Annual Report

2014

年
報
年 報

2010
2014

京都大学
福井謙一記念研究センター

はじめに2014 年度（平成 26 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、科学技術振興機構からの受託研究「多元素協働触媒作用メカニズムの解明と予測の理論・計算化学研究」を推進しておられます。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おられます。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おります。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。
ここで、当センターの歴史を簡単にご紹介いたします。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－i－

て活躍しておられます。この基礎化学研究所は 1998 年（平成 10 年）の福井先生のご逝去の後、2002 年（平成 14 年）に本学に寄贈されて福井謙一記念研究センターとなり、現在に至っております。京都大学の部局となった後、森島 績、中辻 博、榊 茂好、
田中 功、田中 一義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いたしました。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いたしました。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おります。
また、現在本センターの FIFC 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あります。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に存じます。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おります。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 27 年 10 月
京都大学福井謙一記念研究センター長

赤木－ ii －

和夫

目

はじめに

Ⅰ

次

京都大学福井謙一記念研究センター長赤木和夫�������

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 ������������������������

5(3) スーパーバイザー ����������������������

6(4) 専任教員 ��������������������������

17(5) シニアリサーチフェロー �������������������

18(6) リサーチリーダー ����������������������

20

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

21

２．共同研究員 ���������������������������

21

３．博士研究員プロフィール ���������������������

22

４．共同研究員プロフィール ���������������������

44

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 ��������������

45

２．福井謙一記念研究センターセミナー ����������������

46

３．国際交流 ����������������������������

46

４．社会へのアウトリーチ活動 ��������������������

46

５．その他（報告） ��������������������������

47

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

48

２．シニアリサーチフェロー ���������������������

54

３．リサーチリーダー ������������������������

67

４．博士研究員 ���������������������������

76

５．共同研究員 ��������������������������� 167－ iii －

Ⅴ資料
１．研究業績一覧 …………………………………………………………………… 169
２．共同研究者受入れ状況 ………………………………………………………… 179
３．海外渡航一覧 …………………………………………………………………… 180
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 ……… 181
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 …………… 189
６．その他（報告） ………………………………………………………………… 190（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/AnnualReport2014.pdf）－ iv －

Ⅰ 専任教員 ･ スーパーバイザー (2014)Ⅰ

専任教員・スーパーバイザー

１．教員組織平成２６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

工学研究科長伊 藤 紳三郎

工学研究科高分子化学専攻

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

教

授

時 任

宣 博

教

授

八 尾

誠

理学研究科物理学・宇宙物理学専攻

教

授

田 中

功

工学研究科材料工学専攻

教

授

田 中

庸 裕

工学研究科分子工学専攻

教

授

谷 村

吉 隆

理学研究科化学専攻

教

授

山 本

量 一

工学研究科化学工学専攻

教

授

高 田

彰 二

理学研究科生物科学専攻

教

授

林

重 彦

理学研究科化学専攻（工学研究科合成・生物化学専攻）

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

化学研究所物質創製化学研究系

総合研究部門准 教 授

池 田 昌 司理論研究部門

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－

専任

Ⅰ 専任教員 ･ スーパーバイザー (2014)

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.fukui.kyoto-u.ac.jp/organization-j.htm#members【研究分野】 物理化学、量子化学【現在の研究課題】 元素ブロックを有する分子、高分子の理論化学【研究内容キーワード】 分子・高分子の電子物性、量子機能材料、量子統計力学【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、2012 年 4 月京都大学福井謙一記念研究セン
ター長併任、2015 年 4 月京都大学名誉教授ならびに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・日本物理学会・高分子学会【主な著書、学術論文】 1. 炭素学（共編著，化学同人，2011）（過去 5 年以内）
2. 統計力学入門 化学者の視点から（単著，化学同人，2014）
3. Carbon Nanotubes and Graphene（共編著，Elsevier Science, 2014）（以上著書）
1. 今なぜグラフェンか？ ノーベル物理学賞の受賞理由、その本質を考える（単著）化学，66, No. 1, 31-35 (2011).
2. Woodward 教授の見果てぬ夢 －研究メモに遺された室温超伝導への想い（単著）化学，66, No. 10, 12-15 (2011).
3. HOMO-LUMO 概念の誕生（単著）化学，66, No. 11, 26-29 (2011).
4. 未来材料を創成する理論化学の進展（共著）未来材料，12, No. 2, 2-8 (2012).
5. グラフェンとそのフラグメントの電子状態と物性（単著）触媒，54, No. 6,369-374 (2012).
6. 量子化学計算による有機 EL 電荷輸送材料の解析（共著）月刊ディスプレイ，
19, No. 9, 49-52 (2013).
7. 福井先生の未完のテーマ －生命の起源への化学的試論（単著）化学，68,
No. 11, 19-22 (2013).
（以上和文総説）
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－

Ⅰ 専任教員 ･ スーパーバイザー (2014)

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, 8281-8285(2012).
3. Electronic Spectra of Cycl[3.3.2]azine and Related Compounds: Solvent Effect on
Vibronic Couplings (Y. Shigemitsu, M. Uejima, T. Sato, K. Tanaka, and Y. Tominaga)
J. Phys. Chem. A, 116, 9100-9109 (2012).
4. A Triphenylamine Double-Decker: From a Delocalized Radical Cation to a Diradical
Dication with an Excited Triplet State (Y. Yokoyama, D. Sakamaki, A. Ito, K.
Tanaka, and M. Shiro) Angew. Chem. Int. Ed., 51, 9403-9406 (2012).
5. Mechanisms of Localization in Isotope-Substitutes Dynamical Jahn-Teller Systems(N. Iwahara, T. Sato, K. Tanaka, and L. F. Chibotaru) Eur. Phys. Lett., 100, 43001
1-6 (2012).
6. Chemical Reactivity in Nucleophilic Cycloaddition to 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, 6366 (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, 12858-12867(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 andTransition 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, andK. Tamao) Chem. Lett., 43, 432-434 (2014).
19. A Designed Fluorescent Anthracene Derivative: Theory, Calculation, Synthesis, andCharacterization (M. Uejima, T. Sato, M. Detani, A. Wakamiya, F. Suzuki, H. Suzuki,－3－

Ⅰ 専任教員 ･ スーパーバイザー (2014)

T. Fukushima, K. Tanaka, Y. Murata, C. Adachi, and H. Kaji) Chem. Phys. Lett., 602,
80-83 (2014).

20. Quantum Yield in Blue-Emitting Anthracene Derivatives: Vibronic Coupling Density
and Transition Dipole Moment Density (M. Uejima, T. Sato, D. Yokoyama, K.
Tanaka, and J. –W. Park) Phys. Chem. Chem. Phys., 16, 14244-14256 (2014).
21. Synthesis and Polymerization of a para-Disubstituted T8-caged Hexaisobutyl-POSS
Monomer (T. Maegawa, Y. Irie, H. Fueno, K. Tanaka, and K. Naka) Chem. Lett., 43,
1532-1534 (2014).

22. An Isolable Diborane(4) Compound with Terminal B-H Bonds: Structural
Characteristics and Electronic Properties (Y. Shoji, S. Kaneda, H. Fueno, K. Tanaka,
K. Tamao, D. Hashizume, and T. Matsuo) Chem. Lett., 43, 1587-1589 (2014).
23. Electronic Structure of Tetraaza[1.1.1.1]o, p, o, p-Cyclophane and Its Oxidized States(D. Sakamaki, A. Ito, T. Matsumoto, and K. Tanaka) RSC Adv., 4, 39476-39483(2014).

