
Ni(II)-salen
1.28
1.28
1.83
1.28
1.28
1.84
1.28
1.28
1.84
1.28
1.28
1.84
1.29
1.27
1.82
1.30
1.27
1.82

単位

(Me,Me)(OMe,OMe)(Cl,OMe)(Me,Me)(OMe,OMe)(Cl,OMe)

溶媒

対称性

gas
CH2Cl2gas
CH2Cl2gas
CH2Cl2C2-like
C1
C2-like
C1
C1
C1

gas
CH2Cl2gas
CH2Cl2gas
CH2Cl2C2-likeC2-likeC2-likeC2-likeC2-likeC2-likeM-O2

双極子 [Debye]
x 成分

1.84
1.91
1.84
1.91
1.90
1.90

0.5 (非局在)
9.1 (局在)
0.5 (非局在)10.5 (局在)12.8 (局在)15.7 (局在)

1.83
1.84
1.84
1.84
1.85
1.87

0.0 (非局在)0.0 (非局在)0.0 (非局在)0.0 (非局在)
9.0 (局在)15.2 (局在)これらの錯体構造と溶媒和構造を用いて 3D-RISM-GMC-QDPT 計算を行った結果、実験で観測された吸収スペクトルの傾向が再現された（表 2）。 特に ESP 電荷の変化を調べると Ni(II)-salen 錯体では電子遷移に伴う原子価間電荷移動がなく、Mn(III)-salen 錯体では約0.9e の原子価間電荷移動が起こる事が示唆された。一方、気相中の計算では、Mn(III)の(Me,Me)および(OMe,OMe)錯体において実験値との相違が大きく、溶媒効果は構造変化およびラジカルの局在化/非局在化に重要な役割を果たしている事が示された。また C2 対称な構造を調べると金属種のｄ軌道エネルギーの違いから、２つの非局在性軌道と*軌道のエ
ネルギー差を Ni(II)は大きくする一方、Mn(III)は差を小さくする事が分かり、この結果
Mn(III)-salen 錯体の方が非局在性軌道と*軌道が混ざり易く、局在化が起こり易い事で構造の非対称化が進む事が分かった。
表 2: Mn(III)-および Ni(II)-salen 錯体の励起エネルギー E [eV] と振動子強度 f gr,ex(R1, R2)
構造/溶媒和gas /gas
RISM/MD
RISM/RISM
実験値
構造/溶媒和gas /gas
RISM/MD
RISM/RISM(Me, Me)

Mn(III)(OMe,OMe)

0.340
1.078
1.113
0.838

0.388
1.112
1.126
0.976

0.349
0.107
0.103

0.425
0.119
0.117

(OMe, Cl)
(Me, Me)
垂直励起エネルギーE [eV]
1.314
0.479
1.658
0.455
1.699
0.492
1.389
0.620
振動子強度 f gr,ex
0.061
0.404
0.044
0.384
0.042
0.414

Ni(II)(OMe,OMe)(OMe,Cl)

0.460
0.457
0.454
0.579

0.812
1.430
1.465
0.885

0.401
0.396
0.394

0.242
0.129
0.138

[1] T. Kurahashi and H. Fujii, J. Am. Chem. Soc. 2011, 133, 8307-8316.
[2] S.Aono and S. Sakaki, J. Phys. Chem. B 2012, 116, 13045.
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Ⅳ 研究業績 (2013)

2. 論�(1) Shinji Aono, Masayuki Nakagaki, Takuya Kurahashi, Hiroshi Fujii, andShigeyoshi Sakaki, “Theoretical Study of One-Electron Oxidized Mn(III)− andNi(II)−Salen Complexes: Localized vs Delocalized Ground and Excited Statesin Solution” J. Chem. Theory Comput. 10 1062 (2014).
3. 学会��
(1) 青野信治、中垣雅之、榊茂好「Mn(III)- および Ni(II)-salen錯体の局在・非局在性吸収スペクトルと溶媒効果」
第16回理論化学討論会 福岡 2013/5/15 1L08
(2) Shinji Aono, Masayuki Nakagaki, and Shigeyoshi Sakaki「Localized vs. Delocalized Ground and Excited States of Mn(III) and Ni(II)Salen Complexes: Theoretical Study of Solvation Effects」
第33回溶液化学国際会議 京都 2013/7/9 2PJ04(3) 青野信治、中垣雅之、榊茂好「平面四配位型金属サレン錯体の局在・非局在性吸収スペクトルと溶媒効果」
第7回分子科学討論会 京都 2013/9/24 1P099(4) Shinji Aono, Masayuki Nakagaki, and Shigeyoshi Sakaki「Localized vs. Delocalized Ground and Excited States of Mn(III) and Ni(II)Salen Complexes: Theoretical Study of Solvation Effects」
第 5 回 JCS 理論化学国際会議 奈良 2013/12/3 PIb-19
4. �の�
(1) 青野信治、中垣雅之、榊茂好「平面四配位型金属サレン錯体の局在・非局在性吸収スペクトルと溶媒効果」
第11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 2014/1/23 XXXX

4
－ 153 －

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Milind Madhusudan DESHMUKHSPR FellowDeshmukh
Milind Madhusudan(SPR Fellow)
1. Summary of the research carried out during April 2013 to March 2014.
A) Absorption of Gas Molecules into the Porous Coordination Polymer:
Understanding of the Determining Factors for Absorption position and Energy
We recently studied absorption/adsorption of CO2 and CS2 into porous coordination
polymers (PCPs). For details of this work See; published in J. Am. Chem. Soc. 2013, 135,
4840 and previous annual report.
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 1)
followed by a metathesis of Zn-OCOH compound with hydrosilane to generate silyl
formate (cf. Figure 2.)

TS1
P1
1 + CO2a-1(G= -8.33 kcal mol-1)
0.00(G =12.5 kcal mol )Figure 1: Detailed mechanism for the reaction of CO2 with catalyst 1.

P1 + HSi(OEt)3TS2
1(G= +0.71 kcal mol-1)
0.0(G=14.07 kcal mol-1)
Figure 2: The reaction mechanism for the regeneration of catalyst 1 from 2 and HSi(OEt)3

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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.
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 3). Here, on going from TS4 to TS5 via Int 1, the silicon
center gradually changes its structure from tetrahedral to trigonal bipyramidal.

Figure 3: 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.
Also we explored suitability of various hydrosilane molecules for the regenerationof 1. The corresponding activation barrier for various hydrosilane in the regeneration
reaction was correlated with the stabilization energy for the formation of hypervalent
silicon species similar to that in the TS; See scheme 1 for the formation of hypervalent
species. The results are nicely summarized in Table 1.

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Scheme 1: The formation reaction of hypervalent Si species.
Table 1: The Gibbs activation barrier (Go ‡) for the regeneration of 1 from P1 and P4
with hydrosilane, the stabilization energy (ESt.) of hypervalent silicon species (Scheme1) and theoretically predicted Go ‡ to complete the catalytic cycle. Values are presented
in kcal mol-1.
Go‡ for full catalytic
P1 with Hydrosilane
cycle
a)
o‡
G
ESt.
23.1
HSi(OEt)3
4.2-17.3
H2Si(OEt)2
11.9
-14.3
25.9
14.8
-10.2
27.4
H3Si(OEt)
~0b)
-32.5
22.4
HSiF3
6.9
-24.1
25.0
H2SiF2
25.5
10.5
-16.5
H3SiF
16.6
-2.4
30.5
PhSiH3P4 and Hydrosilane
SilaneGo‡ Go
ESt.
0.4
-6.5
-51.5
HSi(OEt)3
3.0
0.1
-39.4
PhSiH3a) The stabilization energy in either eq. (1a) to eq. (1d).
b) This value is -0.8 kcal/mol; This negative value arises from the computational
procedure .

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As seen in Table 1, the reaction energy increases in the order HSiF3 < H2SiF2 <HSi(OEt)3 < H3SiF H2Si(OEt)2 < H3Si(OEt). The ∆G0‡ is 25.9 kcal/mol for H2Si(OEt)2
and 25.5 kcal/mol for H3SiF, which are not different very much from the ∆G0‡ (23.1
kcal/mol) of HSi(OEt)3. Based on these results, we wish to present theoretical predictionthat hydrosilane bearing three electronegative groups is the best and the hydrosilane
bearing two OEt groups or one to three F groups can be applied to the hydrosilylation of
CO2; in other words, not only HSi(OEt)3 but also H2Si(OEt)2, HSiF3, H2SiF2, and H3SiF
are useful in the hydrosilylation of CO2.

2. Original Papers(1) 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).
(2) Deshmukh Milind M. and Sakaki Shigeyoshi"Generation of Dihydrogen Molecule and Hydrosilylation of Carbon Dioxide
Catalyzed by Zinc Hydride Complex: Theoretical Understanding and Prediction"
Inorganic Chemistry, (Revision submitted: 2014)
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. Others4－ 157 －

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Ⅳ 研究業績 (2013)

GuixiangGuixiang
ZENG（會ZENG桂香）

SPR Fellow, SAKAKI GroupSPR Fellow, SAKAKI Group

1. Summary of the research of the year
Catalytic Transfer Hydrogenation by Trivalent Phosphorus Compound: Phosphorus-Ligand
Cooperation Pathway or PIII/PV Redox Pathway? [1]Main-group element compounds experience a renaissance in the past two decades for their excellent
reactivities similar to those of transition metal complexes. Although the elementary steps such as oxidative
addition, reductive elimination, insertions, and metathesis were reported, full catalytic cycles by main-groupelement compounds are limited. It is well-known that the metal-ligand cooperation and the redox process are
ubiquitous in the chemistry of transition metal complexes, but they have not been reported for the maingroup element compounds.
Recently,
reportedaRadosevich

and

his

catalytic reaction

bycoworkersatrivalentIIIphosphorus compound 1P, where the P /PV redox
processes are involved; see Scheme 1. In thisreaction, 1P reacts with NH3BH3 to afford apentavalentsubsequently
azobenzene

4PP,

dihydridophosphoranetransfers
tohydrogenregenerate

1P.

which

atoms

to

However,themechanistic details of these reactions are still
unclear. Such knowledge is necessary for further

Scheme 1. Catalytic cycle of transfer hydrogenation

development of the chemistry of main groupby 1P.

element compounds.
Here, we theoretically investigated this reaction shown in Scheme 1. The discussion was presented basedon the Gibbs energy changes relative to the sum of reactants (1P + ammonia-borane + azobenzene) unlessotherwise noted. For convenience, the tri-ligated moiety coordinating with the phosphorus centre in 1P isnamed as an ONO ligand hereafter.
For the NH3BH3 dehydrogenation step, the phosphorus-ligand cooperation and the concerted oxidative
addition pathways were examined. As shown in Figure 2, the Gibbs energy barrier (G0≠) of the concertedoxidative addition pathway is 42.7 kcal/mol, which is too large for the reaction to occur at 313.15 K; see the
Figure 1 for geometry changes. On the other hand, the PO cooperation pathway occurs more favourablywith a much smaller G0≠ value of 27.1 kcal/mol. Other phosphorus-ligand cooperation pathways such as
P-C1, P-C2, and P-N1 cooperations were found to be unfavourable in energy. This dehydrogenation step
occurs with an endothermicity of 13.5 kcal/mol, where the intermediate 4OP is formed.

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Ⅳ 研究業績 (2013)

Figure 1. Geometry changes along the PO cooperation and concerted oxidative addition pathways for the
NH3BH3 dehydrogenation reaction.

Figure 2. The Gibbs energy changes (in kcal/mol) for the dehydrogenation of NH3BH3 by 1P.
In the absence of the hydrogenation substrate azobenzene, 4OP transforms to a more stable compound
4PP. In the NH2=BH2 assisted pathway, first, the N2 atom of NH2=BH2 lifts the H2 atom from the O2 atom
to form a NH3 moiety. Simultaneously, the boron atom forms a B-N1 bond with the ONO ligand. Then, theBH2-NH3 moiety rotates around the BN1 bond to bring the H2 atom toward the phosphorus atom via thetransition state TS5/6 to afford the intermediate 6. At last, the hydrogen atom migrates from the NH3 moiety
to the phosphorus atom to form 4PP via the transition state TS6/4PP. The last step is the rate-determining step,which occurs with the G0≠ value of 29.1 kcal/mol; see Figure 2. In the presence of azobenzene, 4OP easily
undergoes the transfer hydrogenation reaction through the transition state TS4OP/1P with the G0≠ value of
28.1 kcal/mol; see Figure 3. On the other hand, in order to elucidate the active species of the hydrogenation
reaction, the 4PP-catalyzed hydrogenation reaction was also examined. This reaction involves the2－ 159 －

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Ⅳ 研究業績 (2013)hydrogenation transfer and the reductive elimination steps; see the upper half of Figure 3. The reductive
elimination step (from 9 to TS9/1P) occurs with the G0≠ value of 43.2 kcal/mol, indicating that 4PP is not
active species for the hydrogenation step.

Figure 3. Geometry changes along the transfer hydrogenations starting from 4PP and 4OP, respectively.
Distances are in Å. In parentheses are Gibbs free energy changes, in kcal/mol.
In brief, the transfer hydrogenation reaction by 1P occurs through the P-O cooperation, where theNH3BH3 dehydrogenation reaction leads to the intermediate 4OP, which transfers hydrogen atoms toazobenzene to complete the catalytic cycle; see Scheme 2. In the absence of azobenzene, 4OP transforms to
4PP with the assistance of NH2=BH2 or through the intermolecular hydrogen shuttles.

Scheme 2. The most plausible mechanism for the transfer hydrogenation by 1P.
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As last, we examined the substituent effect and found that the electron withdrawing substituent
enhanced the activity of 1P; see the Figure 4 for energy changes.[2]Figure 4. Reaction profile for the transfer hydrogenation reaction by 1P with the substituents of tBu, Me,
and CF3.
In order to explain the reason why the electron withdrawing ligand is favourable for the reaction, we madeNBO analysis along the reaction pathway; see Figure 5.

Figure 5. NBO analysis along the transfer hydrogenation reaction by 1P.
In the NH3BH3 dehydrogenation step, the electron population of the ONO ligand increases, indicatingthat the ligand accepts electrons during the reaction and thus the electron withdrawing substituent would
enhance the activity of the catalyst in this reaction step. This is consistent with the energy changes that the
Gibbs energy barrier (G0≠) of the NH3BH3 dehydrogenation step decreases in the order tBu(27.1 kcal/mol)> Me (26.6 kcal/mol) > CF3 (20.9 kcal/mol), where tBu, Me and CF3 are substituents on the ONO ligand.
This reaction step is endothermic but the endothermicity decreases in the order tBu(13.5 kcal/mol) > Me(12.1 kcal/mol) > CF3 (5.2 kcal/mol), indicating that the active species 4OP is also stabilized by the electron
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Ⅳ 研究業績 (2013)

withdrawing ligand.
In the azobenzene hydrogenation step, the electron population of the ONO ligand considerably
decreases, indicating that the ONO ligand donates electrons in the reaction. As a result, the electron donating
ligand would be favorable for this reaction step. This is consistent with the calculation results that the energy
difference between TS4OP/1P and (4OP + 7) increases in the order tBu (14.6 kcal/mol) < Me (18.0 kcal/mol) <CF3 (18.3 kcal/mol). However, when the initial reactants (1P + 3 + 7) is taken as the reference, the G0≠
value for the azobenzene hydrogenation step changes in the order Me (30.1 kcal/mol) > tBu (28.1 kcal/mol)> CF3 (23.5 kcal/mol), indicating that R=CF3 enhances the activity of 1P. One reason for this phenomenon isthat the stabilization (8.3 kcal/mol, comparing with R=tBu case) of 4OP by R=CF3 is larger than its
destabilization (3.7 kcal/mol, comparing with R=tBu case) of TS4OP/1P. This is because the increase of theelectron population on the ONO ligand is larger when it goes from 1P to 4OP than its decrease when it goesfrom 4OP to TS4OP/1P. As a result, the electron withdrawing substituent plays more important role instabilizing 4OP than its destabilization role in TS4OP/1P.

Original papers[1] Guixiang ZENG, Satoshi MAEDA, Tetsuya, TAKETSUGU, and Shigeyoshi SAKSKI“Catalytic Transfer Hydrogenation by a Trivalent Phosphorus Compound: Phosphorus-Ligand Cooperation
Pathway or PIII/PV Redox Pathway?” Angew. Chem. Int. Ed. 53, 4633 –4637(2014).
[2] Guixiang ZENG and Shigeyoshi SAKSKI“Transfer Hydrogenation by a Trivalent Phosphorus Compound: Electronic Process and Prediction” In
preparation.
2. Presentation at academic conferences
Guixinag Zeng, Shigeyoshi Sakaki “CC bond Formation between Alkenes and Alcohols Catalyzed by a
Cationic Ru(II) Hydride Complex: A Theoretical Study” The 60th Symposium of Organometallic Chemistry,
Tokyo, September 7, 2013.
3. Others
Guixinag Zeng, Shigeyoshi Sakaki “Mechanistic Study of the Silylation Reaction of Allylic AlcoholMediated by [Pd(MeCN)4](BF4)2” The 10th symposium of Fukui Institute for Fundamental Chemistry, Kyoto,
January. 23, 2014.

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Nozomi TAKAGI
Nozomi TAKAGISPR Fellow
SPR Fellow
1. Summary of the research of the year
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 1). 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, thecatalytic hydrogenation of CF3PhCO by 1
is difficult because the reaction of 2 with adihydrogenmolecule

needs

a

large

activation energy (Figure 2). 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 1. Geometry changes in hydrogenation andhydrosilylation of CF3PhCO by the Ge(II) hydride 1 calculated
at the B3PW91 level.