24. Synthesis of Conjugated Polymers Containing Gallium Atoms and Evaluation of
Conju gation through Four-Coordinate Gallium Atoms (T. Matsumoto, Y. Onishi,
K. Tanaka, H. Fueno, K. Tanaka, and Y. Chujo) Chem. Commun., 50, 15740-15743(2014).
25. Reactivity of Endohedral Metallofullerene La2@C80 in Nucleophilic and Electrophilic
Attacks: Vibronic Coupling Density Approach (N. Haruta, T. Sato, and K. Tanaka) J.
Org. Chem., 80, 141-147 (2014).

26. Fluorescent Triphenylamine Derivative: Theoretical Design Based on Reduced
Vibronic Coupling (Y. Kameoka, M. Uebe, A. Ito, T. Sato, and K. Tanaka) Chem.
Phys. Lett., 615, 44-49 (2015).
27. A Light-Emitting Mechanism for Organic Light-Emitting Diodes: Molecular Designfor Inverted Singlet-Triplet Structure and Symmetry-Controlled Thermally Activated
Delayed Fluorescence (T. Sato, M. Uejima, K. Tanaka, H. Kaji, and C. Adachi) J.
Mater. Chem. C, 3, 870-878 (2015).
28. Enhanced Electroluminescence from a Thermally Activated Delayed-Fluorescence
Emitter by Suppressing Nonradiative Decay (K. Shizu, M. Uejima, H. Nomura, T.
Sato, K. Tanaka, H. Kaji, and C. Adachi) Phys. Rev. Appl., 3, 014001 1-7 (2015).
29. Strategy for Designing Electron Donors for Thermally Activated Delayed
Fluorescence Emitters (K. Shizu, H. Tanaka, M. Uejima, T. Sato, K. Tanaka, H. Kaji,and C. Adachi) J. Phys. Chem., C, 119, 1291-1297 (2015).

30. Reactivity Index for Diels-Alder Cycloadditions to Large Polycyclic Aromatic
Hydrocarbons Using Vibronic Coupling Density (N. Haruta, T. Sato, and K. Tanaka)
Tetrahedron Lett., 56, 590-594 (2015).
31. Synthesis and Characterization of Heterofluorenes Containing Four-coordinatedGroup 13 Elements: Theoretical and Experimental Analyses and Comparison of
Structures, Optical Properties and Electronic States (T. Matsumoto, K. Tanaka, K.
Tanaka, and Y. Chujo) Dalton Trans., 44, 8697-8707 (2015).

32. Luminescent Coordination Glass: Remarkable Morphological Strategy for Assembled
Eu (III) Complexes (Y. Hirai, T. Nakanishi, Y. Kitagawa, K. Fushimi, T. Seki, H.
Ito, H. Fueno, K. Tanaka, T. Satoh, and Y. Hasegawa) Inorg. Chem., 54, 4364-4370(2015).
33. Multiscale Simulation of Charge Transport in a Host Material, N, N’-Dicarbazole3,5-benzene (mCP), for Organic Light-Emitting Diodes (F. Suzuki, K. Shizu, H.
Kawaguchi, S. Furukawa, T. Sato, K. Tanaka, and H. Kaji) J. Mater. Chem. C, 3,
5549-5555 (2015).
（以上学術論文）【学術関係の受賞など】 2002-2007 年 科学技術振興機構 (JST) の戦略的創造研究推進事業 (CREST)「精密分子設計に基づくナノ電子デバイス構築」研究代表者
2004-2005 年 文部科学省知的クラスター創成事業「京都ナノテククラスター」のナノテク共同研究テーマ「mRNA の数理学的特異性抽出ソフトの開発と解析サービスの事業化展開」研究代表者－4－Ⅰ 専任教員 ･ スーパーバイザー (2014)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. S. Matsushita, K. Akagi, “Macroscopically Aligned Graphite Films Prepared from
Iodine-Doped Stretchable Polyacetylene Films Using Morphology-Retaining（過去 5 年以内）
Carbonization”, J. Am. Chem. Soc., 137, 9077 (2015).
2. J. Bu, K. Watanabe, H. Hayasaka, K. Akagi, “Photochemically Colour-Tuneable
White Fluorescence Illuminants consisting of Conjugated Polymer Nanospheres”,
Nat. Commun. 5, 3799 (2014).
3. 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).
4. B. A. San Jose, J. Yan, K. Akagi, “Dynamic Switching of the Circularly Polarized
Luminescence of Disubstituted Polyacetylene by Selective Transmission though a
Thermotropic Chiral Nematic Liquid Crystal”, Angew. Chem. Int. Ed., 53, 10641,(2014).
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）－5－Ⅰ 専任教員 ･ スーパーバイザー (2014)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】 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/【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 月京都大学大学院工学研究科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、2013 年 1月京都大学物質－細胞統合システム拠点・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、アメリカ化学会、イギリス王立化学会【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、第 22 期日本学術会議会員
7. 2013 年 The RSC de Gennes Prize、第 10 回江崎玲於奈賞、平成 25 年度京都大学孜孜賞、The fellow of the UK Royal Society of Chemistry (RSC)
8. 2014 年 2014 Thomson Reuters Highly Cited Researcher
9. 2015 年 マルコ・ポーロ イタリア科学賞－6－Ⅰ 専任教員 ･ スーパーバイザー (2014)【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・誘電的・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【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】 日本セラミックス協会理事、粉体粉末冶金協会理事【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. 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.
4. T. Kawamoto, K. Fujita, H. Akamatsu, T. Nakamura, T. Kinoshita, M. Mizumaki,
N. Kawamura, M. Suzuki, Y. Kususe, S. Murai, and K. Tanaka,“Eu M4,5- andL2,3-edge x-ray magnetic circular dichroism of ferromagnetic amorphous oxides in
EuO-TiO2 system”, Physical Review B 88 (2013) 024405-1-9.
5. X. Meng, A. V. Kildishev, K. Fujita, K. Tanaka, and V. M. Shalaev, “Wavelengthtunable spasing in the visible”, Nano Letters 13 (2013) 4106−4112.
6. 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.
7. M. Nishijima, T. Ootani, Y. Kamimura, T. Sueki, S. Esaki, S. Murai, K. Fujita,
K. Tanaka, K. Ohira, Y. Koyama, and I. Tanaka, “Accelerated discovery ofcathode materials with prolonged cycle life for lithium-ion battery”, Nature
Communications 5 (2014) 4553-1-7.
8. T. Kawamoto, K. Fujita, I. Yamada, T. Matoba, S. J. Kim, P. Gao, X. Pan, S. D.
Findlay, C. Tassel, H. Kageyama, A. J. Studer, J. Hester, T. Irifune, H. Akamatsu,
and K. Tanaka, “Room-temperature polar ferromagnet ScFeO3 transformed from ahigh-pressure orthorhombic perovskite phase”, Journal of the American Chemical
Society 136 (2014) 15291-15299.
【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）－7－Ⅰ 専任教員 ･ スーパーバイザー (2014)【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
－8－