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Ⅳ 研究業績 (2013)

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.

Planar D4h-like vs. Non-planar C2v-like
Structure of η4-TetrasilacyclobutadieneComplexof

Co(I).

Theoretical

Understanding
Heavier homologues of cyclobutadiene

Figure 2. 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.

have been successfully synthesized andisolated as transition metal complexes. The experimentally reported tetrasilacyclobutadiene cobalt
complex [(SiMetBu2)4Si4Co(CO)2]- 1 has a planar Si4-ring structure. This is considered as acomplex between d8 Co(I) and dianionic 6π-electron Si4 (Scheme 1a). However, theoretical
calculations never present a planar Si4-ring structure as an energy minimum but a distorted
non-planar structure (Scheme 1b). In the Fe(II) and Ru(II) analogues, on the other hand, the planar
Si4-ring structure can be well reproduced by theoretical calculations. It is of considerable interest to
elucidate the reason why the D4h-like planar structure is experimentally observed but the non-planar
C2v-like one is calculated, because thisdifference deeply relates to aromaticity
andelectronic

structure.

Here,

we

investigated the geometry and electronic

R

R

Si4

Si3

Si1

Si2

R

R

R

Si4

Si3

Si1

Si2

Co
OC

structure of 1.
As shown in Scheme 2, the Co(CO)2

R

R

Co
CO

1a

R

OC

CO

1b

Scheme 1. Planar D4h-like and non-planar C2v-like structuresof 1.

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Ⅳ 研究業績 (2013)z

moiety has the dxz orbital as the HOMO andthe dyz as the LUMO. Hence, the φ2 ofy[Si4R4]2- overlaps with the dyz to form abonding CT interaction but the φ3 overlaps

charge transfer

2

3

1

Hence, the D4h-like structure is not stable. In

dyz in the Fe(II) and Ru(II) complexes,6

dx2-y2dxz

dxywith the dxz to give rise to exchange repulsion.

contrast, both φ2 and φ3 overlaps with dxz and

dyz

4

x

[R4Si4]2-

dz2

d8 Co

Scheme 2. Orbital interaction diagram of [Si4R4]2- and d8
Co moieties.

because these complexes have d electron
configuration. Though the non-planar C2v structure is the most stable in 1, the D4h-like planar
structure is found as a transition state connecting two non-planar C2v-like structures. The Gibbs
activation barrier is very small (about 2 kcal/mol). This result provides a clear explanation that theD4h-like structure is experimentally observed as an average of two non-planar C2v-like ones. A
comparison was also made with the recently reported neutral tetrasilacyclobutadiene (Si4EMind4)
because it takes a planar rhombic Si4-ring structure.
2. Original papers(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"N. Takagi, and S. Sakaki, J. Am. Chem. Soc., 135, 8955-8965 (2013).
3. Presentation at academic conferences(1) "ゲルマニウム(II)ヒドリド化合物による二酸化炭素およびイミン転換触媒サイクルの理論予測"N. Takagi, and S. Sakaki, 第16回理論化学討論会, Fukuoka, May, 15 – 17, 2013.
(2) "A Theoretical Prediction of Catalytic Hydrosilylation of Ketone, Carbon Dioxide, andImine by Ge(II) Hydride Compound"N. Takagi, and S. Sakaki, 第60回有機金属化学討論会, Tokyo, September, 12 – 14, 2013.
(3) "A theoretical study of geometry and electronic structure of η4-tetrasilacyclobutadiene
complexes of Co(I) and Ru(II)"N. Takagi, and S. Sakaki, Annual Meeting of Japan Society for Molecular Science, Kyoto,
September, 24 – 27, 2013.
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Ⅳ 研究業績 (2013)(4) "遷移金属錯体と高周期典型元素化合物の反応性と触媒活性の相違"
N. Takagi, and S. Sakaki, 化学反応経路探索のニューフロンティア, Kyoto, September,
27 – 28, 2013.
(5) "A Theoretical Study of Geometry and Electronic Structure of η4-tetrasilacyclobutadieneComplex of Co(I) and Relevant Metal Complexes"
N. Takagi, and S. Sakaki, The 11th Fukui Institute for Fundamental Chemistry Symposium,
Kyoto, January 23, 2014.

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Ⅳ 研究業績 (2013)

Masayuki NAKAGAKI
Masayuki Nakagaki
FIFC Fellow
FIFC Fellow
1. Summary of the research of the year
Electronic Structure and Spin Multiplicity of Inverse Sandwich Type Dinuclear
3d Transition Metal Complexes of Ethylene: Comparison with that of Dinitrogen complexes
β-diketiminate ligands make low-valent and low-coordinate transition metal complexes and form theinversed sandwich type complexes (ISTCs). The spin states of ISTCs depend on not only the kind of metal
atoms but also that of sandwiched molecule. The ISTCs of Cr(DDP); (DDPH = 2-(4-{(2,6-diisopropyl-

phenyl)imino}pent-2-ene) were experimentally synthesized with several molecule. The magnetic
moments of ethylene and dinitrogen complexes are 4.2 and 3.9, respectively, which correspond to
the spin state between the triplet and quartet spin states, whereas the benzene and toluene
complexes take septet state. Though the (μ-N2)[Fe(DDP)]2 was also synthesized and it takes septet spinstate which is completely different from that of the Cr complex, the other transition metals of ethylene
complex have not been reported. In this study, we investigated the spin state and of ethylene ISTCs for 3dtransition metals from Sc to Ni. The final goal of our work finding the general rule
We replaced the DDP ligands with AIP (AIPH = 1-amino-3-iminoprop-1-ene; Figure 1) for brevity. Geometry optimizations werecarried out for each spin states by the complete active space
self-consistent field (CASSCF) method. The active space consists ofthe d-orbitals of two metals and π* orbitals of C2H4. The
second-order perturbation theory with a CASSCF reference function(CASPT2) calculations were carried out at CASSCF optimized
structures.

Figure 1. (μ-C2H4)[M(N^N)]2(M= Sc-Ni; N^N = DDP or AIP)

Important structural parameters optimized for the singlet state by the CASSCF method areshown in Figure 2. The CASSCF optimized structures at the singlet to nonet spin states resemble
each other. Both the Cr-Cr distance and the C-C bond length of ethylene are close to theexperimental values. The geometry optimization also carried out under C2h symmetry because twobond distances of Cr and each C atom of ethylene molecule were slightly different in the X-ray
structure of real complex. Unfortunately, the distortion of ethylene molecule was overestimated andstructural parameters are far from experiential values.

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Figure 2. Optimized structure of (μ-C2H4)[M(AIP)]2 (M=Cr, Mn) calculated by the CASSCF
method. The spin states are singlet and parentheses are experimental values.
The relative energies of various spin states of (μ-η2:η2-C2H4)[Cr(AIP)]2 are listed in Table
1. We chose the D2h structure for latter discussion because of the similarity of experimental
structure. Though the C2h structure is more stable than D2h structure, the trends of spin states are
similar in both structures.
The ground state takes a singlet state but the energy difference between the singlet and thenonet spin states is very small. This means that the experimentally observed magnetic moment
corresponds to the thermal average of these spin multiplicities. According to the Boltzmann
distribution law, the average of effective magnetic moments is estimated to be μeff = 3.4 and 1.6 μB
with CASSCF and CASPT2 calculated relative energies, respectively, at 293 K. The calculated
value is different from the experimental one (4.2 μB), compared to N2 complex, which indicate thatthe stability of low spin state was overestimated.
In the (μ-C2H4)[Mn(AIP)]2, on the other hand, the considering of D2h symmetry is not
appropriate assumption because the energy difference between C2h and D2h structures is very large,
as shown in Table 1. The distances between Mn and ethylene C atoms are 2.18 and 3.12 Å,
respectively; therefore the coordination of ethylene to Mn can be regarded as η1-coodination.
The Mn complex also takes a singlet state and the energy difference between the singlet
and the undectet spin states is small. However, different from the Cr complex, these spin states arealmost degenerate at the CASSCF level; see Table 1. It indicates that, in the Mn complex, thestability of low spin state results from dynamical electron correlation and cannot be explained by
the CASSCF wavefunction. The relative energies of various spin states of (μ-C2H4)[M(AIP)]2 (M=Sc toNi) are listed in Table 2. All analogues of 3d transition metals take the singlet state.

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Table 1 Relative energies (kcal/mol) of various spin multiplicities in (μ-C2H4)[M(AIP)]2 (M= Cr,Mn) with D2h and C2h structures.
(a) CASSCF
spin
multi.

(b) CASPT2

Cr
C2h

Mn
D2h

11

Cr

C2h

D2h

C2h

0.00

31.5

Mn
D2h

C2h

D2h

1.8

36.4

9

1.1

6.0

0.02

31.0

4.3

12.5

1.4

35.4

7

0.8

5.4

0.04

30.6

3.0

10.5

1.0

33.9

5

0.4

4.8

0.05

30.3

1.6

8.8

0.6

32.7

3

0.1

4.4

0.06

30.1

0.6

7.5

0.3

31.7

1

0.0

4.2

0.06

30.0

0.0

6.8

0.0

31.2

Table 2 Relative energies (kcal/mol) of various spin multiplicities of (μ-C2H4)[M(AIP)]2 calculated
by CASPT2 method.
spin multi.

Sc

Ti

V

Cr

11

Mn

Fe

Co

Ni

1.8

9

5.7

1.4

1.2

2.3

3.8

1.0

0.9

0.8

1.1

1.3

2.0

0.6

0.6

0.6

0.1

7
5
3

0.2

0.5

0.5

0.7

0.3

0.3

0.3

0.1

1

0.0

0.0

0.0

0.0

0.0

0.0

0.0

0.0

The CASSCF(10,11) optimized orbitals for the 1Ag state of (μ-C2H4)[Cr(AIP)]2 are shown in Figure3(a). The ψ1 MO is a bonding MO and almost doubly occupied. The occupation numbers of 2 to 9 MOs
are close to 1.0. These orbitals and its occupations are understood by the MO interaction diagram of(μ-C2H4)[Cr(AIP)]2, as shown in Figure 4. In the isolated M(AIP), the dyz orbital is considerably destabilized
in energy by the anti-bonding overlap with the two lone pair orbitals of the AIP ligand. Other four d orbitals
are nearly degenerate at lower energy because they are nearly non-bonding. Anti-bonding and bonding pairsof d orbitals in [M(AIP)]2 moiety are named φia and φib (i=1 to 5), respectively. These bonding andanti-bonding MOs are nearly degenerate because of the long M-M distance. The φ5a, an anti-bonding pair of
dyz orbitals of two Cr centers, overlaps well with the π* MO of C2H4 to form a bonding ψ1 MO and ananti-bonding ψ11 MO in (-2:2-C2H4)[Cr(AIP)]2; see Figure4. The 1 MO is very stable in energy becauseof the well -type overlap between the dyz of [Cr(AIP)]2 and the in-plane * MO of C2H4. The 2 to 9 MOs
are essentially non-bonding and singly occupied. Four electrons of them have -spin and the other fourelectrons have -spin in the singlet state. This is not unreasonable because these eight electrons can afford
singlet, triplet, quintet, septet, and nonet spin states through various combinations. In such case, the energy－ 169 －

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Ⅳ 研究業績 (2013)

differences between these states are small, as shown in Table 1. Though the both 8 and 9 are non-bonding
MO which consist of same d orbitals, the occupation numbers of them are 1.03 and 0.97, respectively. This
indicated that the orbital energy 8 is slightly lower than that of 9 by the forming of ISTC. Thus, two Cr
atoms takes low-spin coupling to provide larger occupation numbers in more stable MOs than in theircounterparts. In fact, the occupation numbers of these orbitals correspond to 1.0 in nonet state. The similar
deviation of occupation number from 1.0 is observed in some bonding and anti-bonding pair of d orbitals in
the Sc to V complexes. On the other hand, this deviation did not occur in Mn to Ni complexes, which isconsistent with the fact that the singlet state is not ground state at CASSCF level.
The CASSCF(12,11) optimized orbitals for the 1Ag state of (μ-C2H4)[Mn(AIP)]2 are shown in
Figure 3(b). In the Mn complex, the dyz orbitals are singly occupied like other d orbitals. The doubly
occupied MO ψ1 is localized on C2H4 moiety, which indicated that the orbital energy of C2H4 π* orbital islower than d orbitals in Mn(AIP). Thus, when the all these orbitals are singly occupied, the next electron
occupy to the π* orbital. Because of the complete electron transfer from Mn(AIP) to C2H4, trans vent occurs
for sp3 hybridization. After that, each lone pair orbital of [C2H4]2- coordinate to one Mn atom. This is thereason why the ethylene molecule takes η1-coordination in Mn complex.

(a) (μ-C2H4)[Cr(AIP)]2(a) (μ-C2H4)[Mn(AIP)]2

ψ10,b3u(0.05)

ψ11,b2g(0.01)

ψ10,bu(1.01)

ψ11,ag(0.99)

ψ7,ag(0.98)

ψ8,b3g(1.03) ψ9,b2u(0.97)

ψ7,bu(1.00)

ψ8,bg(1.00)

ψ9,au(1.00)

ψ4,au(1.01)

ψ5,b1g(0.99)

ψ6,b1u(1.02)

ψ4,bg(1.00)

ψ5,au(1.00)

ψ6,ag(1.00)

ψ1,b2g(1.94)

ψ2,ag(1.00)

ψ3,b1u(1.00)

ψ1,ag(2.00)

ψ2,ag(1.00)

ψ3,bu(1.00)

Figure 3. CASSCF optimized orbitals of (a) (μ-C2H4)[Cr(AIP)]2 and (b) (μ-C2H4)[Mn(AIP)]2. The
subscript represents irreducible representation under D2h and C2h symmetries, respectively. Numbers
in parentheses are occupation numbers of natural orbitals in the singlet state.

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Figure 4. Schematical orbital pictures of (μ-C2H4)[Cr(AIP)]2.
Summary

We theoretically investigated the inverse sandwich type complex, (μ-C2H4)[M(AIP)]2(AIPH = 1-amino-3-imino-prop-1-ene) for 3d transition metals from Sc to Ni. We found thesimilarity of the electronic structure between the (μ-C2H4)[M(AIP)]2 and the (μ-N2)[M(AIP)]2 in the
Sc to Cr complexes. In these complexes, the very stable bonding orbital is formed by the dyz orbitalof two metal atoms and the * orbital of C2H4 or N2 molecule, which is completely doubly occupied.
Other singly occupying d electrons take singlet because the orbital energies of bonding andanti-bonding pair MOs slightly split by the interaction with the sandwiched molecule.
On the other hand, in the Mn to Ni complexes, the bonding nature and the spin multiplicity
are completely different in (μ-C2H4)[M(AIP)]2 and the (μ-N2)[M(AIP)]2. In the ethylene ISTCs, theeach carbon atom of ethylene coordinates to individual metal atom, that is, η1-coodination. Because
two electron occupy to the * orbital of C2H4, the trans vent occurs for sp3 hybridization. After that,each lone pair orbital of [C2H4]2- coordinate to individual one metal atom. Though the ground stateof these complexes is a singlet state, the energy differences to high spin state are very small.
2. Original papers(1) Masayuki Nakagaki and Shigeyoshi Sakaki“CASPT2 Study of Inverse Sandwich-Type Dinuclear Cr(I) and Fe(I) Complexes of the
Dinitrogen Molecule: Significant Differences in Spin Multiplicity and Coordination Structure
between These Two Complexes”
J. Phys. Chem. A, 2014, 118 (7), pp 1247–1257(2) Shinji Aono, Masayuki Nakagaki, Takuya Kurahashi, Hiroshi Fujii, and Shigeyoshi Sakaki“Theoretical Study of One-Electron Oxidized Mn(III)– and Ni(II)–Salen Complexes: Localizedvs Delocalized Ground and Excited States in Solution”
J. Chem. Theory Comput., 2014, 10 (3), pp 1062–1073－ 171 －

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3. Presentation at academic conferences(1) 中垣 雅之，青野信治，榊 茂好「金属サレン錯体の電子構造：局在・非局在性に関する支配因子」
第 16 回理論化学討論会 2013 福岡 福岡 2013/5/15-26 2P22 ポスター
(2) 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特異なスピン状態」
第 7 回分子科学討論会 2013 京都 京都 2013/9/24-27 2E18 口頭(3) Masayuki Nakagaki, Shigeyoshi Sakaki“Unique Spin State of Inverted Sandwich Type Complexes with Hetero Dinuclear
Transition Metals Bridged by Dinitrogen Molecule”
5th JCS International Symposium on Theoretical Chemistry, Nara 2013/12/2-6 PIa-13 poster
4. Others(1) Masayuki Nakagaki, Shigeyoshi Sakaki“Unique Spin State of Inverted Sandwich Type Complexes with Hetero Dinuclear Transition
Metals Bridged by Dinitrogen Molecule”
The 2nd International Symposium on Dynamical Ordering of Bipmolecular Systems for
Creation of Integrated Functions 2014/1/11-12 P58 poster(2) Masayuki Nakagaki, Shigeyoshi Sakaki“Unique Spin State of Inverted Sandwich Type Complexes with Hetero Dinuclear Transition
Metals Bridged by Dinitrogen Molecule”
第11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 2014/1/23－ 172 －

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Wei GUAN
Wei GUANSPR Fellow, Fukui kenichi Memorial Research
SPR Fellow, Fukui kenichi Memorial Research
1. Summary of the research of the year
Selective Dual C‒C σ-Bond Activation in Decyanative [4 + 2] Cycloaddition by Ni0 Complex:
The Role of Lewis Acid
Selective activation of inert C−C σ-bond attracts much attention because of its powerful and wide
applications to organic syntheses. It still faces tremendous challenges. An efficient cooperation of transition
metals (TMs) with Lewis acids (LAs) is expected to be a powerful tool in the C−C σ-bond activation.
However, the mechanistic details and the origins of cooperative and synergistic functions of this TM/LA
catalytic system are not clear at all. Also, the role of LA in TM-catalyzed C−C σ-bond activation has not yet
been theoretically investigated.
Here, we theoretically investigated

Scheme 1

the Ni0/LAn (n = 0, 1, 2)-catalyzed
decyanative [4 + 2] cycloaddition ofo-arylcarboxybenzonitrile with alkyne
via

selective

dual

C−C

σ-bondcleavages, using DFT method with the
M06 functional (Scheme 1).
(1) The most favorable catalytic cycle A consists of five key elementary steps: oxidative addition of
C−CN σ-bond to the nickel(0) center (the first C−C σ-bond cleavage), alkyne insertion into the nickel−arylbond, C−C coupling (ring-closing), β-aryl elimination (the second C−C σ-bond cleavage), and reductive
elimination of coumarin (P), as presented in Scheme 2.
(2) In the oxidative addition
to the Ni center, we need toinvestigate

which

of

four

σ-bonds (a, b, c, and d) of S
undergoes the activation; see theinset in Figure 1. The C–CN
σ-bond activation occurs via
TS1a-LA2 with the smallest
ΔG°‡ value (12.9 kcal/mol),whereas the oxidative additionsof the b and c bonds (viaTS1b-LA2
requireandmuch

TS1c-LA2)largerΔG°‡values (30.9 and 23.4 kcal/mol,Figure 1. Energy profiles (ΔG°393.15) of oxidative activation. 2d-LA2 is
a presumed Ni(II) intermediate with a fixed bond d distance of 2.39 Å.

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respectively). In addition, the product of the oxidative addition of the d bond could not be located. It should
be concluded that the first step is the oxidative addition of the a bond (the C–CN σ-bond).
Scheme 2(3) After the oxidative addition, such two possible reaction courses as alkyne insertion into the Ni−C bondand activation of the second C−C (aryl−carbonyl) σ-bond must be investigated. In the alkyne insertion
starting from 2a-LA2, two reaction routes were examined: in one, AL is inserted into the nickel−aryl (Ni−C2)bond and in the other into the nickel−cyanide (Ni−C1) bond. As shown in Figure 2, the former reaction(2a-LA2 → TS2-LA2 → 3-LA2) occurs more easily with a much smaller ΔG°‡ value (14.4 kcal/mol relative
to C1-LA2) than the latter one (8-LA2 → TS5-LA2 → 9-LA2) with a ΔG°‡ value (27.8 kcal/mol). On theother hand, the second C−C σ-bond activation is difficult; as shown in Figure 2, it occurs through TS6-LA2
to afford a six-coordinate Ni(IV) intermediate 10-LA2 with a very large ΔG°‡ value (56.8 kcal/mol relative to
C1-LA2) and a very positive ΔG° value (50.7 kcal/mol). Then, Ph−CN reductive elimination occurs throughTS7-LA2 to form a four-coordinate Ni(II) intermediate 11-LA with a very large ΔG°‡ value (62.9 kcal/mol
relative to C1-LA2). Hence, it is concluded that the second step is not C−C σ-bond cleavage but alkyne
insertion.

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Ⅳ 研究業績 (2013)(4) 3-LA2 isomerizes to aneight-member ring intermediate
4-LA2 with a small ΔG°‡ value of
2.7 kcal/mol (Scheme 2 andFigure 3A). Starting from 4-LA2,
the C−C coupling reaction occurs
between the vinyl C5 and thecarboxyl C6 atoms via TS3-LA2
to generate an intermediate 5-LA2.
In 5-LA2, a new six-member ring(gray color) is formed and its
C4−C5 double bond coordinateswith the Ni center (Scheme 2).
The ΔG°‡ and ΔG° values relative
to 3-LA2 are 14.0 and 0.7
kcal/mol,indicating

respectively,
that

this

process

Figure 2. Energy profiles (ΔG°393.15) of alkyne insertion andaryl-carbonyl bond activation.

easily occurs.

Figure 3. Energy profiles (ΔG°393.15) of the catalytic cycles A and B.
(4) The final step of the catalytic cycle A is the C6−C7 bond cleavage via β-aryl elimination followed by
the C1−C7 bond formation via reductive elimination (Scheme 2). These two processes occur throughTS4-LA2 in one step to afford an intermediate 6-LA2 in which the reductive elimination has been alreadycompleted. In 6-LA2, the C6−C7 bond is completely cleaved and the C1−C7 bond (1.42 Å) is formed－ 175 －

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Ⅳ 研究業績 (2013)(Scheme 2). The ΔG°‡ and ΔG° values relative to 5-LA2 are 16.6 and −18.9 kcal/mol, respectively. Finally, adesired product coumarin P is released with a byproduct ArCN through ligand exchange to regenerate
C1-LA2. The rate-determining step is the β-aryl elimination followed by the reductive elimination. The ΔG°‡
value for the whole catalytic cycle corresponds to the energy difference between TS4-LA2 and 3-LA2, which
is 17.3 kcal/mol. The total ΔG° value is −35.7 kcal/mol. These values indicate that this catalytic reaction
easily occurs with a moderate activation energy.
(5) We investigated the reaction without LA. Figure 3B describes the Gibbs energy profiles without LA(catalytic cycle B). Apparently, the presence of LA significantly stabilizes the stationary points on thepotential energy surface, indicating that two LAs strongly coordinate with the substrate S through the cyano
N and carbonyl O atoms. Also, it should be noted that in the catalytic cycle B the ΔG°‡ value is 21.0, 20.0,
23.8, 20.6, and 2.4 kcal/mol for the oxidative addition, alkyne insertion, C−C coupling, β-aryl elimination,and reductive elimination, respectively. In the catalytic cycle A, on the other hand, those ΔG°‡ values are
considerably lower, 12.9, 14.4, 14.0, and 17.3 kcal/mol, respectively. These results lead to a clear conclusionthat the presence of two LAs dramatically accelerates this catalytic reaction.

2. Original papers(1) Wei Guan, Shigeyoshi Sakaki, Takuya Kurahashi, Seijiro Matsubara“Theoretical Mechanistic Study of Novel Ni(0)-Catalyzed [6 − 2 + 2] Cycloaddition
Reactions of Isatoic Anhydrides with Alkynes: Origin of Facile Decarboxylation”
Organometallics 32, 7564–7574(2013).
(2) Wei Guan, Fareed Bhasha Sayyed, Guixiang Zeng, Shigeyoshi Sakaki“σ‑Bond Activation of Small Molecules and Reactions Catalyzed by Transition-Metal
Complexes: Theoretical Understanding of Electronic Processes”
Inorg. Chem. ic5003429(2014).
(3) Shinichi Yamabe, Gui-Xiang Zeng, Wei Guan, Shigeyoshi Sakaki“SN1-SN2 and SN2-SN3 Mechanistic Changes Revealed by Transition States of theHydrolyses of Benzyl Chlorides and Benzenesulfonyl Chlorides”
J. Comput. Chem. 35, 1140–1148(2014).
(4) Shinichi Yamabe, Gui-Xiang Zeng, Wei Guan, Shigeyoshi Sakaki“Substrate dependent reaction channels of the Wolff–Kishner reduction reaction: A
theoretical study”
Beilstein J. Org. Chem. 10, 259–270(2014).
(5) Zhong-Ling Lang, Guo-Chun Yang, Na-Na Ma, Shi-Zheng Wen, Li-Kai Yan, Wei Guan,
Zhong-Min Su“DFT characterization on the mechanism of water splitting catalyzed bysingle-Ru-substituted polyoxometalates”
Dalton Trans. 42, 10617–10625(2013).

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3. Presentation at academic conferences(1) Wei Guan, Shigeyoshi Sakaki“Oxidative Addition of Anhydride to Nickel(0) Species: Reactivity and Regioselectivity”
The 7th Annual Meeting of Japan Society for Molecular Science (1P098) Kyoto, Sep. 19,
2013.
4. Others(1) Wei Guan, Shigeyoshi Sakaki“Origin of Dramatically Cooperative Catalysis on Selective Dual C‒C Bond Activation in Ni0/LewisthAcid-Catalyzed [4 + 2] Cycloaddition: Theoretical Insights” The 11 symposium of Fukui Institutefor Fundamental Chemistry, Kyoto, Jan. 23, 2014.

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Yue CHEN
Yue Chen
SPR Fellow
SPR Fellow
1. Summary of the research of the year
The important role of the Mo–Mo quintuple bond in catalytic synthesis of benzene fromalkynes. A theoretical study
Because the metal-metal multiple bond has ݀ఋ and/or ݀గ bonding orbitals at a high energy and theiranti-bonding counterparts at a lower energy, the metal-metal multiple bond is expected to exhibit highreactivity. However, the reaction of the metal-metal multiple bond has not been reported until recent several
pioneering works: Kempe, Theopold, and Tsai groups reported interesting reactions of the dichromium
complexes with AlMe3, N2O, RN3, NO, P4, As4, AsP3, group 16 and 17 elements, and alkynes. Tsai andcoworkers recently reported an interesting catalytic synthesis of benzene derivative by a dinuclear
molybdenum complex Mo2(N^N)2 (N^N = N,N’-(DipN)2CH, Dip = 2,6-iPr2C6H3) bearing a Mo-Mo
quintuple bond, as shown in Scheme 1.
In

this

investigated

work,
this

we

R1

theoreticallyinteresting

benzeneformation reaction from alkyne catalyzed

R1

by 1. Our purposes here are to (1) explore

Reductive
Elimination

why the [2+2] cycloaddition reaction
between the Mo-Mo quintuple bond andalkyneeasilyoccursdespiteofthesymmetry-forbidden character, (2) elucidate

R1

N

Mo

N

Mo

N R1

4

N

R1

how 3 reacts with one more alkyne tocomplete a full catalytic cycle, and (3)

Mo

N

N

R1

1

2+2

Mo
R1

R1

N
Mo

N
N
R1

2

R1
N

R1

4+2
N

Mo

N

Mo

R1

goal is to theoretically clarify the origin of[2+2] cycloaddition between 1 andMoR1

R1=2,6-Me2C6H3

R1

perform this catalytic reaction. Our final

bond.

N

6+2

uncover why the Cr analogue of 1 cannot

the high reactivity of the Mo-Mo quintuple

N

3

N

R1

N
R1

Scheme 1. Proposed catalytic cycle of benzene synthesis fromthree alkyne molecules by a Mo-Mo quintuple bond.

alkyne: We evaluated the potential energy surface of this pathway with the large model 1 bearing bulky
substitutes (R1 = 2,6-Me2-C6H3). As shown in Figure 1, the coordination of propyne with one Mo atom
occurs through a transition state TS1 to afford a Mo-propyne complex INT1. Though TS1 could be
optimized with BS-I, it disappears in the DFT/BS-II calculation; Ea = -6.3 kcal/mol and ΔG0‡ = -1.8 kcal/mol
at the DFT/BS-II level. The exothermicity is considerably larger (ΔE = -30.2 kcal/mol). It is concluded thatthe acetylene coordination with the Mo center easily occurs with a negligible small activation barrier. The
η2-coordinate INT1 converts to a four-member ring complex 2 through a transition state TS2. The ΔG0‡
1
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Ⅳ 研究業績 (2013)

value is small (3.7 kcal/mol) and the ΔG0 value is large (-8.6 kcal/mol) relative to INT1. These values are
consistent with the experimental observation that the reaction occurs at very low temperature (-35 ℃).
1.231

N

Mo

G/[ kcal/mol]E/[ kcal/mol]

R1

N

Mo

R1
N

R1

C1 1.330 C2

.4
165

N
R1
RMo-Mo = 2.083

-1.8
-6.3

0.0
0.0
R1

R1

7
1.31

TS1

1

N

N

Mo

Mo

N

N

R1 N

Mo
R1

R1

Mo1

N

Mo

N

.4
N
111
R1
RMo-Mo = 2.152

INT1
R1

R1

N

-24.5
-30.2

R1

Mo2

R1

N

N

.7
N
109
R1
RMo-Mo = 2.096

R1

1.3
82

Mo
R1 N

TS2

-20.8
-27.0

RMo-Mo = 2.060

Mo
N

R1

N
.2
107

N

R1

R1
RMo-Mo = 2.110(C1-Mo1-Mo2-C2) =

°

2

-33.1
-40.0

Figure 1. Energy change in the [2+2] cycloaddition via an asymmetric pathway
Formations of six-member dimolybdenacyclic compound 3. Because of the presence of bulky
substituents of the N^N ligand, the incoming propyne interacts not with the ���� MO but with the ���� MO toafford an intermediate INT2 through a transition state TS3a, as shown in Figure 2. The ΔG0‡ is 4.7 kcal/mol

relative to 2, which is moderately higher than that of the first propyne coordination. This is because the ���� ismore stable than the ���� and the steric repulsion with the bulky substituents on the N^N ligand becomes larger
in TS3a than in TS2; note that TS3a is more congested than TS2. INT2 turns into a less stableintermediate INT3 via a transition state TS3b, where one N atom of the N^N ligand dissociatesfrom the Mo2 center to provide a vacant site and the second propyne moves to this vacant site.
Starting from INT3, the C3 of the second propyne approaches the C2 of the first propyne to afford adimolybdenacyclic compound 3 through a transition state TS3c. This elementary step is understood
to be the coupling reaction between the C1-C2 double bond of 2 and the C3-C4 triple bond of theincoming propyne. The ΔG0‡ of this C2-C3 bond formation is 13.5 kcal/mol and the ΔG0 is very
negative (ΔG0 = -66.0 kcal/mol) relative to INT3.
[6+2] cycloaddition reaction to produce benzene. The next step is the reaction between the third
propyne and 3. Though the Mo-Mo ���� and ���� MOs of 3 can interact with the � ∗ MO of theincoming propyne through CT interaction, the bulky substituents on the N^N ligand and thecongested six-member ring suppress the approach of propyne in both of the yz and xy planes.
Because of this congested geometry, one N atom of the N^N ligand must dissociate from the Mo
center to form an intermediate INT4a through a transition state TS4a, as shown in Figure 3. The
ΔG0‡ of this step is somewhat large (22.4 kcal/mol), which is consistent with the higher reaction
temperature in the experiment compared to those of the previous steps. The subsequent C-C bondformation between the incoming propyne and INT4a leads to the generation of INT4b with a very2
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Ⅳ 研究業績 (2013)

small ΔG0‡ value of 4.6 kcal/mol. In INT4b, an eight-member ring has not been formed yet but afused ring structure consisting of four-member and six-member rings is found interestingly. Then,the Mo-C bond breaking occurs to induce the ring extension, which leads to the formation of aneight-member ring complex 4 concomitantly with re-coordination of the N atom of the N^N ligand
with the Mo center. These two steps both occur facilely; see ΔG0‡ = -4.2 kcal/mol for TS4c and 4.6
kcal/mol for TS4d, as shown in Figure 3.