Ⅰ 専任教員 ･ スーパーバイザー (2014)【氏名】 Norihiro Tokitoh【職名】 Professor, Director【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); Director of ICR (2014-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 Organo-metallics,
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; 2014- The Society of Silicon
Chemistry, Japan, Vice-president【主な著書、学術論文】 1. Synthesis, Structure and Reactivity of 1-Bromoalumole, Wasano, T.; Agou, T.;
Sasamori, T.; Tokitoh, Chem. Commun. 2014, 50, 8148-8150.
（過去 5 年以内）
2. 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.
3. Synthesis and Properties of 4,5,6-Triphospha[3]radialene, Miyake, H.; Sasa-mori, T.;
Tokitoh, N. Angew. Chem. Int. Ed. 2012, 51, 3458-3461.
4. 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.
5. 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.
【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－9－

Ⅰ 専任教員 ･ スーパーバイザー (2014)【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【直通電話】 075-753-3774

物理学第一教室
128 号室【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).
4. Pulse delay effect in angular distribution of near-threshold EUV+IR two-photon
ionization of Ne, S. Mondal, H. Fukuzawa, K. Motomura, T. Tachibana, K. Nagaya,
T. Sakai, K. Matsunami, S. Yase, M. Yao, S. Wada, H. Hayashita, N. Saito, C.
Callegari, K. C. Prince, C. Miron, M. Nagasono, T. Togashi, M. Yabashi, K. L.
Ishikawa, A. K. Kazansky, N. M. Kabachnik, and K. Ueda. Phys. Rev. A 89. 013415(2014).
5. Inelastic x-ray scattering study of plasmon dispersions in solid and liquid Rb, K.
Kimura, K. Matsuda, N. Hiraoka, T. Fukumaru, Y. Kajihara, M. Inui, M. Yao, Phys.
Rev. B. 89, 014206 (2014).
6. Nanoplasma Formation by High Intensity Hard X-rays, T. Tachibana, Z. Jurek, H.
Fukuzawa, K. Motomura, K. Nagaya, S. Wada, P. Johnsson, M. Siano, S. Mondal,Y. Ito, M. Kimura, T. Sakai, K. Matsunami, H. Hayashita, J. Kajikawa, X.-J. Liu, E.
Robert, C. Miron, R. Feifel, J. P. Marangos, K. Tono, Y.Inubushi, M. Yabashi, S.K. Son,, B. Ziaja, M. Yao, R. Santra, and K. Ueda, Science Report 5, 10977; doi:
10.1038/srep10977 (2015).
7. Inelastic X-ray Scattering Study on Plasmon Dispersion in Liquid Cs, Koji Kimura,
Kazuhiro Matsuda, Nozomu Hiraoka, Yukio Kajihara, Tetsu Miyatake, Yotaro
Ishiguro, Toru Hagiya, Masanori Inui, and Makoto Yao, J. Phys. Soc. Japan,(accepted).
－ 10 －

Ⅰ 専任教員 ･ スーパーバイザー (2014)【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，材料情報学，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【主な著書、学術論文】 1. Togo, A., Chaput, L. & Tanaka, I. Distributions of phonon lifetimes in Brillouinzones. Physical Review B 91, 094306 (2015).
（過去 5 年以内）

2. Seko, A. & Tanaka, I. Special quasirandom structure in heterovalent ionic systems.
Physical Review B 91, 024106 (2015).
3. Seko, A., Takahashi, A. & Tanaka, I. Sparse representation for a potential energy
surface. Physical Review B 90, 024101 (2014).
4. Seko, A., Shitara, K. & Tanaka, I. Efficient determination of alloy ground-state
structures. Physical Review B 90, 174104 (2014).
5. Seko, A., Maekawa, T., Tsuda, K. & Tanaka, I. Machine learning with systematic
density-functional theory calculations: Application to melting temperatures ofsingle- and binary-component solids. Physical Review B 89, 054303 (2014).
6. Nishijima, M. et al. Accelerated discovery of cathode materials with prolonged
cycle life for lithium-ion battery. Nature Communications 5, 4553 (2014).
7. Ikeda, Y., Seko, A., Togo, A. & Tanaka, I. Phonon softening in paramagnetic bcc Fe
and its relationship to the pressure-induced phase transition. Physical Review B 90,
134106 (2014).

8. Akamatsu, H. et al. Inversion Symmetry Breaking by Oxygen Octahedral Rotationsin the Ruddlesden-Popper NaRTiO4 Family. Physical Review Letters 112, 187602,
187602 (2014).
9. Akamatsu, H. et al. Strong Spin-Lattice Coupling Through Oxygen Octahedral
Rotation in Divalent Europium Perovskites. Advanced Functional Materials 23,
1864-1872 (2013).
【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）－ 11 －

Ⅰ 専任教員 ･ スーパーバイザー (2014)【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. Effect of Chloride Ion as a Hole Scavenger on the Photocatalytic Conversion of（過去 5 年以内）
CO2 in an Aqueous Solution over Ni-Al Layered Double Hydroxides, Shoji Iguchi,
Kentaro Teramura, Saburo Hosokawa, Tsunehiro Tanaka , Phys. Chem. Chem.
Phys., 2015, 17, 17995-18003.
2. Popping of Graphene Oxide: Application in Preparing Metal Nanoparticle
Catalysts, Yongjun Gao, Xi Chen, Jiaguang Zhang, Hiroyuki Asakura, Tsunehiro
Tanaka, Kentaro Teramura, Ding Ma, Ning Yan , Adv. Mater., 2015, in press.
3. Oxygen Storage Capacity of Sr3Fe2O7-δ Having High Structural Stability , Kosuke
Beppu, Saburo Hosokawa, Kentaro Teramura, Tsunehiro Tanaka , J. Mater. Chem. A,
2015, 3, 13540-13545.
4. Highly Efficient Photocatalytic Conversion of CO2 into Solid CO Using H2O as a
Reductant over Ag-Modified ZnGa2O4, Zheng Wang, Kentaro Teramura, Saburo
Hosokawa, Tsunehiro Tanaka, J. Mater. Chem. A, 2015, in press
5. A Theoretical Approach to La L1-edge XANES Spectra of La Complex Oxides andTheir Local Configuration, Hiroyuki Asakura, Tetsuya Shishido, Kentaro Teramura,
Tsunehiro Tanaka, J. Chem. Phys., 2015, 142(16):164507 (8 pages)
6. Local Structure and L1 and L3-edge X-ray Absorption Near Edge Structure of Late
Lanthanide Elements (Ho, Er, Yb) in Their Complex Oxides, Hiroyuki Asakura,
Tetsuya Shishido, Kentaro Teramura, Tsunehiro Tanaka, J. Phys. Chem. C, 2015,
119(15), 8070-8077.
7. Noble-Metal-Free NOx Storage over Ba-Modified TiO2 Photocatalysts under UVLight Irradiation at Low Temperatures, Akira Yamamoto, Yuto Mizuno, Kentaro
Teramura, Saburo Hosokawa, Tetsuya Shishido, Tsunehiro Tanaka, ACS Catalysis,
2015, 5, 2939-2943.
8. The Support Effect on the Size and Catalytic Activity of Thiolated Au25
Nanoclusters as Precatalyst, Jun Fang, Jingguo Li, Bin Zhang, Xun Yuan, Hiroyuki
Asakura, Tsunehiro Tanaka, Kentaro Teramura, Jianping Xie, and Ning Yan,
Nanoscale, 2015, 7, 6325-6333.
－ 12 －

Ⅰ 専任教員 ･ スーパーバイザー (2014)【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
（過去 5 年以内）
Brownian System Driven by a Biharmonic Force, J. Phys. Chem. B 117, 1313213144 (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 hierarchical equations of motion in real and imaginary time:
Correlated initial states and thermodynamic quantities, J. Chem, Phys 141, 044114[13 pages] (2014). [2014 JCP Editors’Choice]
5. Y. Tanimura, Real-Time and Imaginary-Time Quantum Hierarchal Fokker-Planck
Equations, J. Chem, Phys 142, 144110 [20 pages] (2015).
【学術関係の受賞】 2002 Morino Foundation Award
2012 Humboldt Research Award from the Alexander von Humboldt Foundation inGermany
2014 J. Chem. Phys. Editors’choice in Theoretical Methods and Algorithms
2015 American Physical Society, fellow－ 13 －

Ⅰ 専任教員 ･ スーパーバイザー (2014)【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【学位】 1996 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
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. A. J. Dunleavy, K. Wiesner, R. Yamamoto, and C. P. Royall, Mutual information（過去 5 年以内）
reveals multiple structural relaxation mechanisms in a model glassformer, Nature
Communications 6, 6089 (2015).
2. S. Yasuda and R. Yamamoto, Synchronized molecular dynamics simulation via
macroscopic heat and momentum transfer: an application to polymer lubrication,
Phys. Rev. X 4, 041011 (2014).
3. J. J. Molina and R. Yamamoto, Direct numerical simulations of rigid bodydispersions. I. Mobility/Friction tensors of assemblies of spheres, J. Chem. Phys.
139, 234105 (2013).
4. R. Tatsumi and R. Yamamoto, Velocity relaxation of a particle in a confinedcompressible fluid, J. Chem. Phys. 138, 184905 (2013).
5. J. J. Molina, Y. Nakayama, and R. Yamamoto, Hydrodynamic interactions of selfpropelled swimmers, Soft Matter 9, 4923-4936 (2013).
6. H. Mizuno and R. Yamamoto, General constitutive model for supercooled 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－ 14 －

Ⅰ 専任教員 ･ スーパーバイザー (2014)【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
課程退学【学位】 1994 年 3 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
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】 日本生物物理学会理事【主な著書、学術論文】 1. W. Li, W. Wang, and S. Takada, Energy landscape views for interplays among（過去 5 年以内）
folding, binding, and allostery of calmodulin domain, Proc. Nat. Acad. Sci. USA,111: 10550-10555, 2014.
2. M.J.McGrath, I.F.Kuo, S.Hayashi, and S.Takada, ATP hydrolysis mechanism
in kinesin studied by combined quantum-mechanical molecular-mechanicalmetadynamics, JACS, 103: 8908-8919, 2013.
3. 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.
4. 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.
5. S.Takada, Coarse-grained molecular simulations of large biomolecules, Curr
Opinion in Struct Biol, 22: 130-137, 2012.
6. 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.
7. 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.
－ 15 －

Ⅰ 専任教員 ･ スーパーバイザー (2014)【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).

－ 16 －

Ⅰ 専任教員 ･ スーパーバイザー (2014)

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【学位】 2008 年 3 月 博士（工学）、京都大学【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 “Glass transition of the monodisperse
gaussian core model” Phys. Rev. Lett. (Editors’ Suggestion) 106, 015701 (2011).
（過去 5 年以内）

2. Atsushi Ikeda and Kunimasa Miyazaki ”Slow Dynamics of the High Density
Gaussian Core Model” J. Chem. Phys. 135, 054901 (2011).
3. Patrick Charbonneau, Atsushi Ikeda, Giorgio Parisi and Francesco Zamponi “Glass
Transition and Random Close Packing above Three Dimensions” Phys. Rev. Lett.
107, 185702 (2011).
4. 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).
5. Atsushi Ikeda, Ludovic Berthier and Giulio Biroli “Dynamic criticality at the
jamming transition” J. Chem. Phys. 138, 12A507 (2013).
6. Atsushi Ikeda, Ludovic Berthier and Peter Sollich “Disentangling glass andjamming physics in the rheology of soft materials” Soft Matter (Highlight Article) 9,7669 (2013).
7. Misaki Ozawa, Walter Kob, Atsushi Ikeda, Kunimasa Miyazaki “Equilibrium phase
diagram of a randomly pinned glass-former” Proc. Natl. Acad. Sci. USA 112, 6914
(2015).

【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)、2015 年 4 月 文部科学省「平成 27 年度科学技術分野の文部科学大臣表彰」若手科学者賞－ 17 －

Ⅰ 専任教員 ･ スーパーバイザー (2014)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【学位】 1975 年 3 月

大阪大学大学院基礎工学研究科博士課修了
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

－ 18 －

Ⅰ 専任教員 ･ スーパーバイザー (2014)【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 130 報（過去 5 年以内） 1. R. I. Kaiser, L. G. Muzangwa, T. Yang, D. S. N. Parker, A. M. Mebel, A. Jamal,
and K. Morokuma, A Crossed Molecular Beam and Ab Initio Study on theFormation of 5- and 6-Methyl-1,4-Dihydronaphthalene (C11H12) via the Reaction ofMeta-Tolyl (C7H7) with 1,3-Butadiene (C4H6). Phys. Chem. Chem. Phys. 17, 76997706 (2015).
2. B. Liu, J. Liu, H.-B. Li, R. Bhola, E. A. Jackson, L. T. Scott, A. J. Page, S.
Irle, K. Morokuma and C. Zhou, Nearly Exclusive Growth of Small Diameter
Semiconducting Single-Wall Carbon Nanotubes from Organic Chemistry Synthetic
End-Cap Molecules, Nano Lett. 15, 586-595 (2015).
3. M. Hatanaka and K. Morokuma, Exploring the reaction coordinates for f-f emission
and quenching of lanthanide complexes – thermo-sensitivity of terbium(III)luminescence. J. Chem. Theo. Comp. 10, 4184-4188 (2014).
4. M. Isegawa, F. Liu, S. Maeda and K. Morokuma, Complete active space second
order perturbation theory (CASPT2) study of N(2D) + H2O reaction paths on D1
and D0 potential energy surfaces: direct and roaming pathways, J. Chem. Phys.
141, 154303/1-9 (2014).
5. S. Maeda, Y. Harabuchi, T. Taketsugu, and K.Morokuma, Systematic Exploration of
Minimum Energy Conical Intersection Structures near the Franck-Condon Region, J.
Phys. Chem. A 118, 12050-12058 (2014).
6. S. Maeda, Y. Harabuchi, Y. Ono, T. Taketsugu, and K. Morokuma, Intrinsic
Reaction Coordinate: Calculation, Bifurcation, and Automated Search, Int. J.
Quant. Chem. 115, 258-269 (2015).
7. X. Li, L. W. Chung, K. Morokuma and G. Li, A Theoretical Study on the
UVR8 Photoreceptor: Sensing Ultraviolet-B by Tryptophan and Dissociation of
Homodimer, J. Chem. Theo. Comp. 10, 3319-3330 (2014).
8. M. Isegawa, F. Liu, S. Maeda, and K. Morokuma, Ab initio reaction pathways
for photodissociation and isomerization of nitromethane on four singlet potential
energy surfaces with three roaming paths, J. Chem. Phys. 140, 244310/1-11 (2014).
9. G. P. Petrova, H.-B. Li, K. Maruoka and K. Morokuma, Asymmetric phase-transfer
catalysis with homo- and heterochiral quaternary ammonium salts: a theoretical
study, J. Phys. Chem. B, 118, 5154-5167 (2014). doi:10.1021/jp501520g【学術関係の受賞など】 International Academy of Quantum Molecular Science Medal, 1978; 日本化学会賞，
1992; Schrödinger Medal, World Association of Theoretical Organic Chemists, 1993;
Fukui Medal, Asian Pacific Association of Theoretical & 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－ 19 －