2.
08
9

Figure 2. Energy change in the [4+2] cycloaddition between 2 and propyne.
2.843

Mo

R1 N

Mo

R1
N
N R
1

2.149
Mo
R1 N

N

R1

TS4a

N

Mo

N

Mo N

R1

N

RMo-Mo = 2.167

R1

R1
RMo-Mo = 2.177

1.284

-91.1
-111.1

N

Mo
7

N

2.795

R1

N

1
2.1

R1 N

R1

Mo
3
N 2.92

R1

TS4b

-97.0
-117.5

3-113.5-126.8

Mo

N
Mo

R1 N
N
R1

RMo-Mo = 2.205

R1
N

N

Mo
Mo

R1 N

R1

R1 N
1.346

N

N

R1
RMo-Mo = 2.201

R1R1-100.8-123.3

4-105.4-127.8

N
Mo
78
2 .0

N

RMo-Mo = 2.180

INT4c

2.077
R1

Mo

R1

TS4d

-100.9-122.2-96.7-118.4

N

N

TS4c

INT4b

1.589
R1

N

RMo-Mo = 2.195-92.4-113.9

INT4a

R1

R1

RMo-Mo = 2.201

R1Mo-107.2-129.0

2.231
R1

R1 N

Mo

N

R1

Mo
N
R1
N 2.290
R1
RMo-Mo = 2.217

R1

N
N

R1

Mo
Mo

N R1
N

R1
RMo-Mo = 2.143

Figure 3. The energy change in the [6+2] cycloaddition between 3 and propyne.
Starting from 4, two reaction pathways are possible; in one, benzene is produced via reductive
elimination (blue line in Figure 4) and in another, one more propyne is inserted into the Mo-C bondto produce a ten-member ring which is ring extension (black line in Figure 4). In the reductive
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Ⅳ 研究業績 (2013)

elimination, the ΔG0‡ value is 6.9 kcal/mol and the ΔG0 is -55.3 kcal/mol relative to 4, indicating thatthe reductive elimination easily occurs with a moderate activation barrier and a significantly large
exothermicity. In the ring extension pathway, the ΔG0‡ value of alkyne insertion is 13.5 kcal/mol andthe ΔG0‡ value of reductive elimination of 1,3,5,7-tetramethyl-cyclooctatetraene is 13.6 kcal/mol,indicating that this reaction can occur thermally but it is more difficult than the reductive
elimination of benzene.
1.907

2.408

R1
N

Mo

3.322 Mo
N
8
2.98

R1

R1
N

Mo
N

R1 R1

N

N

2.091

C1

2.133

Mo
N

Mo

R1

R1

Mo

-93.7
-125.0N-108.4-131.3

Mo

R1

Mo

N

Mo

R1

-116.4-146.9

C2

N R1

3.117
R1

C1
N

Mo
N

N

N

R1

Mo

N

R1

N

R1

RMo-Mo = 2.151

N

Mo

1

R1

N

2.287

2.154

RMo-Mo = 2.208

2.370

2.857
Mo

R1

-162.6-192.6-165.4-189.0

R1

2.114

6

2

-162.5-186.0

R1

C2
R

Mo
R1

5

2.153

RMo-Mo = 2.143

TS6c-101.3-132.7-127.4-158.3

INT6a
N

R1

INT6c
INT6b

N

R1

-114.9-146.3

3.612
C1

N

RMo-Mo = 2.161-102.0 -101.5-132.7 -124.5

N

N R1

N
R1

TS6b TS5a

INT5

Mo

N R1

RMo-Mo = 2.132

2.100
Mo

R1

4

N
N
R1

2.120

RMo-Mo = 2.131

TS6a-107.2-129.0

2.199
Mo

R1

R1

RMo-Mo = 2.188

R1

3.051

N

N

R1

RMo-Mo = 2.142

2.185

R1
C2
N

N

N

R1

2.116

N

Mo

N

N

N

Mo

R1

R1

N

R1

Mo

N

2.229

R1
N

N

R1

R1

RMo-Mo = 2.139

RMo-Mo = 2.141

Mo

R1

N

R1

N R1

Mo

N

N

R1

R1

RMo-Mo = 2.138

Figure 4. The energy change in the reductive elimination of benzene and [8+2] cycloaddition
between 4 and propyne.
Cr
R1 N

The [4+2] cycloaddition forwhere the superscript “Cr” means
the Cr analogue. In 2Cr, the dihedral
1

1

2

2

angle φ(C -Cr -Cr -C ) is -31.4º,
whichagrees

well

with

the

N

6
1.2
RCr-Cr = 1.954
TS3aCrreaction between propyne and thestudied with the DFT method,

N

N
R1

the Cr-Cr analogue of 2. The
Cr-Cr analogue of 2 (2Cr) was

Cr

2.152

R1

1.2

R1
Cr
R1 N

-23.9
-36.2

2

Cr
42
N 2.0
R1

N

N

Cr

INT2
-56.1
-68.0

R1

RCr-Cr = 1.723

formation of 2Cr from 1Cr and

R1 N

Cr

N

and one

N

Cr

N

N

R1

RCr-Cr = 1.801
TS3cCr

-28.4
-41.7

INT3Cr
-33.3
-46.0

R1

Cr
N C3
C4
N

C2 R
N

Cr

N

R1
RCr-Cr = 1.780

1

R1
R1

N

R1

N

Cr
Cr

N R1
N

R1
RCr-Cr = 1.786
Cr
3

-94.4
-107.5

R1
RCr-Cr = 2.237

propyne is significantly exothermic
cycloaddition between 2

R1
N
Cr 1 N
.9
04 R1
16
1.3

R1

R1

R1

C1

2.218

Cr

N

N

R1

R1

experimental value (-33.6º). The

by -43.9 kcal/mol. The [4+2]

N

-37.0
-52.6

-38.7
-43.9

R1 N

Cr

R1

N
R1
RCr-Cr = 2.038
TS3bCr

Cr

Cr

Cr

1.937

2.317

0

87

Figure 5. The energy change in the [4+2] cycloaddition
between 2Cr and propyne.
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Ⅳ 研究業績 (2013)

more propyne occurs similarly to the Mo system, as follows: Propyne coordinates with 2Cr to afford a stableintermediate INT2Cr via a transition state TS3aCr. The ΔG0‡ value is 14.8 kcal/mol, which is much larger
than that (4.7 kcal/mol) of the Mo reaction system; see Figure 5. The ΔG0‡ value of the C-C bond formation
is 27.7 kcal/mol, which is also much larger than that (15.5 kcal/mol) of the Mo system. In TS3aCr, thedistance between the Cr2 and the C3-C4 bond is about 2.09Å, which is shorter than that of 2.43Å in TS3a.
The larger coordination barrier of TS3aCr is likely due to (1) the smaller radius of the Cr 3d orbital than the
Mo 4d orbital, which leads to a more congested geometry around the Cr center, and (2) the much more stableߨௗ೤೥ (-6.86 eV) in 2Cr than that (-6.25 eV) in 2, which is unfavorable for the alkyne coordination with the Cr
center.

Based on these results it should be concluded that 1Cr cannot be applied to catalytic synthesis ofbenzene from three molecules of alkyne.
In this work, the reaction mechanism of catalytic synthesis of benzene from alkynes by the

Mo-Mo quintuple bonded complex 1 was investigated by DFT method. The [2+2] cycloaddition
occurs with a negligibly small activation barrier in which alkyne interacts with one Mo center in asymmetry-allowed manner. The next [6+2] reaction between 3 and one more alkyne occurs with themoderate ΔG0‡ value of 22.4 kcal/mol to afford an eight-member ring compound 4. This is therate-determining step of the whole catalytic cycle. The subsequent reductive elimination of benzene easily
occurs and a μ2-η2:η2-C6H6 coordinated Mo-Mo complex is formed. The [8+2] cycloaddition between 4 andone more alkyne is much more difficult than the reductive elimination of benzene. In should be emphasizedthat the ݀ఋ െ ‫݌‬஠ π MO plays crucial roles in this catalytic cycle.

In the case of the Cr-Cr quintuple bond, the [4+2] cycloaddition needs a much more larger ΔG0‡ value

because of the much more stable ߨௗ೤೥ orbital and the more congested transition state arising from the small
radius of Cr atom.

2. Original papers(1) Yue Chen and 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 andBonding Nature.”
Inorg. Chem., 52, 13146-13159 (2013).
(2) Yue Chen and Shigeyoshi Sakaki“The important role of the Mo-Mo quintuple bond in catalytic synthesis of benzene fromalkynes. A theoretical study.”
Dalton Trans., 2014, Advance Article. DOI: 10.1039/C4DT00595C
3. Presentation at academic conferences(1) Yue Chen and Shigeyoshi Sakaki
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Ⅳ 研究業績 (2013)“Catalytic Synthesis of Benzene from Acetylene with Dinuclear Molybdenum Complex: A
Theoretical Study”
第 60 回有機金属化学討論会 (P1A-09),Tokyo, Sept. 12, 2013
(2) Yue Chen and 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 andBonding Nature”
第 7 回分子科学討論会, Kyoto, Sept. 24, 2013
(3) Yue Chen and Shigeyoshi Sakaki“Electronic Structure of N2-bridged lanthanide single-molecule magnet”
5th JCS International Symposium on Theoretical Chemistry, Kyoto, Dec. 2, 20136
－ 183 －

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Ⅳ 研究業績 (2013)

SayyedSayyedFareed
FareedBHASHA
BhashaSPR Fellow
1.

Summary of the research of the year

The Crucial role of Ni(I) species in Ni-catalyzed Carboxylation of Aryl Halides with CO2
The increasing concentration of carbon dioxide (CO2) in the atmosphere poses a severe threat
to environmental safety due to greenhouse effect. Over the past few years efforts have been increased
to reduce the CO2 emission from the industries or to store CO2 and most of these attempts areinauspicious. Although reducing the CO2 concentration directly from the atmosphere is a difficult
task but indirectly it can be reduced by utilizing CO2 to prepare useful chemicals. CO2 isthermodynamically stable and kinetically inert, the transformation of CO2 to useful materials need
powerful catalysts. Transition metal complexes have been used as promising catalysts for CO2
activation. In particular, synthesis of carboxylic acids and its derivatives from CO2 is of much recent
interest because they are important chemicals in the industry and they can also serve as starting
materials for other organic transformations. However, the direct carboxylation of aryl halides with
CO2 has remained elusive. Correa and Martin proposed a Pd-catalyzed direct carboxylation reactionof aryl bromides with CO2. However, this reaction occurs only when reactive aryl bromides are
employed but cannot when aryl chlorides are employed. Very recently, Tsuji and his co-workers
succeeded to overcome this limitation by developing a nickel catalytic system. As shown in Scheme 1,
aryl chloride is directly transformed to corresponding carboxylic acids with CO2 in the presence ofNi(0) complex and Mn.

Scheme 1. Ni(0) catalyzed direct carboxylation of phenyl chloride with CO2.
As shown in Scheme 1, aryl chlorides can be easily converted to the carboxylic acids using
Ni-catalyst. This is the first example showing the metal mediated C-C coupling of carbon dioxide andaryl halides at ambient temperature. This reaction is selective only to the aryl chlorides and bromides
but not the flourides. Why aryl chlorides and bromides are susceptible to carboxylation? What is themechanism of the catalytic reaction? what Ni(I) species participates in the reaction? why Ni(I)species is necessary? what elementary step is accelerated by the Ni(I) species? The originality of the
proposal comes out by unveiling the origin of these facts, and I expect that probably some guidelines
would be feasible for the designing of new and efficient catalysts.
Shown in Scheme 2 is the most plausible mechanism for the Ni-catalyzed direct
carboxylation of PhCl with CO2. The reaction starts with oxidative addition of PhCl to Ni(PPh3)2.
1－ 184 －

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Ⅳ 研究業績 (2013)

Coordination of PhCl leads to the formation of a 2-coordinated precursor complex Ni(PPh3)2(PhCl)
3 in which the C=C bond of PhCl coordinated with the Ni-center. From 3, the C-Cl bond cleavage
occurs through a 3-membered transition state TS3-4 to afford a cis-nickel chlorophenyl complex 4 asshown in Scheme 2. Complex 4

Scheme 2. Catalytic cycle of Ni(0) catalyzed carboxylation of aryl chlorides with CO2.
isomerizes to the more stable squareplanar trans-form 5. Because 5 is a Ni(II) complex, it canundergo one electron reduction by Mn to afford 6. CO2 approaches 6 to form a 2-coordinated
Ni(Ph)(PPh3)2(CO2) adduct 7. From 7, CO2 insertion into the Ni(I)-Ph bond gives a 1-coordinated
NiI(PPh3)2(1-OCOPh) 8 through a transition state TS7-8. The most important result is the existence ofNi(I) intermediate which is essential for the conversion of CO2 to COOH group. We hope that thisinteresting result will open up new Ni-catalysts in the transition metal catalyzed conversion of CO2.

2.

List of original papers(1)

Sayyed Fareed Bhasha, Yasushi Tsuji, and Shigeyoshi Sakaki,“The crucial role of a Ni(i) intermediate in Ni-catalyzed carboxylation of aryl chloride with CO2: A
theoretical study”
Chem. Commun. 49(91), 10715-10717 (2013).

3.

List of review articles(1) Guan, Wei, Sayyed Fareed Bhasha, Guixiang Zeng, Shigeyoshi Sakaki.
“σ-Bond Activation of Small Molecules and Reactions Catalyzed by Transition-Metal Complexes:
Theoretical Understanding of Electronic Processes“2－ 185 －

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Ⅳ 研究業績 (2013)

Inorg. Chem. DOI: 10.1021/ic5003429 (2014).
4.

List of presentations at meetings(1) CO2 Insertion into Ni(I)-Alkyl and Ni(II)-Alkyl Bonds.Interesting Differences. Sayyed, F. B and
Sakaki, S. The 7th Annual Meeting of Japan Society for Molecular Science, Kyoto, September 24-27,
2013.
(2) Crucial role of a Ni(I) intermediate in Ni-catalyzed carboxylation of aryl chloride with CO2.
F.B. Sayyed, Y. Tsuji and S. Sakaki*, FIFC symposium, k The 6th symposium of Fukui Institute for
Chemistry, Kyoto, January 23, 2014.

3－ 186 －

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Ⅳ 研究業績 (2013)

山田
��

健太
�太

特推研究フェロー

特�研究��ロー
1. 今年度の研究の要�
今年度は、プロトン還元触媒作用を示す Ni(II)錯体の構造や電子状態に関する研究を行った。
䛆䛿䛨䜑䛻䛇
水素ガスは、燃焼で二酸化炭素を生成しない、かつ高いエネルギー密度をもつ優れた燃料であり、低炭素社会に向けた次世代エネルギーの１つとして大きな期待が寄せられている。しかしながら、入手可能な天然資源として決して大量にあるわけではない。そこで、近年、遷移金属錯体の存在下で、電気化学的な酸化・還元反応を用いた水の分解による水素ガスの生成が注目されている[1]。この分解では副次生成物は酸素ガスであり、有害な物質を排出しないことが特長である。
水１分子の分解（式１）は吸熱反応であり、必要であるエネルギーは 2.46 eV と知られている。
H2O → H2 + (1/2)O2(1)

逆に言えば、これは水素ガスの酸化（燃焼）によって 2.46 eV ものエネルギーが得られることを示している。分解を進行させるために必要なエネルギーとして化石燃料によるものを使うのは、明らかに本末転倒である。そこで、「人口光合成」、つまり、太陽光などの光エネルギーを用いて水の分解を実施し、そのエネルギーを化学エネルギーに変換し蓄えることが考えられてきた。
可能な限り少ないエネルギーによって水素ガスを生成するために、これまで多くの実験研究によって、プロトン還元活性をもった遷移金属触媒が報告されてきた。特に、コスト面から Pt などの貴金属ではなく、Co や Ni、Mo などを用いた触媒の提案が盛んになっている。本研究では、これまで提案されてきた遷移金属触媒のなかで、長時間にわたって高い水素発生活性を示す Ni(II)錯体[2]を取り上げ、その１電子還元体、２電子還元体、プロトン付加体のスピン状態や電子構造を明らかにするとともに、Ni(II)−H と配位子に付加したプロトン(N–H)とのカップリングにより、水素ガスを生成する素反応の電子的過程の解明を目指した。
䛆ィ⟬᪉ἲ䛇
DFT(B3PW91 汎関数)法を使用し、CPCM 法で溶媒効果を考慮して構造最適化を行なった。このとき、GD3BJ 経験的分散力モデルを用いた。Ni には、内殻電子を Stuttgart グループの ECP(SSD)で置
き換え、原子価電子には(311111/22111/411/11)基底を用いた。生成する水素ガスに関与する H には6-311++G(d,p)基底を、そして残りの原子には 6-311G(d)基底を使用し、N と S には diffuse 関数を加えた。また、CPCM 法で使用する誘電率は、288 K で EtOH:H2O=1:1 の混合溶媒を用いている実験
条件を再現するために、複数の温度での実験値を使った内挿によって決定した。
䛆⤖ᯝ䛸⪃ᐹ䛇1－ 187 －

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Ⅳ 研究業績 (2013)

注目する Ni(II)錯体には、図１に示す
ように meridional 型(1)と facial 型(1’)の異性体が考えられる。ただし、X
線結 晶構造解析 で観測でき るのは
mer 型だけである。電子状態について
は、1、1’ともに一重項状態より 18–23
kcal/mol 程度、三重項状態が安定になった。
実験報告では、1, 1’が仲介する水素発生サイクルは、スキーム１に示す

図１: 注目した Ni(II)錯体における異性体の構造。図中の数字はように、プロトン付加→１電子還元

結合長を表し、単位は Å である。

→プロトン付加→１電子還元で進むと考えられている。
まず、プロトン非存在下ならびに存在下における cyclic voltammetry(CV)の結果と比較するために、1 と 1’のプロトン付加体(1_2)、および、
その１電子還元体(1_3)を求め、これらの自由エ
ネルギーから還元電位を計算した。１回目のプロトン付加では、プロトンはピリジン環の Nに付加し、結果として４つの異性体を生じる。
この４つの異性体に対して、式２による還元電位の結果を表１にまとめた。
E = –ΔG×27.211 – ESRP

(2)
スキーム１

ここで、ΔG は自由エネルギー差であり、ESRP
は標準還元電位（ここでは飽和カロメル電極、
SCE）である。表１より、実験を概ね再現していることが分かった。しかしながら、実験は単一水溶媒を使用していないため、用いる ESRP に議論の表１：４つの異性体をもつプロトン付加体(1_2)の還元電位 [in V vs SCE]

ESRP

余地がある。

4.522a

２回目のプロトン付加(1_4)は、Ni に付加するよ
りも、ピリジン環の N に付加する方が安定である。
そのため、２回目の１電子還元（1_5）の前後で、プロトンが N から Ni(I)に移動する異性化反応が起こっていると考えられる。ただし、２回目の１電子還元が、２回目のプロトン付加に先んじて起こっている可能性があり、現在検討を行っている。

1_2/1_3a4.681b

–1.3

–1.4

–1.5

–1.6

–1.3

–1.5

–1.5

–1.6

Exptl.
–1.2

実験値から求めた、真空中 0 K での電子エネ

ルギーを基準としたときの、水中における SCE
還元電位[3]b

水中 298.15 K での IUPAC 推奨値

Ni(II)–H とピリジル環の N に付加したプロトンのカップリングにより、水素ガスが発生する素反応(1_6→TS1_6/INT→INT1_6/1)に関し、異性体における構造および点電荷(Natural charges)の変化を図２に示す（４つの異性体のうち、１つのみ示した）。電荷の変化から、水素分子の生成はプロトンと2－ 188 －

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Ⅳ 研究業績 (2013)

ヒドリドによるヘテロカップリング反応であることを確認した。この異性体における反応障壁は、
自由エネルギーでわずか 0.58 kcal/mol であり、さらに INT1_6/1 からは障壁なく H2 が解離するので、
1 と 1’は効率よく水素を発生すると予想される。これは、実験報告にある、単位時間あたり発生する水素分子の数である初期ターンオーバー頻度(initial TOF)が高いことに対応している。また、実験
では、ピリジル基の５位の H を Cl や CF3 に置換した系も取り扱っている。そこで、このような電子求引基だけでなく、CH3 といった電子供与基を用いた計算の実施により、スキーム１における各構造の特徴や反応障壁の変化について引き続き調査を行なっていく。

図２：Ni(II)–H とピリジル基に付加した H の反応に付随した構造および点電荷(Natural charges)の変化。
図中の数字のうち、構造に付したものは結合長で単位は Å であり、構造下の数値が電荷であり単位は eである。また、点線で囲んだ部分が反応中心である。

䛆ᩥ⊩䛇
[1] (a) Dempsey, J. L.; Brunschwig, B. S.; Winkler, J. R.; Gray, H. B. Acc. Chem. Res. 2009, 42, 1995–2004.
(b) Artero, V.; Chavarot-Kerlidou, M.; Fontecave, M. Angew. Chem. Int. Ed. 2011, 50, 7238–7266.
[2] (a) Han, Z.; McNamara, W. R.; Eum, M.-S.; Holland, P. L.; Eisenberg, R. Angew. CHem. Int. Ed. 2012,
51, 1667–1670. (b) Han, Z.; Shen, L.; Brennessel, W. W.; Holland, P. L.; Eisenberg, R. J. Am. Chem. Soc.
2013, 135, 14659–146669.
[3] Isse, A. A.; Gennaro, A. J. Phys. Chem. B 2010, 114, 7894−7899.