Ⅰ 専任教員 ･ スーパーバイザー (2014)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】 075-781-4757【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・遷移金属錯体・反応解析・触媒作用・金属微粒子【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. A Theoretical Study of an Unusual Y-Shaped Three-Coordinate Pt Complex: Pt(0)（過去 5 年以内）
sigma-Disilane Complex or Pt(II) Disilyl Complex? N. Takagi, S. Sakaki, J. Am.
Chem. Soc., 134, 11749-11759 (2012).
2. 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).
3. 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).
4. 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).
5. 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).
6. Efficient Catalyst for Acceptorless Alcohol Dehydrogenation: Interplay ofTheoretical and Experimental Studies, G. Zeng, S. Sakaki, K. Fujita, H. Sano, R.
Yamaguchi, ACS Catal. 4, 1010-1020 (2014).
7. Catalytic Transfer Hydrogenation by Trivalent Phosphorus Compound:
Phosphorus-Ligand Cooperation Pathway or PIII/PV Redox Pathway? G. Zeng, S.
Maeda, T. Taketsugu, and S. Sakaki, Angew. Chem. Int. Ed., 128, 4721-4725 (2014).
8. The Crucial Roles of MgCl2 as a Non-innocent Additive in the Ni-Catalyzed
Carboxylation of Benzyl Halide with CO 2, F. B. Sayyed, S. Sakaki, Chem.
Commun., 50, 13026 - 13029 (2014).
9. σ-Bond Activation of Small Molecules and Reactions Catalyzed by TransitionMetal Complexes: Theoretical Understanding of Electronic Processes, W. Guan, F.
B. Sayyed, G. Zeng, and S. Sakaki, Inorg. Chem., 53, 6444-6457 (2014).
10. Reasons Two Nonstrained C–C σ-Bonds Can Be Easily Cleaved in Decyanative[4 + 2] Cy-cloaddition Catalyzed by Nickel(0)/Lewis Acid Systems. Theoretical
Insight, W. Guan, S. Sakaki, T. Kurahashi, S. Matsubara, ACS Catalysis, 5, 1-10
(2015).
【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）
Fukui Medal (2015; from APATCC)－ 20 －

Ⅱ 博士研究員 (2014)

Ⅱ

博士研究員

１．博士研究員組織
平成２６年度職

名福井センターフェロー

氏

名

嶺澤

範行

齋藤

拓也

John Jairo Molina
永瀬グループ

特推研究フェロー

Jingdong Guo
Wei-Wei Wang
畑中

福井センターフェロー

美穂

Romain Ramozzi
鈴木聡

Travis Harris

諸熊グループ研究フェロー伊勢川

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

Guixiang Zeng（會中垣
榊グループ
特推研究フェロー

桂 香）

雅之

Yue Chen
Sayyed Farred Bhasha
山田

健太

Shuwei Tang
Hong Zheng

２．共同研究員職
諸熊グループ名氏

名

Maneeporn Puripat

共同研究員－ 21 －

Ⅱ 博士研究員 (2014)

３. 博士研究員プロフィール【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・円錐交差【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, “Vertical excitation energies of linear cyanine dyes by spin-flip timedependent density functional theory”, Chem. Phys. Lett. 622, 115-119 (2015).
（過去 5 年以内）

2. N. Minezawa, “State-specific solvation effect on the intramolecular charge transfer
reaction in solution: A linear-response free energy TDDFT method”, Chem. Phys.
Lett. 608, 140-144 (2014).
3. N. Minezawa, “Optimizing minimum free-energy crossing points in solution:
Linear-response free energy/spin-flip density functional theory approach”, J. Chem.
Phys. 141, article No. 164118 (2014).
4. 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).
5. 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).

－ 22 －

Ⅱ 博士研究員 (2014)【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】 Polymer dynamics, Fluctuation of driven polymer【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, “Rate in template-directed polymer synthesis”, Phys. Rev. E, 89,
062716 (8 pages total) (2014).
（過去 5 年以内）
2. Takuya Saito, Takahiro Sakaue, “Cis-trans dynamical asymmetry in driven polymertranslocation”, Phys. Rev. E, 88, 042606 (5 pages total) (2013).
3. Takuya Saito, Takahiro Sakaue, “Process time distribution of driven polymertransport”, Phys. Rev. E, 85, 061803 (7 pages total) (2012).
4. 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).
5. 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－ 23 －

Ⅱ 博士研究員 (2014)【氏名】 John Jairo Molina【職名】 Assistant Professor【所属】 Department of Chemical Engineering, Kyoto University【研究室】 A4 - 113【直通電話】 075 383 2671
【FAX】 075 383 2651
【電子メールアドレス】 john@cheme.kyoto-u.ac.jp【電子メールアドレス】 http://www-tph.cheme.kyoto-u.ac.jp【研究分野】 Computational Soft Matter【現在の研究課題】 Dynamics of Active Particles【研究内容キーワード】 Active particles, swimmers,【学歴】 July 2008, Master of Sci., Dept. Physics, ENS Lyon
Sept. 2011, Doctor of Sci., Physical and Analytical Chemistry, Paris 6【学位】 Doctor of Science from University of Paris 6【略歴】 Oct. 2011, Postdoctoral Fellow, Kyoto University
Apr. 2014, FIFC Fellow, Kyoto University【主な著書、学術論文】 1. Thangh-Nghi Nguyen, Magali Duvail, Arnaud Villard, John J. Molina, Philippe
Guilbaud, and Jean-François Dufrêche, “Multi-scale modeling of uranyl chloride（過去 5 年以内）
solutions”, J. Chem. Phys. 142, 024501 (2015)
2. John J. Molina and R. Yamamoto, “Diffusion of colloidal particles in swimming
suspensions”, Mol. Phys. 112, 1389 (2014)
3. Adnan Hamid, John J. Molina, and Ryoichi Yamamoto, “Direct numericalsimulations of sedimenting spherical particles at finite Reynolds number”, RSC
Adv. 4, 53681 (2014)
4. Bertrand Siboulet, John J. Molina, Benoît Coasne, Pierre Turq and Jean-FrançoisDufrêche, “Water self-diffusion at the surface of silica glasses: effect of hydrophilic
to hydrophobic transition”, Mol. Phys. 111, 3410 (2013)
5. John J. Molina and Ryoichi Yamamoto, “Direct Numerical simulations of rigid
body dispersions. I. Mobility/friction tensors of assemblies of spheres”, J. Chem.
Phys. 139, 234105 (2013)－ 24 －

Ⅱ 博士研究員 (2014)【氏名】 Jingdong Guo【職名】 Research Fellow【所属】 Institute for Chemical Research【研究室】 Room M441

【電子メールアドレス】 guo_jd@boc.kuicr.kyoto-u.ac.jp【研究分野】 Theoretical Chemistry【現在の研究課題】 Dispersion Force Effects on the Dissociation of“Jack-in-the-Box”Diphosphanes
and Diarsanes.

【研究内容キーワード】 Dispersion effect【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
2012-2015, Research Fellow, Institute for Chemical Research, Kyoto University【主な著書、学術論文】 1. Jing-Dong Guo, Shigeru Nagase, and Philip P. Power, Dispersion Force
Effects on the Dissociation of “Jack-in-the-Box” Diphosphanes and Diarsanes,（過去 5 年以内）
Organometallics 2015, 34, 2028.
2. Takahiro Sasamori, Tomohiro Sugahara, Tomohiro Agou, Jing-Dong Guo, Shigeru
Nagase, Rainer Streubel, and Norihiro Tokitoh, Synthesis and Characterization of a
1,2-Digermabenzene, Organometallics 2015, 34, 2106.
3. Takuya Kuwabara, Jing-Dong Guo, Shigeru Nagase, Takahiro Sasamori, Norihiro
Tokitoh, and Masaichi Saito, Synthesis, Structures, and Electronic Properties of
Triple- and Double-Decker Ruthenocenes Incorporated by a Group 14 Metallole
Dianion Ligand, J. Am. Chem. Soc. 2014, 136, 13059－ 25 －

Ⅱ 博士研究員 (2014)【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.

－ 26 －

Ⅱ 博士研究員 (2014)【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】 ・ 柔らかな不斉触媒を用いる C-C 結合生成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ランタノイド発光プローブの発光・消光・
励起エネルギー移動の機構解明
・ 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、理論化学研究会【主な著書、学術論文】 1. M. Hatanaka, K. Morokuma, “How Can Fluctional Chiral Lanthanide(III)Complexes Achieve a High Stereoselectivity in Aqueous Mukaiyama-Aldol（過去 5 年以内）
Reaction?” ACS Catal. 5, pp 3731-3739 (2015).
2. M. Hatanaka, K. Morokuma, “Exploring the reaction coordinates for f-f emission
and quenching of lanthanide complexes – thermosensitivity of terbium(III)luminescence”, J. Chem. Theory Comput. 10, pp 4184-4188 (2014).
3. 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,
pp 2640-2646 (2014).
4. 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

5. 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).
【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－ 27 －

Ⅱ 博士研究員 (2014)【氏名】 Romain Ramozzi【職名】 Postdoctoral Fellow【所属】 Fukui Kenichi Memorial Research Group 1, Fukui Institute for Fundamental
Chemistry【研究室】 202
【直通電話】 075-711-7831【FAX】 075-781-4757【電子メールアドレス】 ramozzi@fukui.kyoto-u.ac.jp【研究分野】 Computational Chemistry【現在の研究課題】 Mechanistic studies of organic and organometallic reactions.
【研究内容キーワード】 DFT, Multicomponent reactions, AFIR method【学歴】 2009, Master degree, Ecole Polytechnique and Ecole Normale Supérieure de Cachan,
Palaiseau and Cachan, France
2013, Ph.D., Ecole Normale Supérieure de Lyon, Lyon, France【学位】 Doctor of Philosophy, Ecole Normale Supérieure de Lyon, Lyon, France【略歴】 2014, Chemistry Laboratory, ENS de Lyon, Lyon, France
2010, Organic Chemistry Laboratory, ENSTA, Paris, France
2008, Chemistry Laboratory, ENS de Cachan, Cachan, France
2007, Physical-Chemistry Laboratory, Paris XI University, Orsay, France【主な著書、学術論文】 1. R. Ramozzi, K. Morokuma, Revisiting the Passerini reaction mechanism: existenceof the nitrilium, organocatalysis of its formation and solvent effect, J. Org. Chem.,（過去 5 年以内）
2015, doi:10.1021/acs.joc.5b00594.
2. L. Wa Chung, W. M. C. Sameera, R. Ramozzi, A. J. Page, M. Hatanaka, G. P.
Petrova, T. V. Harris, X. Li, Z. Ke, F. Liu, H.B. Li, L. Ding, and K. Morokuma, The
ONIOM Method and its Applications, Chem. Rev., 2015, doi:10.1021/cr5004419,
120 pages.
3. R. Ramozzi, N. Chéron, L. El Kaïm, L. Grimaud, and P. Fleurat-Lessard Predicting
new Ugi-Smiles couplings: a combined experimental and theoretical study, Chem.
Eur. J., 2014, 20 (29), 9094-9099.
4. R. Ramozzi, N. Chéron, B. Braïda, P. C. Hiberty, P. Fleurat-Lessard, A Valence
Bond view of isocyanides’ electronic structure, New. J. Chem., 2012, 36 (5), 11371140.
5. N. Chéron, R. Ramozzi, L. El Kaïm, L. Grimaud, P. Fleurat-Lessard Challenging 50
years of established views on Ugi reaction : a theoretical approach, J. Org. Chem.,
2012, 77 (3), 1361-1366.
【学術関係の受賞など】 FIFC fellowship, 2015
JSPS Fellowship, 2014
Ecole Normale Supériere de Cachan, PhD Fellowship, 2010-2013
Ecole Normale Supérieure de Cachan fellowship, 2007-2010－ 28 －

Ⅱ 博士研究員 (2014)【氏名（ふりがな）】 鈴木

聡 （すずきさとし）【職名】 研究員【所属】 福井謙一記念研究センター
212 号室【研究室】 福井謙一記念研究センター【直通電話】 075-711-7647【電子メールアドレス】 suzuki@fukui.kyoto-u.ac.jp【研究分野】 理論化学

計算化学

【現在の研究課題】 蛍光分子の円錐交差探索【研究内容キーワード】 励起状態、項間交差【学歴】 2014 年 3 月

九州大学理学府【学位】 2014 年 3 月

博士（理学） 九州大学

【略歴】 2014 年 4 月

福井謙一記念研究センター

化学専攻修了【所属学会】 分子科学会、理論化学研究会【主な著書、学術論文】 1. T. Tsuneda, J.-W. Song,S. Suzuki, and K. Hirao ”On Koopmans'theorem in density
functional theory” J. Chem. Phys. 133, 174101 (2010).
（過去 5 年以内）
2. S. Suzuki, T. Tsuneda, and K. Hirao “A theoretical investigation on photocatalyticoxidation on the TiO2 surface”
3. S. Suzuki, R. Ebisuzaki, Y. Watanabe, and H. Nakano “Relativistic Multireference
Perturbation Theory and its Semi-Approximate Second-Order Form” J. Comput.
Chem. Jpn. Vol.13, No.1, pp32 (2014)【学術関係の受賞など】 2012 年 9 月

Best Poster Awardsat the Annual Meeting of the Japan Society for
Molecular Science－ 29 －

Ⅱ 博士研究員 (2014)【氏名】 Travis Harris【職名】 Visiting Assistant Professor【所属】 University of Puget Sound, Tacoma, WA, USA【直通電話】 360-220-5625【FAX】 253-879-6022【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】 2014, Visiting Assistant Professor, SUNY Oswego
2012, Postdoctoral Fellow, Fukui Institute【主な著書、学術論文】 1. Chung, L. W.; Sameera, W. M. C.; Ramozzi, R.; Page, A. J.; Hatanaka, M.; Petrova,
G. P.; Harris, T. V.; Li, X.; Ke, Z.; Liu, F.; Li, H. B.; Ding, L.; Morokuma, K. The（過去 5 年以内）
ONIOM Method and its Applications. Chem. Rev. [Online early access]. DOI:
10.1021/cr5004419. Published Online: Apr 8, 2015.
2. 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.
3. 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.
4. 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.
5. Harris, T. V.; Szilagyi, R. K. Comparative Assessment of the Composition andCharge State of Nitrogenase FeMo-Cofactor. Inorg. Chem., 2011, 50 (11), 4811.
【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－ 30 －