2. ��(1) Hiyama, M.; Akiyama, H.; Yamada, K.; Koga, N. “Theoretical Study of Fluorescence
Spectra Utilizing the pKa Values of Acids in Their Excited States” Photochem. Photobio.
3－ 189 －

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Ⅳ 研究業績 (2013)2014, 90, 35–44.
(2) Mashiko, T.; Yamada, K.; Kojima, T.; Hiraoka, S.; Nagashima, U.; Tachikawa, M.
“Molecular dynamics and principal component analysis for a self-assembled nanocube inaqueous solution” Chem. Lett. 2014, 43, 366–368.
(3) Yamada, K.; Kawashima, Y.; Tachikawa, M. “Muon-electron hyperfine coupling constantsof muoniated ethyl radical: a path integral simulations study with semiempirical molecularorbital method” Chin. J. Phys. 2014, 52, 126–137.
(4) Hiyama, M.; Akiyama, H.; Mochizuki, T.; Yamada, K.; Koga, N. “Analysis of
Photoexcitation Energy Dependence in the Photo Luminescence of Firefly Luciferin”
Photochem. Photobio. 2014, 90, 820–828.
3. 学会発�(1) ○山田健太、青野信治、榊茂好 “水還元活性を示すコバルト錯体の酸化還元電位に関する理論的研究”、日本コンピュータ化学会 2013 秋季年会、2P19、福岡、2013 年
10 月(2) Koyanagi, K.; Kita, Y.; Yamada, K.; Kawashima, Y.; ○Tachikawa, M. “Quantum simulationfor exotic molecules: Quantum Monte Carlo and Path Integral approach”, 3rd International
Conference on Molecular Simulation (ICMS2013), 2P03, Kobe (Nov, 2013)(3) ○Hiyama, M; Yamada, K.; Mochizuki, T.; Akiyama, H.; Koga, N. “Theoretical study for
excited states of firefly-bioluminescence-related molecules”, 5th JCS International
Symposium on Theoretical Chemistry, PIIa-17, Nara (Dec, 2013)
4. �の�
(1) ○山田健太、榊茂好「ニッケル錯体の水素発生に関する理論的研究」第11回京都大学福井謙一記念研究センターシンポジウム、P36、京都、2013年１月

4－ 190 －

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Ⅴ 資料 (2013)

Ⅴ資料

１．外国人共同研究者受入れ状況（平成 25 年度）

氏名

PETROVA Galina

受入れ身分

受入れ期間

所属機関・職外国人

平成24年5月13日～

University of Sofia

共同研究者

平成25年5月29日（ブルガリア）・教授

受入れ教員

研究内容

DNAのキラリティ
諸熊奎治に基づいた銅触媒の立体化学選択性の理論モデルRYAZANTSEV

外国人

平成25年3月1日～

Mikhail

Emory University

共同研究者

平成25年4月30日（アメリカ）・研究員

DANG

外国人

平成25年4月16日～

西安交通大学（中国）Jing-Shuang

共同研究者

平成25年10月15日

・博士課程学生

ZHAO Xiang

招へい

平成25年7月19日～

西安交通大学（中国）

趙

外国人学者

平成25年9月1日

・教授

外国人

平成26年2月2日～

Raoul Marcel

共同研究者

平成27年2月1日

PURIPAT

外国人

平成26年2月27日～

共同研究者

平成27年2月26日

翔

RAMOZZI Romain

Maneeporn

諸熊奎治

永瀬

茂

金属内色フラーレ永瀬茂

ン生成機構に関する理論解析

有機多成分反応の諸熊奎治

反応機構と設計の理論化学的研究

Chualongkorn
PhD 学生遷移金属元素化学種の理論化学程学生

University（タイ）・

力学の理論的研究

高周期典型元素とリヨン高等師範大学（フランス）・博士課

ロドプシンの光動諸熊奎治

複雑分子系の理論
化学・計算化学－ 191 －

fukui2013.indb 191

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Ⅴ 資料 (2013)

２．海外渡航一覧（平成 25 年度）

職

名

氏

名

期間（自）

期間（至）

目

研究員（学術研究奨励）諸熊奎治

2013.5.7

2013.5.10

中研究員（学術研究奨励）諸熊奎治

2013.5.13

2013.6.7

特定研究員

畑中

美穂

2013.7.10

2013.7.13

韓国

研究員（学術研究奨励）諸熊奎治

2013.7.10

2013.7.13

韓国

研究員（学術研究奨励）榊茂好2013.7.10

2013.7.13

韓国

研究員（学術研究奨励）永瀬茂

2013.7.10

2013.7.13

韓国

研究員（学術研究奨励）諸熊奎治

2013.8.25

2013.8.31

アメリカ合衆国

特定研究員

岡本

隆一

2013.9.14

2013.9.21

イタリア

研究員（学術研究奨励）榊茂好2013.10.13

2013.10.19

スウェーデン

研究員（学術研究奨励）榊茂好2013.10.23

2013.10.28

アメリカ合衆国研究員（学術研究奨励）諸熊 奎治

2013.11.11

2013.11.19

アメリカ合衆国研究員（学術研究奨励）諸熊2014.1.6

2014.1.13

アメリカ合衆国

奎治

的

地

国

アメリカ合衆国－ 192 －

fukui2013.indb 192

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Ⅴ 資料 (2013)

３．研究業績一覧（平成 25 年度）№

池田

Authors

Title

JournalVolume (Number),first page tolast page

year

昌司

1

Daniele Coslovich, andAtsushi Ikeda

Cluster and reentrant anomalies of nearly
Gaussian core particles

Soft Matter

9, 6786-6795

2013

2

Atsushi Ikeda, Ludovic
Berthier, and Peter Sollich

Disentangling glass and jamming physics
in the rheology of soft materials

Soft Matter

9, 7669-7683

2013

3

Atsushi Ikeda and Ludovic
Berthier

Yield stress in amorphous solids: A
mode-coupling-theory analysis

Physical Review
E88, 052305(1-14)

2013

4

池田昌司

ガラス転移とジャミング転移を分離する

日本物理学会誌

68 (7), 464-467

2013

永瀬

茂

5

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

6

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

7

Y. Maeda, J. Higo, Y.
Amagai, J. Matsui, K.
Ohkubo, Y. Yoshigoe, M.
Hashimoto, K. Eguchi,
M. Yamada, T. Hasegawa,Y. Sato, J. Zhou, J. Lu, T.
Miyashita, S. Fukuzumi,
T. Murakami, K. Tohji, S.
Nagase, and T. Akasaka

Helicity-Selective Photoreaction ofSingle-Walled Carbon Nanotubes with
Organosulfur Compounds in the Presenceof Oxygen

J. Am. Chem.
Soc.

135, 6356-6362

2013

8

Y. Xie, M. Suzuki, W. Cai,
N. Mizorogi, S. Nagase, T.
Akasaka, and X. Lu

Highly Regioselective Addition of
Admantylidene Carbene to Yb@
C2v(3)-C80 to Afford the First Derivativeof Divalent Metallofullerenes

Angew. Chem.
Int. Ed.

52, 5142-5145

2013

9

T. Akasaka, T. Tsuchiya,
L. Feng, Y. Takano, and S.
NagaseNew Vistas in Fullerene Chemistry:
Organosulfer Compounds Expand the
Performance of Carbon Nanomaterials

Phosphorus,
Sulfur Silicon
Relat. Elem.

188, 317-321

2013

10

P. Jin and S. Nagase

Density Functional Theory Study of
Fullerene-Carbene Lewis Acid-Base
Adducts: Critical Role of Dispersion
Interactions

RSC Adv.

3, 10177-10180

2013

11

J. –S. Dang, W. –W. Wang, S.
Nagase, and X. Zhao

Regiochemistry of Nonclassical C62
Fullerene: Role of Tetragonal Carbocyclic
Ring in Cycloadditions and Thermal/
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J. Phys. Chem. C

117,12882-12889

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G. Luo, Q. Zheng, W. –N.
Mei, J. Lu, and S. Nagase

Structural, Electronic, and Optical
Properties of Bulk Graphdiyne

J. Phys. Chem. C

117,13072-13079

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13

Y. Takano, C. Schubert, N.
Mizorogi, L. Feng, A. Iwano,
M. Katayama, M. A. Herranz,
D. M. Guldi, N. Martion, S.
Nagase, and T. Akasaka

Intramolecular versus IntermolecularElectronic Interactions between [5,6]Open and [6,6]-Closed Adducts with
exTTF

Chem. Sci.

4, 3166-3171

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X. Lu, T. Akasaka, and S.
NagaseCarbide Cluster Metallofullerenes:
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A Metallofullerene Electron Donor thatPowers an Efficient Spin Flip in a Linear
Electron Donor- Acceptor Conjugate

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135,
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R. Fei, G. Luo, Y. Wang, Z.
Gao, S. Nagase, D. Yu, and J.
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Enhanced Many-Body Effects in OneDimensional Linear Atomic Chains

Phys. Status.
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250, 1636-1643

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W. Zhang, M. Suzuki, Y. Xie,
L. Bao, W. Cai, Z. Slanina, S.
Nagase, M. Xu, T. Akasaka,
and X. Lu

Molecular Structure and Chemical
Property of a Divalent Metallofullerene
Yb@C2(13)-C84

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T. Yang, X. Xhao, and S.
Nagase

1,3-Dipolar Cycloadditions of StoneWales Defective Single-Walled Carbon
Nanotubes: A Theoretical Study

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34, 2223-2232

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M. Yamada, T. Akasaka, and
S. Nagase

Carbene Additions to Fullerenes

Chem. Rev.

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T. Agou, T. Wasano, P. Jin, S.
Nagase, and N. Tokitoh

Synthesis and Structures of an Alumoleand its Dianion

Angew. Chem.
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C. Schubert, M. Rudolf, D.
M. Guldi, Y. Takano, N.
Mizorogi, M. A. Herranz,
N. Martín, S. Nagase, and T.
AkasakaRates and Energetics of IntramolecularElectron Transfer Processes in ConjugatedMetallofullerenes

Phil. Trans. R.
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M. Tanaka, M. Katouda, and
S. Nagase

Optimization of RI-MP2 Auxiliary Basis
Functions for 6-31G** and 6-311G**
Basis Sets for First-, Second-, and ThirdRow Elements

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34, 2568-2575

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H. Zheng, X. Zhao, W. –W,
Wang, J. –S. Dang, and S.
NagaseQuantum Chemical Insight into
Metallofullerenes M2C98: M2C2@C96 or
M2@C98, Which Will Survive?

J. Phys. Chem. C

117,25195-25204

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C. -Y. Lin, J. –D. Guo, J.
C. Fettinger, S. Nagase, F.
Grandjean, G. J. Long, N. F.
Chilton, and P. P. Power

Dispersion Force Stabilized TwoCoordinate Transition Metal-Amido
Complexes of the -N(SiMe3)Dipp (Dipp= C6H3-2,6-Pr i2) Ligand: Structural,
Spectroscopic, Magnetic, andComputational Studies

Inorg. Chem.

52,
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T. Yang, X. Zhao, and S.
NagaseCycloaddition of Benzyne to Armchair
Single-Walled Carbon Nanotubes: [2+2]or [4+2]?

Org. Lett

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M. Suzuki, N. Mizorogi, T.
Yang, F. Uhlik, Z. Slanina, X.
Zhao, M. Yamada, Y. Maeda,
T. Hasegawa, S. Nagase, X.
Lu, and T. Akasaka

La2@Cs(17490)-C76: A New Non-IPR
Dimetallic Metallofullerene Featuring
Unexpectedly Weak Metal-Pentalene
Interactions

Chem. Eur. J.

19, 17125-17130

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F. Uhlík, Z. Slanina, S. –L.
Lee, T. Akasaka, and S.
NagasePredicting Stabilities of Endohedral
Metallofullerenes Yb@C84

Phys. Status
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J. N. Boynton, J. –D. Guo, F.
Grandjean, J. C. Fettinger,
S. Nagase, G. J. Long, P. P.
Power

Synthesis and Characterization of the
Titanium Bisamide Ti{N(H)Ar iPr6}2 (Ar iPr6
= C6H3-2,6-(C6H2-2,4,6-iPr3)2 and its
TiCl{N(H)Ar iPr6}2 Precursor: Ti(II)® Ti(IV) Cyclization

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52,
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J. N. Boynton, J. –D. Guo, J.
C. Fettinger, C. E. Melton, S.
Nagase, and P. P. PowerLinear and Nonlinear Two-Coordinate
Vanadium Complexes: Synthesis,
Characterization, and Magnetic
Properties of V(II) Amides

16

M. Rudolf, L. Feng, Z.
Slanina, T. Akasaka, S.
Nagase, and D. M. Guldi

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Diversity of the Structures in a
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J. Ruan, Y. Xie, W. Cai, Z.
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Nagase, T. Akasaka, and X.
Lu

Chemical Properties of Divalent
Metallofullerenes Yb@D3h(1)-C74 andYb@C2(13)-C84

Fullerenes,
Nanotubes,
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22, 138-146

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Z. Slanina, F. Uhlík, S. –L.
Lee, M. Suzuki, X. Lu, N.
Mizorogi, S. Nagase, and T.
AkasakaCalculated Temperature Developmentof the Relative Stabilities of Yb@C82
Isomers

Fullerenes,
Nanotubes,
CarbonNanostruct.

22, 147-154

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Z. Slanina, F. Uhlík, S. –L.
Lee, L. Adamowicz, H.
Kurihara, H. Nikawa, X. Lu,
M. Yamada, S. Nagase, and T.
AkasakaComputations on Metallofullerenes
Derivatized during Extraction: La@C80C6H3Cl2 and La@C82-C6H3Cl2

Fullerenes,
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22, 173-181

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Z. Slanina, F. Uhlík, S. –L.
Lee, L. Adamowicz, L. Feng,
M. O. Ishituka, T. Tsuchiya,
X. Zhao, and S. Nagase

Sm@C74: Computed Relative Isomeric
Populations

Fullerenes,
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22, 235-242

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Z. Slanina, F. Uhlík, S.
–L. Lee, B. C. Wang, L.
Adamowicz, M. Suzuki, M.
Haranaka, L. Feng, X. Lu, S.
Nagase, and T. Akasaka

Towards Relative Populations of NonIsometric Metallofullerenes: La@C76(Td) vs. La2@C76 (Cs, 17490)

Fullerenes,
Nanotubes,
CarbonNanostruct.

22, 299-306

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S. Nagase

Theory and Calculations of Molecules
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and Fullerenes Encaging Transition
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奎治
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J. –S. Dang, W. –W. Wang, X.
Zhao, and S. Nagase

Regioselective Derivatization of C84 byDiels-Alder Reactions: Applications to
Photovoltaic Solar Cells and Fullerene
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T. Kuwabara, J. D. Guo, S.
Nagase, and M. Saito

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M. Hatanaka, S. Maeda andK. Morokuma

Sampling of Transition States for
Predicting Diastereoselectivity Using
Automated Search Method – Aqueous
Lanthanide-Catalyzed Mukaiyama Aldol
Reaction

39

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

Nucleation of Graphene Precursors on
Transition Metal Surfaces: Insights from
Theoretical Simulations

J. Phys. Chem. C.

117,14858-14864

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40

H. Xiao, S. Maeda and K.
Morokuma

Theoretical Study on the
Photodissociation of Methylamine
Involving S1, T1, and S0 States

J. Phys. Chem. A

117, 5757–5764

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41

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

the Dual Role of Hydrogen for DefectHealing and Growth Inhibition In
Polycyclic Aromatic Hydrocarbon
Formation with QM/MD Simulations

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4, 2323-2327

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F. Liu and K. Morokuma

Multiple Pathways for Primary Step of
Spiropyran Photochromic Reaction: a
CASPT2//CASSCF Study

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135,
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S. Maeda, T. Taketsugu, and
K. Morokum,

Exploring Pathways of Photoaddition
Reactions by Artificial Force Induced
Reaction Method: A Case Study on thePaternò-Büchi Reaction

Zeit. Phys. Chem.