Ⅱ 博士研究員 (2014)【氏名（ふりがな）】 伊勢川

美穂 （いせがわみほ）【職名】 Postdoctoral Fellow【所属】 Max Planck Institute for Chemical Energy Conversion, Department of Molecular
Theory and Spectroscopy【研究室】“Water Splitting”Group【直通電話】 +49 208-306-3588【電子メールアドレス】 miho.isegawa@cec.mpg.de【研究分野】 理論化学、計算化学【現在の研究課題】 (1) Modeling of blue copper protein for computation of EPR hyper fine coupling
tensors, (2) Construction of basis set for 3d-transition metal for highly accurate abinitio method, (3) Redox potentials of organic molecules and 3d-transition metal
complexes【研究内容キーワード】 ハイブリッド分子理論、化学反応機構、スペクトロスコピー、機能分子【学歴】 2009 年 9 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】 2009 年 9 月

京都大学理学博士【略歴】 2010 年 1 月
2013 年 3 月
2014 年 6 月

米国ミネソタ大学博士研究員 ,京都大学福井謙一記念研究センター研究員
独マックスプランク研究所化学エネルギー変換博士研究員【主な著書、学術論文】 1. Photochemical Ring Opening and Closing of Three Isomers of Diarylethene:（過去 5 年以内）
Spin-Flip Time Dependent Density Functional Study, M. Isegawa and K.
Morokuma, J. Phys. Chem. A. 119, 4191 (2015)
2. Complete active space second order perturbation theory (CASPT2) study of N(2D)+ H2O reaction paths on D1 and D0 potential energy surfaces: Direct and roaming
pathway, M. Isegawa, F. Liu, S. Maeda, K. Morokuma, J. Chem. Phys. 141, 154303(2014)
3. Ab initio reaction pathways for photodissociation and isomerization of nitromethane
on four singlet potential energy surfaces with three roaming paths, M. Isegawa, F.
Liu, S. Maeda, K. Morokuma, J. Chem. Phys. 140, 244310 (2014)
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).
5. Electrostatically Embedded Molecular Tailoring Approach and Validation for
Peptides, M. Isegawa, B. Wang, D. G. Truhlar, J.Chem. Theory Comput. 9, 1381
(2013)
6. Valence excitation energies of alkenes, carbonyl compounds, and azabenzenes
by time-dependent density functional theory: linear response of the ground statecompared to collinear and noncollinear spin-flip TDDFT with the Tamm-Dancoff ,approximation. M. Isegawa. D. G. Truhlar, J. Chem. Phys. 138, 134111 (2013).

－ 31 －

Ⅱ 博士研究員 (2014)【氏名】 W. M. C. Sameera【職名】 JSPS 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 catalysis, florescent probs.
【研究内容キーワード】 QM/MM and QM/QM methods, reaction mechanisms.
【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. W. M. C. Sameera, F. Maseras, “Quantum mechanics/molecular mechanics methods
can be more accurate than full quantum mechanics in system involving dispersion（過去 5 年以内）
correlations”, Phys. Chem. Chem. Phys., 2011, 13, 10520-10526.
2. 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.
3. 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. 2014, 136, 14, 5342-5350.
4. 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.
5. L. W. Chung, W. M. C. Sameera, R. Ramozzi, A. J. Page, M. Hatanaka, G. P.
Petrova, T. V. Harris, X. Li, Z. Ke, F. Liu, H-B. Li, L. Ding and K. Morokuma, , “TheONIOM Method and its Applications”, Chem. Rev. 2015, 115, 5678-5796.
【学術関係の受賞など】 JSPS postdoctoral fellowship, Japan. (2014)
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)－ 32 －

Ⅱ 博士研究員 (2014)【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 (The United Kingdom)【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, Piotr Raubo, “A Mechanistic Study of the Lewis Base
Directed Cycloaddition of 2-Pyrones and Alkynylboranes”, J. Am. Chem. Soc.
2014, 136, 8642-8653.
3. Julong Jiang, Jin-Quan Yu, Keiji Morokuma, “Mechanism and Stereoselectivityof Directed C(sp3)-H Activation and Arylation Catalyzed by Pd(II) with Pyridine
Ligand and TFA. A Computational Study”, ACS Catal. 2015, 5, 3648-3661.
4. Julong Jiang, Romain Ramozzi, Keiji Morokuma, “Rh(III)-Catalyzed C(sp 3)-H
Bond Activation via an External Base Metalation Deprotonation Mechanism: A
Theoretical Study”, Chem. Eur. J. Accepted.
5. Julong Jiang, Romain Ramozzi, Shin Moteki, Asuka Usui, Keiji Maruoka, Keiji
Morokuma, “The Mechanism of Metal-Free C-H Activation of Branched Aldehydes
and Acylation of Alkenes Using Hypervalent Iodine Compound: A Theoretical
Study”, J. Org. Chem. Submitted.
【学術関係の受賞など】 Faculty of Science Scholarship, University of Sheffield, 2010-2013－ 33 －

Ⅱ 博士研究員 (2014)【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（平成 27 年 3 月末まで）

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. “Substrate dependent reaction channels of the Wolff-Kishner reduction reaction: A
theoretical study”, Shinichi Yamabe, Guixiang Zeng, Wei Guan, Shigeyoshi Sakaki,（過去 5 年以内）
Beilstein Journal of Organic Chemistry 2014, 10, 259-270.
2. “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.
3. “Proton transfers in the Strecker reaction revealed by DFT calculations”, Shinichi
Yamabe, Guixiang Zeng, Wei Guan, Shigeyoshi Sakaki, Beilstein Journal of
Organic Chemistry 2014, 10, 1765-1774.
4. “A DFT Study on Proton Transfers in Hydrolysis Reactions of Phosphate Di-Anionand Sulfate Mono-Anion”, Shinichi Yamabe, Guixiang Zeng, Wei Guan, Shigeyoshi
Sakaki, Journal of Computational Chemistry, Volume 35, Issue 30, November 15,
2014, Pages: 2195-2204.
5. “Atmospheric pressure chemical ionization (APCI) of explosives using alternating
current corona discharge ion source”, D. T. Usmanov, L. C. Chen, Z. Yu, S.
Yamabe*, S. Sakaki and K. Hiraoka*, Journal of Mass Spectrometry (a cover story,
Wiley), vol. 50, No. 4, page 651-710 (2015)
6. “Study of structures, energies and vibrational frequencies of (O2)n+(n=2-5) clusters
by GGA and meta-GGA density functional methods”, Govinda P. Khanal, Rajendra
Parajuli, Elangannan Arunan, Shinichi Yamabe, Kenzo Hiraoka and Eiko Torikai,
Computational and Theoretical Chemistry (Elsevier), vol. 1056, page 24-36 (2015),
DOI information: 10.1016/j.comptc.2014.12.022
7. “Frontier orbitals and transition states in the oxidation and degradation of
L-ascorbic acid: a DFT study”, Shinichi Yamabe, Noriko Tsuchida, Shoko
Yamazaki and Shigeyoshi Sakaki, Org. Biomol. Chem., 2015, vol. 13, 4002-4015.
8. “Transition States of the 3MLCT to 3MC Conversion in Ru(bpy)2(phenderivative)2+ Complexes”, Naokazu Yoshikawa, Shinichi Yamabe, Shigeyoshi
Sakaki, Nobuko Kanehisa, Tsuyoshi Inoue,and Hiroshi Takashima, Journal of
Molecular Structure, vol.1094 (2015) 98-108. DOI: 10.1016/j.molstruc.2015.04.011
9. “A DFT study of hydride transfers to the carbonyl oxygen of DDQ”, Shinichi
Yamabe, Shoko Yamazaki and Shigeyoshi Sakaki, International Journal of
Quantum Chemistry, in press.
－ 34 －