227, 1421-1433

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H. Xiao, S. Maeda and K.
MorokumaA CASPT2 Study of Photodissociation
Pathways of Ketene

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T. V. Harris and K.
Morokuma

QM/MM Structural and Spectroscopic
Analysis of the Di-iron(II) and Diiron(III) Ferroxidase Site in M Ferritin

Inorg. Chem.

52, 8551-8563

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Y. Harabuchi, S. Maeda, T.
Taketsugu, N. Minezawa, and
K. Morokuma,

Automated search for minimum energy
conical intersection geometries between
the lowest two singlet states S0/S1-MECIs
by the spin-flip TDDFT method

J. Chem. Theory
Comput.

9, 4116-4123

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47

W. Piao, S. Tsuda, Y.
Tanaka, S. Maeda, F. Liu, S.
Takahashi, Y. Kushida, T.
Komatsu, T. Ueno, T. Terai, T.
Nakazawa, M. Uchiyama, K.
Morokuma, T. Nagano, andK. Hanaoka

Development of a New Class of Azobased Fluorescence Probes to Detect
Different Levels of Hypoxia

Angew. Chem.
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M. Hatanaka and K.
Morokuma

Role of Water in Mukaiyama–Aldol
Reaction Catalyzed by Lanthanide Lewis
Acid: A Computational Study

J. Am. Chem.
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135,
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F. Liu, Y, Kurashige, T.
Yanai, and K. Morokumq

Multireference Ab Initio Density Matrix
Renormalization Group (DMRG)CASSCF and -CASPT2 Study on
the Photochromic Ring-Opening of
Spiropyran

J. Chem. Theory.
Comput.

9, 4462-4469

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50

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

Temperature Dependence of CatalystFree Chirality-Controlled Single-Walled
Carbon Nanotube Growth from Organic
Templates

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2013

51

S. Komagawa, C. Wang, K.
Morokuma, S. Saito and M.
Uchiyama

Mechanistic Origin of Chemo- andRegioselectivity of Nickel-Catalyzed[3+2+2] Cyclization Reaction

J. Am. Chem.
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135,
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S. Maeda, T. Taketsugu, and
K. Morokuma

Exploring Transition State Structures for
Intramolecular Pathways by the Artificial
Force Induced Reaction (AFIR) Method

J. Comput.
Chem.

35, 166-173

2014

53

Y. Wang, A. J. Page, H.-B. Li,
H.-J. Qian, M.-G, Jiao, Z.-J.
Wu, K. Morokuma, and S.
Irle

Step-Edge Self-Assembly During
Graphene Nucleation on a Ni Surface:
QM/MD Simulations

Nanoscale6, 140-144

2014

54

L. Ding, N. Ishida,
M. Murakami, and K.
Morokuma

sp3–sp2 vs sp3–sp3 C-C Site-Selectivity
in Rh-Catalyzed Ring Opening of
Benzocyclobutenol: A DFT Study

J. Am. Chem.
Soc.

136, 169-178

2014

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Y. Wang, X. Gao, H.-J. Qian,
Y. Ohta, X. Wu, G. Eres, K.
Morokuma, and S. Irle

Quantum Chemical Simulations Reveal
Acetylene-Based Growth Mechanisms in
the Chemical Vapor Deposition Synthesis
of Carbon Nanotubes

Carbon72, 22-37

2014

56

T. V. Harris, Y. Kurashige, T.
Yanai, and K. Morokuma

Ab Initio Density Matrix Renormalization
Group Study of Magnetic Coupling in
Dinuclear Iron and Chromium Complexes

J. Chem. Phys.

140,054303/1-10

2014

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L. Ding, L. W. Chung, and K.
MorokumaExcited-State Proton Transfer Controls
Irreversibility of Photoisomerization in
Mononuclear Ruthenium(II) Monoaquo
Complexes: A DFT Study

J. Chem. Theory
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10, 668-675

2014

58

M. Isegawa, S. Maeda, D. J.
Tantillo and K. Morokuma

Predicting Pathways for Terpene
Formation from First Principles – Routes
to Known and New Sesquiterpenes

Chem. Sci.

5, 1555-1560

2014

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M. Hatanaka, M. Saito, M.
Fujita and K. Morokuma

σ-Aromaticity in Hexa-Group 16 AtomSubstituted Benzenes Dications. A
Theoretical Study

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79, 2640-2646

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JournalVolume (Number),first page tolast page

year

60

前田理，畑中美穂，
植松遼平，武次徹也，
諸熊奎治

人工力誘起反応法による化学反応経路の自動探索：有機合成化学への応用と展望

有機合成化学協会誌

72, 567-579

2014

61

諸熊奎治

この人に聞く“見えないものを理論と計算で探る”諸熊奎治博士

現代化学507, 20-25

2013

62

諸熊奎治

複雑化学系のマルチスケールモデルの開発

現代化学521, 38-42

2013

63

諸熊奎治

2013年度ノーベル化学賞に寄せて

科学

84, 29

2014

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茂好

64

Toru Matsui, Yasutake
Kitagawa, Mitsutaka
Okumura, Yasuteru Shigeta,
Shigeyoshi SakakiConsistent scheme for computing
standard hydrogen electrode and redox
potentials

J. Comp. Chem.

34 (1), 21-26

2013

65

Shinji Aono, Takashi Hosoya,
and Shigeyoshi Sakaki

A 3D-RISM-SCF method with dual
solvent boxes for a highly polarized
system: ap-plication to 1,6-anhydrosugar
formation reaction of phenyl a- and b-Dglucosides under basic conditions

Phys. Chem.
Chem. Phys.

15, 6368-6381

2013

66

Milind Madhusudan
Deshmukh, Masaaki
Ohba,Susumu Kitagawa, andShigeyoshi Sakaki

Absorption of CO2 and CS2 into the
Hofmann-Type Porous Coordination
Polymer: Electrostatic versus Dispersion
Interactions

J. Am. Chem.
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135, 4840-4849

2013

67

Guixiang Zeng, S. Sakaki

Unexpected Electronic Process of H2
Activation by a New Nickel Borane
Complex: Comparison with the Usual
Homolytic and Heterolytic Activations

Inorg. Chem.

52, 2844-2853

2013

68

Shinya Tsukamoto andShigeyoshi Sakaki

A theoretical study of luminescentvapochromic compounds including an
AuCu2(NHC)2 core

Dalton Trans.

42, 4809-4821

2013

69

Terutaka Yoshizawa,
Shigeyoshi 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–Hesshamiltonian

J. Comp. Chem.

34, 1013-1023

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70

Wei Guan, Shinichi Yamabe
and Shigeyoshi Sakaki

Interests in new heterodinuclear
transition-metal/main-group-metal
complexes: DFT study of electronic
structure and mechanism of fluoride
sensing function

Dalton Trans.

42 (24),8717-8728.

2013

71

Nozomi Takagi and
Shigeyoshi Sakaki

Theoretical Study of Reactivity of Ge(II)hydride Compound: Comparison withRh(I)- Hydride Complex and Predictionof Full Catalytic Cycle by Ge(II)-hydride

J. Am. Chem.
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135, 8955-8965

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72

Fareed Bhasha Sayyed,aYasushi Tsujib andShigeyoshi Sakaki

Crucial Role of Ni(I) Intermediate in NiCatalyzed Direct Carboxylation of Aryl
Chloride with CO2: A Theoretical Study

Chem. Commun.

49 (91),10715-10717

2013

73

Masayuki Wakioka, Yuki
Nakamura, Yoshihiro Hihara,
Fumiyhuki Ozawa, andShigeyoshi Sakaki

Factors Controlling the Reactivity ofHeteroarenes in Direct Arylation with
Arylpalladium Acetate Complexes

Organometallics

32, 4423 4430

2013

74

Wei Guan, Shigeyoshi
Sakaki, Tetgsuya Kurahashi,and Seijiro Matsubara.

Theoretical Mechanistic Study of Novel
Ni(0)-Catalyzed [6-2+2] Cycloaddition
Reactions of Isatoic Anhydrides
with Alkynes: Origin of Facile
Decarboxylation

Organometallics

32, 7564-7574

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75

Yue Chen and Shigeyoshi
Sakaki

Theoretical Study of Mononuclear
Nickel(I), Nickel(0), Copper(I), andCobalt(I) Dioxygen Complexes: New
Insight into Differences and Similaritiesin Geometry and Bonding Nature

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52,
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Takashi Hosoya andShigeyoshi Sakaki

Levoglucosan Formation from Crystalline
Cellulose: Importance of a Hydrogen
Bonding Network in the Reaction

ChemSusChem

6, 2356-2368

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貴史

77

Shunsuke F. Shimobayashi1,
Takafumi Iwaki, Toshiaki
Mori, and Kenichi Yoshikawa

Probability of double-strand breaks ingenome-sized DNA by g-ray decreases
markedly as the DNA concentration
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138, 174907(4 pages)

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Masatoshi Ichikawa, Fumi
Takabatake, Keitaro Miura,
Takafumi Iwaki, Nobuyuki
Magome, and Kenichi
YoshikawaControlling negative and positive
photothermal migration of centimetersized droplets

Physical Review
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Noriyuki Minezawa

Excited-state free energy surfaces
in solution: Time-dependent density
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Yu Harabuchi, Satoshi
Maeda, Tetsuya Taketsugu,
Noriyuki Minezawa, andKeiji Morokuma

Automated search for minimum energy
conical intersection geometries between
the lowest two singlet states S0/S1-MECIs
by the spin-flip TDDFT method

J. Chem. Theory
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81

Nuwan De Silva, Noriyuki
Minezawa, and Mark S.
GordonExcited-state hydrogen atom transfer
reaction in solvated 7-hydroxy-4methylcoumarin

J. Phys. Chem. B

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Ryuichi Okamoto, Youhei
Fujitani and Shigeyuki
KomuraDrag coefficient of a rigid sphericalparticle in a near-cirtical binary fluid
mixtureJ. Phys. Soc. Jpn

82, 084003

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Ryuichi Okamoto and Akira
Onuki

Attractive interaction and bridging
transition between between neutral
colloidal particles due to preferential
adsorption in a near-critical binary
mixturePhys. Rev. E

88, 22309

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Cis-trans dynamical asymmetry in driven
polymer translocation

Phys. Rev. E

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齋藤
84

隆一

拓也
Takuya Saito and Takahiro
SakaueFu-Quan Bai
85

Jie Chen, Jian Wang, FuQuan Bai, Li Hao, Qing-Jiang
Pan, and Hong-Xing Zhang

Connection style and spectroscopic
properties: Theoretical understanding of
the interface between N749 and TiO2 in
DSSCs

Dyes andPigments

99 (1), 201-208

2013

86

Jie Chen, Jian Wang, FuQuan Bai, Qing-Jiang Pan,and Hong-Xing Zhang

Theoretical Studies on Structuraland Spectroscopic Properties of
Photoelectrochemical Cell Ruthenium
Sensitizers, Derivatives of AR20

Int. J. Quant.
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113 (7), 891-901

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Juan Jin, Fu-Quan Bai, MingJun Jia, Yan-Ning Wang,
Hong-Li Jia, Jie-Hui Yu, andJi-Qing Xu

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New Cd2+, Pb2+ complexes withacylhydrazidate molecules from in situ
acylation reactions

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42 (24),8771-8780

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88

Vladimir Ya. Lee, Shinji
Aoki, Taka Yokoyama, Satoru
Horiguchi, Akira Sekiguchi,
Heinz Gornitzka, Jing-Dong
Guo, and Shigeru Nagase

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

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135, 2987-2990

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89

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-PentamethylcyclopentadieneJ. Am. Chem.
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Takuya Kuwabara, Masaichi
Saito, Jing-Dong Guo,
Shigeru Nagase

Unexpected Formation of Ru2Sn2
Bicyclic Four-Membered Ring Complexes
with Butterfly and Inverse-Sandwich
Structures

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52, 3585-3587

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91

Chun-Yi Lin, Jing-Dong Guo,
James C. Fettinger, Shigeru
Nagase, Fernande Grandjean,
Gary J. Long, Nicholas F.
Chilton, and Philip P. Power

Dispersion Force Stabilized TwoCoordinate Transition Metal−Amido
Complexes of the −N(SiMe3)Dipp (Dipp= C6H3‑2,6-Pri Structural, Spectroscopic,
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Jessica N. Boynton, JingDong Guo, James C.
Fettinger, Christopher E.
Melton, Shigeru Nagase, andPhilip P. PowerLinear and Nonlinear Two-Coordinate
Vanadium Complexes: Synthesis,
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J. –S. Dang, W. –W. Wang, S.
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Regiochemistry of Nonclassical C62
Fullerene: Role of Tetragonal Carbocyclic
Ring in Cycloadditions and Thermal/
Photoinduced Interconversions ofFulleroid Derivatives

J. Phys. Chem. C

117,12882-12889

2013

94

H. Zheng, X. Zhao, W. –W,
Wang, J. –S. Dang, and S.
NagaseQuantum Chemical Insight into
Metallofullerenes M2C98: M2C2@C96 or
M2@C98, Which Will Survive?

J. Phys. Chem. C

117,25195-25204

2013

95

J. –S. Dang, W. –W. Wang, X.
Zhao, and S. Nagase

Regioselective Derivatization of C84 byDiels-Alder Reactions: Applications to
Photovoltaic Solar Cells and Fullerene
Polymerization

Org. Lett.

16, 170-173

2014

Jingdong Guo

Wei-Wei Wang

畑中

美穂

96

Miho Hatanaka, Masaichi
Saito, Masahiro Fujita, andKeiji Morokuma

σ-Aromaticity in Hexa-Group 16 Atom
Substituted Benzene Dications. A
Theoretical Study

J. Org. Chem.

79 (6),
2640-2646

2014

97

Miho Hatanaka, and Keiji
Morokuma

Role of Water in Mukaiyama–Aldol
Reaction Catalyzed by Lanthanide Lewis
Acid: A Computational Study

J. Am. Chem.
Soc.

135 (37),
13972-13979

2013

98

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.

9 (7),
2882-2886

2013－ 199 －

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Ⅴ 資料 (2013)№

Authors

Title

JournalVolume (Number),first page tolast pageyear

Fengyi Liu
99

Fengyi Liu and Keiji
MorokumaMultiple Pathways for the Primary Step of
the Spiropyran Photochromic Reaction: A
CASPT2//CASSCF Study

J. Am. Chem.
Soc.

135,
10693-10702

2013

100

Fengyi Liu, Yuki
Kurashige, Takeshi Yanai,
and Keiji Morokuma

Multireference Ab Initio Density Matrix
Renormalization Group (DMRG)CASSCF and DMRG-CASPT2 Studyon the Photochromic Ring Opening of
Spiropyran

J. Chem. Theory
Comput.

9, 4462-4469

2013

101

Piao, W., Tsuda, S., Tanaka,Y., Maeda, S., Liu, F.,
Takahashi, S., Kushida, Y.,
Komatsu, T., Ueno, T., Terai,T., Nakazawa, T., Uchiyama,M., Morokuma, K., Nagano,T. and Hanaoka, K.

Development of Azo-Based Fluorescent
Probes to Detect Different Levels ofHypoxia

Angew. Chem.
Int. Ed.

52,
13028-13032

2013

Lina Ding
102

Lina Ding, Lung Wa, Chung,
Keiji Morokuma

Excited-State Proton Transfer Controls
Irreversibility of Photoisomerization in
Mononuclear Ruthenium(II) Monoaquo
Complexes: A DFT Study

J. Chem. Theory
Comput.

10 (2), 668-675

2014

103

Lina Ding, Naoki Ishida,
Masahiro Murakami, andKeiji Morokuma

sp3–sp2 vs sp3–sp3 C–C Activationin Rh-Catalyzed Ring Opening of
Benzocyclobutenol: A DFT Study

J. Am. Chem.
Soc.

136 (1),169-178

2014

104

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

117 (4),1075-1084

2013

Graphene Nucleation on a Surface-Molten
Copper Catalyst: Quantum Chemical
Molecular Dynamics Simulations

Chem. Sci

accepted

2014

Hai-Bei Li

105

Hai-Bei Li, Alister J.
Page,Christian Hettich,Bálint
Aradi,Christof Köhler,Thomas Frauenheim,Stephan
Irle, and Keiji Morokuma

Lung Wa Chung
106

Lina, Ding, Lung Wa Chung,
Keiji Morokuma

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

J. Phys. Chem. B

117 (4),1075-1084

2013

107

Shengtao Ding, Lijuan
Song, Lung Wa Chung,
Xinhao Zhang, Jianwei Sun,
Yundong, Wu

Ligand-Controlled Remarkable Regioand Stereodivergence in Intermolecular
Hydrosilylation of Internal Alkynes:
Experimental and Theoretical Studies

J. Am. Chem.
Soc.

135 (37),
13835-13842

2013

108

Lina, Ding, Lung Wa Chung,
Keiji Morokuma

Excited-State Proton Transfer Controls
Irreversibility of Photoisomerization in
Mononuclear Ruthenium(II) Monoaquo
Complexes: A DFT Study

J. Comput.
Theory Chem.

10 (2), 668-675

2014

Asymmetric Phase-Transfer Catalysis
with Homo- and Heterochiral QuaternaryAmmonium Salts: A Theoretical Study

J. Phys. Chem. B

118 (19),
pp 5154-5167

2014

Galina P. Petrova
109

Galina P. Petrova, Hai-Bei
Li, Keiji Maruoka, and Keiji
Morokuma－ 200 －

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Authors

110

Galina P. Petrova, Zhuofeng
Ke, Soyoung Park, Hiroshi
Sugiyama, and Keiji
Morokuma

Title

JournalVolume (Number),first page tolast pageyear

The origin of enantioselectivity for
intramolecular Friedel–Crafts reaction
catalyzed by supramolecular Cu/DNA
catalyst complex

Chem. Phys.
Lett.

600, pp 87-95

2014

Travis Harris
111

Travis V. Harris, Yuki
Kurashige, Takeshi Yanai,
and Keiji Morokuma

Ab Initio Density Matrix Renormalization
Group Study of Magnetic Couplingin Dinuclear Iron and Chromium
Complexes.

J. Chem. Phys.

140 (5), 054303(10 pages)

2014

112

Travis V. Harris and Robert
K. Szilagyi

Iron-Sulfur Bond Covalency from
Electronic Structure Calculations forClassical Iron-Sulfur Clusters.

J. Comput.
Chem.

35 (7), 540-552

2014

113

Travis V. Harris and Keiji
Morokuma

QM/MM Structural and Spectroscopic
Analysis of the Di-iron(II) and Diiron(III) Ferroxidase Site in M Ferritin

Inorg. Chem.

52 (15),8551-8563

2013

Predicting pathways for terpene fromfirst principles-routes to known and newsesquiterpenes

ChemicalScience5, 1555-1560

2014

115

J. Llaveria, Á. Beltrán, W. M.
C. Sameera, A. Locati, M. M.
Díaz-Requejo, M. I. Matheu,
S. Castillón, F. Maseras, P. J.
Pérez

Regio- and Stereoselective Silvercatalyzed aziridination of dienes: scope,mechanistic studies and ring-opening
reactions

J. Am. Chem.
Soc.

136, 14,5342-5350.

2014

116

E. M. Zueva, R. Herchel,
S. Borshch, E. V. Govor, W.
M. C. Sameera, R. McDonald,
J. Singleton, Y. Sanakis, J.
Krzystek, J. E. McGrady, andR. G. Raptis.

E. M. Zueva, R. Herchel, S. Borshch, E. V.
Govor, W. M. C. Sameera, R. McDonald,
J. Singleton, Y. Sanakis, J. Krzystek, J. E.
McGrady, and R. G. Raptis.

Dalton Trans.

In Press.

2014

117

L. Maestre, W. M. C.
Sameera, M. M. DíazRequejo, F. Maseras, P. J.
Pérez.

A General Mechanism for the Copperand Silver-Catalyzed olefin aziridination
reactions: concomitant involvement of thesinglet and triplet pathways

J. Am. Chem.
Soc.

135, 1338-1348

2013

118

I. Rivilla, W. M. C. Sameera,
E. Alvarez, M. M. DíazRequejo, F. Maseras, P. J.
Pérez.

Catalytic cross-coupling of diazo
compounds with coinage metal-based
catalysts: an experimental and theoretical
study

Dalton Trans.

42, 4132-4138.

2013

伊勢川
114

美穂

Miho Isegawa, Satoshi
Maeda, Dean J. Tantillo, Keiji
Morokuma

W. M. C. Sameera

山邊

信一

119

Shinichi Yamabe, Takeshi
Fukuda and Shoko Yamazaki

A new intermediate in the Prins reaction

Beilstein J. Org.
Chem.

9, 476-485

2013

120

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),
pp 2527-2533

2013

121

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

122

Wei Guan, Shinichi Yamabe
and Shigeyoshi Sakaki

Interest in new heterodinuclear transitionmetal/main-group-metal

Dalton Trans.

42, 8717-8728

2013－ 201 －

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Ⅴ 資料 (2013)№

Authors

Title

JournalVolume (Number),first page tolast page

year

123

Shinichi Yamabe, Guixiang
Zeng, Wei Guan, Shigeyoshi
SakakiSubstrate dependent reaction channels of
the Wolff-Kishner reduction reaction: A
theoretical study

Beilstein J. Org.
Chem.

10, 259-270

2014

124

Naokazu Y., Shinichi Y.,*,
Shigeyoshi S., Nobuko K.,

A DFT Study of the Triplet Excited
States of Iridium(III) Complexes with
Terpyridine Ligands

Canadian
ChemicalTransactions

vol.2, issue 2,
134-1482014

125

Shinichi Yamabe, Guixiang
Zeng, Wei Guan and
Shigeyoshi Sakaki

SN1-SN2 and SN2-SN3 mechanisticchanges revealed by transition states of
the hydrolyses of benzyl chlorides andbenzenesulfonyl

Journal ofComputational
Chemistry

vol.35,
issue 15, pages
1140-1148

2014

126

Shinichi Yamabe, Guixiang
Zeng, Wei Guan, Shigeyoshi
SakakiProton Transfers in the Strecker
Reactions revealed by DFT calculations

Beilstein Journalof Organic
Chemistry

in press

2014

土方

優

127

Shin-ichiro Noro, Katsuo
Fukuhara, Yuh Hijikata,Kazuya Kubo and Takayoshi
Nakamura

Rational synthesis of a porous copper (II)coordination polymer bridged by weak
Lewis-base inorganic monoanions using
an anion-mixing method

Inorg. Chem.

52, 5630-5632

2013

128

Hiroyuki Nakashima,
Yuh Hijikata, and Hiroshi
Nakatsuji

Solving the non-Born-Oppenheimer
Schrödinger equation for the hydrogenmolecular ion with the free complement
method II. Highly accurate electronic,
vibrational and rotational excited states

Astrophys. J

770, 144-1-9

2013

129

Yasuko Mito-oka, Satoshi
Horike, Yusuke Nishitani,
Tadao Masumori, Munehiro
Inukai, Yuh Hijikata, andSusumu Kitagawa

Siloxane D4 capture by hydrophobic
microporous materials

J. Mater. Chem.
A

1, 7885-7888

2013

130

Shin-ichiro Noro, Katsuo
Fukuhara, Kunihisa
Sugimoto, Yuh Hijikata,Kazuya Kubo, and Takayoshi
Nakamura

Anion-dependent host-guest propertiesof porous assemblies of coordination
complexes (PACs), [Cu(A)2(py)4] (A =PF6, BF4, CF3SO3, and CH3SO3; py =pyridine), based on Werner-type copper(II) complexes in the solid state

Dalton Trans.

42, 11100-11110

2013

131

Hiroshi Sato, Wataru
Kosaka, Ryotaro Matsuda,
Akihiro Hori, Yuh Hijiakta,
Shigeyoshi Sakaki, Masaki
Takata, and Susumu
Kitagawa

Self-accelerating CO sorption in a soft
nanoporous crystal

Science343, 167-170

2014

132

Yuh Hijikata and Shigeyoshi
SakakiInteraction of various gas molecules withpaddle-wheel-type open metal sites ofporous coordination polymers: theoreticalinvestigation

Inorg. Chem.

53, 2417-2426

2014

Theoretical Study of One-Electron
Oxidized Mn(III)− and Ni(II)−Salen
Complexes: Localized vs Delocalized
Ground and Excited States in Solution

J. Chem. Theory
Comput.

10, 1062-1073

2014

J. Am. Chem.
Soc.

135, 4840-4849

2013

青野
133

信治
Shinji Aono, Masayuki
Nakagaki, Takuya Kurahashi,
Hiroshi Fujii, and Shigeyoshi
Sakaki

Milind Madhusudan Deshmukh
134

Deshmukh, Milind M.;
Ohba, Massaki.; Kitagawa,Susumu.; Sakaki Shigeyoshi

Absorption of CO2 and CS2 into the
Hofmann-type Porous Coordination
Polymer:Electrostatic versus Dispersion
Interactions－ 202 －

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Ⅴ 資料 (2013)№

135

Authors

Title

Deshmukh, Milind, M.
Sakaki Shigeyoshi

Guixiang Zeng（會JournalVolume (Number),first page tolast page

Generation of dihydrogen moleculeand hydrosilylation of carbon
dioxide catalyzed by zinc hydridecomplex:Theoretical understanding andprediction

Inorg. Chem.

(Revision
submitted)

year

桂香）

136

Shinichi Yamabe, Guixiang
Zeng, Wei Guan, andShigeyoshi Sakaki

Substrate Dependent Reaction Channelsof the Wolff-Kishner Reduction Reaction:
A Theoretical Study

Beilstein J. Org.
Chem.

10 (1), 259-270

2014

137

Guixiang Zeng, Shigeyoshi
Sakaki, Ken-ichi Fujita,
Hayato Sano, and Ryohei
Yamaguchi

Efficient Catalyst for Acceptorless
Alcohol Dehydrogenation: Interplay ofTheoretical and Experimental Studies

ACS Catal.

4 (3), 1010-1020

2014

138

Guixiang Zeng, Satoshi
Maeda, Tetsuya Taketsugu,
and Shigeyoshi Sakaki

Catalytic Transfer Hydrogenation by
a Trivalent Phosphorus Compound:
Phosphorus-Ligand Cooperation Pathway
or PIII/PV Redox Pathway?

Angew. Chem.
Int. Ed.

53 (18),4633-4637

2014

139

Shinichi Yamabe, Guixiang
Zeng, Wei Guan, andShigeyoshi Sakaki

SN1-SN2 and SN2-SN3 Mechanistic
Changes Revealed by Transition States ofthe Hydrolyses of Benzyl Chlorides andBenzenesulfonyl Chlorides

J Comput. Chem.

35 (15),1140-1148

2014

140

Wei Guan, Ferred Bhasha
Sayyed, Guixiang Zeng, andShigeyoshi Sakaki

σ-Bond Activation of Small Molecules
and Reactions Catalyzed by TransitionMetal Complexes: Theoretical
Understanding of Electronic Processes

Inorg. Chem.

DOI 10.1021/
ic5003429

2014

Substrate Dependent Reaction Channelsof the Wolff-Kishner Reduction Reaction:
A Theoretical Study

Beilstein J. Org.
Chem.

10 (1), 259-270

2014

J. Phys. Chem. A

118 (7),1247-1257

2014

高木
141

中垣

望
Shinichi Yamabe, Guixiang
Zeng, Wei Guan, andShigeyoshi Sakaki

雅之

142

Masayuki Nakagaki and
Shigeyoshi Sakaki

CASPT2 Study of Inverse Sandwich-Type
Dinuclear Cr(I) and Fe(I) Complexesof the Dinitrogen Molecule: Significant
Differences in Spin Multiplicity and
Coordination Structure between These
Two Complexes

143

Shinji Aono, Masayuki
Nakagaki, Takuya Kurahashi,
Hiroshi Fujii, and Shigeyoshi
Sakaki

Theoretical Study of One-Electron
Oxidized Mn(III) and Ni(II) Salen
Complexes: Localized vs Delocalized
Ground and Excited States in Solution

J. Chem. Theory
Comput.

10 (3),
1062-1073

2014

144

Wei Guan, Shigeyoshi
Sakaki, Takuya Kurahashi,
Seijiro Matsubara

Theoretical Mechanistic Study of Novel
Ni(0)-Catalyzed [6 − 2 + 2] Cycloaddition
Reactions of Isatoic Anhydrides
with Alkynes: Origin of Facile
Decarboxylation

Organometallics

32, 7564-7574

2013

145

Wei Guan, Fareed Bhasha
Sayyed, Guixiang Zeng,
Shigeyoshi Sakaki

σ‑Bond Activation of Small Molecules
and Reactions Catalyzed by TransitionMetal Complexes: Theoretical
Understanding of Electronic Processes

Inorg. Chem.

ic5003429

2014

146

Shinichi Yamabe, Gui-Xiang
Zeng, Wei Guan, Shigeyoshi
Sakaki

SN1-SN2 and SN2-SN3 Mechanistic
Changes Revealed by Transition States ofthe Hydrolyses of Benzyl Chlorides andBenzenesulfonyl Chlorides

J. Comput.
Chem.

35, 1140-1148

2014

Wei Guan－ 203 －

fukui2013.indb 203

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Ⅴ 資料 (2013)

Volume (Number),first page tolast pageyear

Beilstein J. Org.
Chem.

10, 259-270

2014

DFT characterization on the mechanismof water splitting catalyzed by single-Rusubstituted polyoxometalates

Dalton Trans.

42,10617-10625

2013

Inorg. Chem.

52 (22),13146-13159

2013

№

Authors

Title

Journal147

Shinichi Yamabe, Gui-Xiang
Zeng, Wei Guan, Shigeyoshi
SakakiSubstrate dependent reaction channels of
the Wolff–Kishner reduction reaction: A
theoretical study

148

Zhong-Ling Lang, Guo-Chun
Yang, Na-Na Ma, Shi-Zheng
Wen, Li-Kai Yan, Wei Guan,
Zhong-Min Su

Yue Chen149

Yue Chen, Shigeyoshi Sakaki

Theoretical Study of Mononuclear
Nickel(I), Nickel(0), Copper(I), andCobalt(I) Dioxygen Complexes: New
Insight into Differences and Similaritiesin Geometry and Bonding Nature

150

Yue Chen, Shigeyoshi Sakaki

The important role of the Mo-Mo
quintuple bond in catalytic synthesisof benzene from alkynes. A theoretical
study

Dalton Trans.

DOI: 10.1039/
C4DT00595C

2014

Sayyed Fareed Bhasha
151

Fareed Bhasha Sayyed andShigeyoshi Sakaki

The crucial role of a Ni(I) intermediate
in Ni-catalyzed carboxylation of aryl
chloride with CO2: a theoretical study

Chem. Commun.

49, 10715-10717

2013

152

Wei Guan, Fareed Bhasha
Sayyed, Guixiang Zeng, andShigeyoshi Sakaki

σ-Bond Activation of Small Molecules
and Reactions Catalyzed by TransitionMetal Complexes: Theoretical
Understanding of Electronic Processes

Inorg. Chem.

53, in press

2014

山田

健太

153

Miyabi Hiyama, Hidefumi
Akiyama, Kenta Yamada andNobuaki Koga

Theoretical Study of Fluorescence
Spectra Utilizing the pKa Values of Acids
in Their Excited States

Photochem.
Photobio.

90 (1), 35-44

2014

154

Takako Mashiko, Kenta
Yamada, Tatsuo Kojima,
Shuichi Hiraoka, Umpei
Nagashima and Masanori
Tachikawa

Molecular dynamics and principal
component analysis for a self-assembled
nanocube in aqueous solution

Chem. Lett.

43 (3), 366-368

2014

155

Kenta Yamada, Yukio
Kawashima and Masanori
TachikawaMuon-electron hyperfine coupling
constants of muoniated ethyl radical:
a path integral simulations study withsemiempirical molecular orbital method

Chin. J. Phys.

52 (1-I),
126-137

2014

156

Miyabi Hiyama, Hidefumi
Akiyama, Toshimitsu
Mochizuki, Kenta Yamada
and Nobuaki Koga

Analysis of Photoexcitation Energy
Dependence in the Photo Luminescenceof Firefly Luciferin

Photochem.
Photobio.

90 (4), 820-8282014＊以下に表示の研究業績（論文）は、共著である
No5&90. No6&89. No11&93. No15&92. No24&94. No25&91. No30&95.
No38&98. No42&99. No45&113. No46&80. No47&101. No48&97.
No49&100. No54&103. No56&111. No57,102&108. No58&114. No59&96.
No66&134. No70&122. No72&151. No74&144. No75&149. No104&106.
No123,141&147. No125&146. No133&143. No140,145&152.

－ 204 －

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Ⅴ 資料 (2013)

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－ 205 －

fukui2013.indb 205

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Ⅴ 資料 (2013)ģ

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2014(平成 26)年 1 月 23 日(木)場所

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北野 正雄 (京都大学 工学研究科長)・・・10:05-10:15●	
 谷口 正輝 (大阪大学 産業科学研究所 教授)

司会: 榊 茂好 (福井センター)・・・10:15-11:15

H µÖñÂWČéI—	  休憩 —●	 永瀬 茂 (福井謙一記念研究センター シニアリサーチフェロー)

司会: 山邊 信一 (福井センター)

HšÅ÷®ħ_ŠûVîRµÖTI・・・11:30-12:30—	  昼休み —
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 時任 宣博 (京都大学 化学研究所 教授)

司会: 永瀬 茂 (福井センター)

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Ohno[2],and
andSadamichi
SadamichiMaekawa[3]Maekawa[3]bgoµĴŎħWŎħÎŀİÂ«WĘ¢¬ĔWđĺĴøbgoµĴŎħWŎħÎŀİÂ«WĘ¢¬ĔWđĺĴø(阪大院基礎工[1]、東大生産技術研[2]、立教大理[3])(阪大院基礎工[1]、東大生産技術研[2]、立教大理[3])○安東寛之[1]、馬場剛史[1]、重○安東寛之[1]、馬場剛史[1]、重田育照[1]、渡邉千鶴[2]、沖山佳生[2]、望月祐志[3]、中野雅由[1]田育照[1]、渡邉千鶴[2]、沖山佳生[2]、望月祐志[3]、中野雅由[1]šÅ÷±Ì®ħ_ÃZŖāŐŝīĒ°æĦWrrhéTśĩå¯ØĐšÅ÷±Ì®ħ_ÃZŖāŐŝīĒ°æĦWrrhéTśĩå¯ØĐĿVŗO]đĺėĚġĿVŗO]đĺėĚġ(阪大院基礎工[1]、阪大基礎工[2])(阪大院基礎工[1]、阪大基礎工[2])○廣崎裕多[1]、福田幸太郎[1]、松井啓史[1]、高椋○廣崎裕多[1]、福田幸太郎[1]、松井啓史[1]、高椋章太[2]、上田幸平[2]、岸亮平[1]、中野雅由[1]章太[2]、上田幸平[2]、岸亮平[1]、中野雅由[1]}iq~ĦrrhµÖWýňT¯ÄÁčéVŗO]đĺĚġ}iq~ĦrrhµÖWýňT¯ÄÁčéVŗO]đĺĚġ(阪大院基礎工[1]、(阪大院基礎工[1]、
阪市大院理[2]、
阪市大院理[2]、青山学院大理工[3])	
 ○中村亮太[1]、青山学院大理工[3])	
 ○中村亮太[1]、重田育照[1]・
重田育照[1]・
奥野克樹[1]、鈴木修一[2]、小嵜正敏[2]、岡田惠次[2]、長谷川美貴[3]、中野雅由[1]奥野克樹[1]、鈴木修一[2]、小嵜正敏[2]、岡田惠次[2]、長谷川美貴[3]、中野雅由[1]qkwqk w rrh½ÂČWŖāéTśĩå¯ØčéVÜO]rrh½ÂČWŖāéTśĩå¯ØčéVÜO]~akuwĬòÎºùWđĺĚġ~akuwĬòÎºùWđĺĚġ(阪大院基礎工[1]、広島大院理[2])(阪大院基礎工[1]、広島大院理[2])○齋藤○齋藤真和[1]、岸亮平[1]、福田幸太郎[1]、松井真和[1]、岸亮平[1]、福田幸太郎[1]、松井啓史[1]、高椋章太[1]、安倍学[2]、中野雅由[1]啓史[1]、高椋章太[1]、安倍学[2]、中野雅由[1]22－ 207 －

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Ⅴ 資料 (2013)878;FDF878; é_öO]ŖāŐŝµÖĦWrrhÊÖTģ¡ŃµüďVŗO]đĺėĚġ(阪大院基礎工) ○福田幸太郎、中野雅由auWřĂ¨ÝWÒÏçĤTŖāéWĘŗVRJSWđĺ(阪大院基礎工) ○竹林拓、福田幸太郎、重田育照、中野雅由  rrhÌ½ÂČWýň¯ØçĤčéĘŗVRJSWđĺĚġ(阪大院基礎工) ○村田裕介、岸亮平、齋藤真知、中野雅由ŖāŐŝµÖĦWŖāéTřÖxbksWĘŗVRJSWđĺĚġ(阪大院基礎工) ○森田啓介、	  岸亮平、	  中野雅由Ü ĝ ¿ X ś Ü ĝ     g  o   Ĺ Ý « W  Ő ŝ Ŗ ā é V ŗ O ] đ ĺ ėĚġ(阪大院基礎工) ○上田幸平、福田幸太郎、松井啓史、廣崎裕多、高椋章太、中野雅由šÅ÷±Ì®ħ_ÃZÈÇĒ½ÂČWŖāŐŝéTģ¡ŃµüďWĘŗ(阪大院基礎工) ○松井啓史、福田幸太郎、廣崎裕多、高椋章太、中野雅由
a i q a  Ì ō ª Ö _ ö O ] Ŗ ā  Ő ŝ ¡ ú Ŋ Ğ ő ß Ŕ « W r  r h  ÊÖTĀśĩå¯ØČéVRJSWđĺėĚġ(阪大院基礎工) ○山田大志、 高椋章太、中野雅由Ā®ĕúŊĞőßŕWŐŝŖāéTĀśĩå¯ØČéWĘŗ(阪大院基礎工) ○高椋章太、山田大志、中野雅由Ŗ ā  Ő ŝ i  b x  g  o y g  d  W Ŗ ā é T  Ā ś ĩ å ¯ Ø č é VRJSWđĺėĚġ(阪大院基礎工) ○岸亮平、植中英樹、村田裕介、森田啓介、齋藤真和、中野雅由  (# ĄŗôWśĨşėylĆţrae{ĹÝ«W¹
łejĶĥYWçĔ(阪大院基礎工) ○奥野克樹、重田育照、岸亮平、中野雅由
3－ 208 －

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Ⅴ 資料 (2013)

$+<# W &# ¸ăµĴĵÕ¬ĔVŗO]đĺėĚġ(京大院理[1]、琉球大理[2]、分子研[3])	
 ○公文啓瑛[1]、	
  東雅大[2]、斎藤真司[3]、	
 林重彦[1]
ĉĈ²VKM]

rWŃšŇĪÆŉğVRJSWđĺėĚġ(京大院・理[1], 分子研[2]) ○中野勝博[1], 森俊文[2], 林重彦[1], 加藤重樹[1]Ťpb}ĜãÌ~s|zĘWýňĴøTČé(京大院工[1]、京都大学学際融合教育研究推進センター[2]、ペンシルバニア州立大[3]、ドレクセル大[4]) ○久家俊洋[1]、藤田晃司 [1]、田中功[1]、田中勝久[1]、東後篤史 [2]、赤松寛文 [3]、Arnab S. Gupta [3]、Shiming Lei [3]、Fei Xue [3]、Greg Stone[3]、Long-Qing Chen [3]、Venkatraman Gopalan [3], and James M. Rondinelli [4]Ýřéőßŏ½ČWŁÒÍVKM]tzkčéWĸ­
(京大院工) ○鎌倉涼介、藤田晃司、村井俊介、田中勝久
àřÖÚäTðřĘ¢¬ĔVÜO]Ó«ºùţńŅµÖYWçĔ(京大院工[1]、京大触媒電池[2]、京大化研[3]) ○三村貴信[1]、佐藤徹[1, 2]、田中一義[1]、梶弘典[3]62 ĕé«L\W ŢĮŘWćé½ej2(京大院工[1]、京大触媒電池[2]) ○長島大[1]、佐藤徹[1, 2]、田中一義[1]őß²¼WĒ½¦¸ÀçVKM]ªĬŋìéţðřĘ¢¬ĔÚäĴø
(京大院工[1]、京大触媒電池[2]) ○春田直毅[1]、佐藤徹[1, 2]、田中一義[1]%=;>-=>;/80)*B-589+;+92/7B5/7/+7.#</>.8+27&/55/;00/-=
(Grad. School of Eng. Kyoto Univ.[1], ESICB, Kyoto Univ.[2], Grad. School of
Human and Environ. Stud., Kyoto Univ.[3], Kyoto Univ. Institute for Liberal Arts
and Sciences[4]) ○○ Yuichiro Kameoka [1], Tohru Sato [1, 	  2], Takahiko
Koyama[3], Kazuyoshi Tanaka[1], and Tatsuhisa Kato[3, 4]

4－ 209 －

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Ⅴ 資料 (2013)

ö
öÿ
ÿ
r
rh
h
_
_Ĕ
ĔJ
JP
Pö
öÿ
ÿµ
µÖ
Ö
b
b
 W
Wř
řÖ
Ö}
}



l
lV
VÜ
ÜO
O]
]Ķ
Ķĥ
ĥ
½Øėay½Øėay
(京大院工[1]、(京大院工[1]、 北大触セ[2])	
 ○西澤尚平[1]、北大触セ[2])	
 ○西澤尚平[1]、 長谷川淳也[2]、長谷川淳也[2]、 松田建児[3]松田建児[3]ycbg¡ĀřąWřĴŀĉĈycbg¡ĀřąWřĴŀĉĈ VKM]µĴÀçTbgíó
VKM]µĴÀçTbgíó(京大院工[1]，京大触媒電池[2])(京大院工[1]，京大触媒電池[2]) ○笠原健人[1]，佐藤啓文[1,2]○笠原健人[1]，佐藤啓文[1,2]įřÑWċ^ţŚ·ØT»·ØįřÑWċ^ţŚ·ØT»·Ø(京大福井セ[1],(京大福井セ[1], 京大理[2])
京大理[2])○岡本隆一[1]、小貫明[2]○岡本隆一[1]、小貫明[2];>695/.58,>5/
;>695/.58,>5/VKM]þĽN^PWĕáíóĐĿ
VKM]þĽN^PWĕáíóĐĿ(京大福井セ[1]、九州大学理[2])(京大福井セ[1]、九州大学理[2])○齋藤拓也[1]、坂上貴洋[2]○齋藤拓也[1]、坂上貴洋[2]&+7.&&+7.&  /=28.<08;
/=28.<08; /-2+73<=3-+7.%/5/-=3?3=B%=>.3/<80
/-2+73<=3-+7.%/5/-=3?3=B%=>.3/<80
&;+7<3=387
&;+7<3=387 /=+58681/7/8><+=+5B<3</=+58681/7/8><+=+5B<3<(京大福井セ[1],(京大福井セ[1], ICIQ[2],ICIQ[2], Departament
Departament dede Química,
Química, Universitat
Universitat Autónoma
Autónoma dedeBarcelona[3])Barcelona[3])○
○W.
○W.M.
M.C.
C.Sameera[1,Sameera[1,2]2]andandFeliu
FeliuMaseras[2,Maseras[2,3]3]
³Œ¤àVKM]ĉÕºùWđĺėĚġ³Œ¤àVKM]ĉÕºùWđĺėĚġ(京大福井セ)(京大福井セ) 嶺澤範行
嶺澤範行
";313780;+6+=3-+55B889/;+=3?/+=+5B<3<87%/5/-=3?/>+5E";313780;+6+=3-+55B889/;+=3?/+=+5B<3<87%/5/-=3?/>+5E87.-=3?+=38737!3/@3<-3.+=+5BC/.) 
*B-58+..3=387*B-58+..3=38787.-=3?+=38737!3 /@3<-3.+=+5BC/.)&2/8;/=3-+57<312=<&2/8;/=3-+57<312=<(京大福井セ)(京大福井セ)Wei
WeiGuanGuanz½Čag_ÃZÓ×éōªšµÖWz½Čag_ÃZÓ×éōªšµÖW""2 ÄęVŗO]đĺėĚġÄęVŗO]đĺėĚġ(京大福井セ)(京大福井セ)○土方優、榊茂好○土方優、榊茂好ĳœÌ
ĳœÌ8/8/Ŕ«WýňTřÖĎêŔ«WýňTřÖĎê(京大福井セ)(京大福井セ)○塚本晋也、榊茂好○塚本晋也、榊茂好

55－ 210 －

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Ⅴ 資料 (2013)

ĕ
ĕ
ĠĠ
őő
ßß
¾¾
ÖÖ
VV
[[
]]
ĢĢ
ħħ
µµ
ÖÖ
__
ïï
``
QQ
ņņ
pp

~~
bb
zz
yy
ÌÌ
ŔŔ
««
WW
čč
ĕĕ
UU
ss
Ďê
Ďê
(京大福井セ)(京大福井セ)○中垣雅之，榊茂好○中垣雅之，榊茂好âŜÈōªÌőßpŔ«WÞËśÞËéÄÁsk}TĉÕºùâŜÈōªÌőßpŔ«WÞËśÞËéÄÁsk}TĉÕºù
(京大福井セ)(京大福井セ)○青野信治、○青野信治、中垣雅之、榊茂好
中垣雅之、榊茂好Ð½rTÐ½vsfW¸ăµĴWŊĞĎêýňÐ½rTÐ½vsfW¸ăµĴWŊĞĎêýň(京大福井セ)(京大福井セ)○山邊信一、Guixiang○山邊信一、GuixiangZeng,
Zeng,Wei
WeiGuan,	 Guan,	 榊茂好
榊茂好
zmŔ«WăħĖēVŗO]đĺėĚġzmŔ«WăħĖēVŗO]đĺėĚġ(京大福井セ)(京大福井セ)○山田健太、榊茂好○山田健太、榊茂好
{}qqkwreGn}Ŕ«K[XŞ©WŊĞőßŔ«{}qqkwreGn}Ŕ«K[XŞ©WŊĞőßŔ«WµÖýňTřÖýňVŗO]đĺėĭÛWµÖýňTřÖýňVŗO]đĺėĭÛ(京大福井セ)(京大福井セ)○高木望、榊茂好○高木望、榊茂好&2/8;/=3-+5
&2/8;/=3-+5%=>.B
%=>.B87
87=2/
=2/5/-=;873-5/-=;873-%=;>-=>;/%=;>-=>;/80
80! 2!,;3.1/.
,;3.1/.
+7=2+73./8695/A
+7=2+73./8695/A
○○YueChen(京大福井セ)(京大福井セ)○Yue
Chenand
andShigeyoshi
ShigeyoshiSakaki
Sakaki&2/
&2/-;>-3+5
-;>-3+5;85/
;85/80
80++!3!337=/;6/.3+=/
37=/;6/.3+=/37
37!3-+=+5BC/.
!3-+=+5BC/.
2
-+;,8AB5+=38780+;B5-258;3./@3=2"-+;,8AB5+=38780+;B5-258;3./@3=2"(京大福井セ)(京大福井セ)○S.
Bhasha,Y.Y.Tsuji,
Tsuji,andandS.S.Sakaki
Sakaki○○S.F.F.Bhasha,&2/8;/=3-+5
&2/8;/=3-+5
%=>.B
%=>.B
80
80
=2/
=2/
%35B5+=387
%35B5+=387
+7.
+7.
8;B5+=38780
8;B5+=38780
55B53-55B53-/!
* 2/-2+73<6+7.%=/;/8</5/-=3?3=B
/-2+73<6+7.%=/;/8</5/-=3?3=B
5-8285,B)#.
5-8285,B)#./!
4 *
○○GuixiangZeng(京大福井セ)(京大福井セ)○Guixiang
Zengand
andShigeyoshi
ShigeyoshiSakaki
Sakaki&2/;6+5$/.>-=387+7.!3=;81/78937180;+92/7/"A3./
&2/;6+5$/.>-=387+7.!3=;81/78937180;+92/7/"A3./
○○Wei-WeiWang(京大福井セ)(京大福井セ)○Wei-Wei
Wangand
andShigeru
ShigeruNagase
Nagase66－ 211 －

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Ⅴ 資料 (2013)7+5B<3<7+5B<3<80
80=2/
=2/%7
%74 ;371,/7.371
;371,/7.3710/+=>;/
0/+=>;/37
37=2;//
=2;//<=+7785/$>
<=+7785/$>
-8695/A/<-8695/A/<○(京大福井セ)(京大福井セ)○Jing-Dong○Jing-DongGuo
GuoandandShigeru
ShigeruNagase
Nagase #;/.3-=371
#;/.3-=371 #+=2@+B<#+=2@+B< 08;08; &/;9/7/
&/;9/7/ 8;6+=3878;6+=387 0;86
0;86 3;<=
3;<=
#;37-395/<$8>=/<=878@7+7.!/@%/:>3=/;9/7/<#;37-395/<$8>=/<=878@7+7.!/@%/:>3=/;9/7/<(京大福井セ[1]、(京大福井セ[1]、北大理[2]、
北大理[2]、
University
UniversityofofCarfornia[3])Carfornia[3])○伊勢川美穂[1]、○伊勢川美穂[1]、前田理[2]、
前田理[2]、D.
D.J.J.Tantillo[3]、Tantillo[3]、諸熊奎治[1]諸熊奎治[1]&2/8;/=3-+5
&2/8;/=3-+5%=>.B
%=>.B80
803125B
3125B%=/;/8</5/-=3?/%=/;/8</5/-=3?/ >4+3B+6+5.85
>4+3B+6+5.85
/.3+$/+-=38737:>/8><$/+-=38737:>/8>< /.3+
(京大福井セ)(京大福井セ)○Miho○MihoHatanaka
Hatanakaand
andKeiji
KeijiMorokuma
Morokuma○,73=38/7<3=B,73=38/7<3=B +=;3A$/78;6+53C+=387;8>9%=>.B80
+=;3A$/78;6+53C+=387;8>9%=>.B80 +17/=3-+17/=3-8>953713737>-5/+;;87+7.2;863>68695/A/<8>953713737>-5/+;;87+7.2;863>68695/A/<(京大福井セ[1],(京大福井セ[1], 分子研[2])分子研[2])○○○Travis
Travis V.
V. Harris[1],Harris[1], Yuki
Yuki Kurashige[2],Kurashige[2], Takeshi
Takeshi
Yanai[2],Yanai[2],and
andKeiji
KeijiMorokuma[1]Morokuma[1]77－ 212 －

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Ⅴ 資料 (2013)

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－ 213 －

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Ⅴ 資料 (2013)

６．その他（報告）

その他(報告)：諸 熊 奎 治 シニアリサーチフェロー
諸熊奎治シニアリサーチフェローは、スウェーデン王立科学アカデミーが発表した２０１３年のノーベル化学賞の授賞研究の業績説明の中で、重要な貢献をした７人に含まれていることが判った。
今回受賞したマーティン・カープラス氏など３人の米国の科学者は、排ガスの浄化から光合成までさまざまな化学反応がどのように起きているのか、その過程を理解するためのコンピュータ－・シミュレーションの基礎を築き、複雑な化学反応を伴う新薬の開発などに貢献した。
これらのことが、平成２５年１０月１０日付けの京都・読売・朝日・毎日・産経の各新聞に取り上げられている。
１０月１７日付け以降の朝日新聞では、諸熊奎治シニアリサーチフェローが、複雑な分子のふるまいをコンピューターで効率よく計算出来る「オニオム(ＯＮＩＯＭ)法」という手法を１９９５年に開発し、それが、計算化学ソフトに組み込まれ、世界中で活用されていることを「キセキを語る」のシリーズで紹介している。
また、１２月２２日にＢＳフジテレビで放映された「ガリレオＸ(ｴｯｸｽ)」の番組で、諸熊シニアリサーチフェロー他の科学者による計算化学の分野の今後の発展によって生命現象の解明が促進され、コンピューターが描く化学現象が医療の分野などで新しい未来を拓くことが大きく期待されていると紹介されている。

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京都大学福井謙一記念研究センター

年報

2013

2014 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）

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Annual Report

2013

Annual Report
2013

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