Ⅱ 博士研究員 (2014)【氏名】 Yuh Hijikata【職名】 Designated Assistant Professor【所属】 Institute of Transformative Bio-Molecules【研究室】 Irle group【直通電話】 052-747-6452【電子メールアドレス】 hijikata@itbm.nagoya-u.ac.jp【研究分野】 Quantum Chemistry, Coordination Chemistry【現在の研究課題】 Proton conductivity【研究内容キーワード】 Coordination polymer【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】 Sep. 2014Designated Assistant Professor (Nagoya University)
Oct. 2011-Aug. 2014 FIFC 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－ 35 －

Ⅱ 博士研究員 (2014)【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
2015 年 4 月 京都大学 福井謙一記念研究センター フェロー（榊研）【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).
－ 36 －

Ⅱ 博士研究員 (2014)【氏名】 Guixiang Zeng （會桂 香）【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., 53,
6444-6457 (2014).
－ 37 －

Ⅱ 博士研究員 (2014)【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 3d transition metal complexes of ethylene and dinitrogen molecules:（過去 5 年以内）
similarities and differences in geometry, electronic structure, and spin multiplicity”
Phys. Chem. Chem. Phys. 17, 16294-16305(2015)
2. Masayuki Nakagaki and Shigeyoshi Sakaki “CASPT2 Study of Inverse SandwichType 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, 118, 1247-1257 (2014)
3. 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)－ 38 －

Ⅱ 博士研究員 (2014)【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 Metal-metal Multiple 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 ~ April 2015, Postdoctoral Fellow, Kyoto University
May, 2015, Postdoctoral Fellow, Hokkaido University【主な著書、学術論文】 1. Yue Chen, Juan Han, Wei-Hai Fang “Mechanism of Water Oxidation to Molecular
Oxygen with Osmocene as Photocatalyst: A Theoretical Study” Inorg. Chem., 51,（過去 5 年以内）
4938-4946 (2012)
2. 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).
3. Yue Chen, Shigeyoshi Sakaki The important role of the Mo-Mo quintuple bond in
catalytic synthesis of benzene from alkynes. A theoretical study. Dalton Trans. 43,
11478-11492 (2014)
4. Shubin Yang, Changlun Chen, Yue Chen, Jiaxing Li, Dongqi Wang, Xiangke
Wang “Competitive Adsorption of PbII, NiII, and SrII Ions on Graphene Oxides:
A Combined Experimental and Theoretical Study” ChemPlusChem 80(3), 480-484(2015)－ 39 －

Ⅱ 博士研究員 (2014)【氏名】 Sayyed Fareed Bhasha【職名】 Advanced Scientist【所属】 Momentive Performance Materials【研究室】 Opp.Infosys gate 3, Electronic city-1, Bengaluru, India【直通電話】 +91 80 49352278【電子メールアドレス】 bashasayyed@gmail.com【研究分野】 Computational Chemistry【現在の研究課題】 Catalysis, CO2 activation【研究内容キーワード】 QSAR/QSPR, Substituent Effect, CO2 activation, Ni-catalyst【学歴】 January 2008, Master of Science, University of Pune
September 2013, Doctor of Science, University of Kerala【学位】 Doctor of Science from University of Kerala【略歴】 Fukui Institute for Fundamental Chemistry (Feb 2013-July 2014)【主な著書、学術論文】 1. Sayyed, F. B.; Sakaki, S. “The Crucial Roles of MgCl2 as a Non-innocent Additivein the Ni-Catalyzed Carboxylation of Benzyl Halide with CO2”. Chem.Commun.
（過去 5 年以内）
2014, 50, 13026-13029.
2. Fujihara, T; Horimoto, Y; Mizoe, T; Sayyed, F. B; Tani, Y; Terao, J; Sakaki, S;
Tsuji, Y.“Nickel-Catalyzed Double Carboxylation of Alkynes Employing Carbon
Dioxide”. Org. Lett. 2014, 16, 4960-4963.
3. Guan, W.; Sayyed, F. B.; Zeng, G. and Sakaki, S. “σ-Bond Activation of Small
Molecules and Reactions Catalyzed by Transition-Metal Complexes: Theoretical
Understanding of Electronic Processes”. Inorg. Chem. 2014, 53, 6444-6457.
4. Sayyed, F. B.; Tsuji, Y.; Sakaki, S. “The Crucial Role of Ni(I) Intermediate in NiCatalyzed Direct Carboxylation of Aryl Chlorides with CO2: A Theoretical Study”.
Chem. Commun. 2013, 49, 10715-10717.
5. Suresh, C. H.; Sayyed, F. B. “Resonance Enhancement via Imidazole Substitution
Predicts New Cation Receptors”. J. Phys. Chem. A 2013, 117, 10455-10461.

－ 40 －

Ⅱ 博士研究員 (2014)【氏名（ふりがな）】 山田

健太 （やまだけんた）【職名】 特別研究員【所属】 国立研究開発法人 理化学研究所【研究室】 杉田理論分子科学研究室【電子メールアドレス】 kenta.yamada@riken.jp【ホームページ】 www.riken.jp/TMS2012/tms/ja/index.html【研究分野】 理論分子科学・計算化学【現在の研究課題】 膜タンパク質シミュレーションによる構造解析・機能解析【研究内容キーワード】 膜タンパク質、分子動力学シミュレーション、量子化学計算【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2015 年 4 月 理化学研究所 杉田理論分子科学研究室 特別研究員【所属学会】 日本化学会【主な著書、学術論文】 1. 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（過去 5 年以内）
Interatomic Electrostatic Interactions in QM/MM Simulations” J. Comput. Chem.
32, 3092-3104, 2011.
2. 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.
3. 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.
4. 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.
5. Yamada, K.; Kawashima, Y.; Tachikawa, M. “Accurate Prediction of Hyperfine
Coupling Constants in Muoniated and Hydrogenated Ethyl Radicals: Ab Initio
Path Integral Simulation Study with Density Functional Theory Method” J. Chem.
Theory. Comput. 2014, 10, 2005-2015.
6. Hiyama, M.; Noguchi, Y.; Akiyama, H.; Yamada, K.; Koga, N. “Vibronic Structuresin Absorption and Fluorescence Spectra of Firefly Oxyluciferin in Aqueous
Solutions” Photochem. Photobio. 2015, 91, 819-827.
【学術関係の受賞など】 横浜学術教育振興財団 平成24年研究費助成－ 41 －

Ⅱ 博士研究員 (2014)【氏名（ふりがな）】 Shuwei Tang
【職名】 SPR Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 303【直通電話】 075-711-7907【FAX】 075-781-4757【電子メールアドレス】 tangsw911@ gmail.com【研究分野】 Computational Quantum Chemistry【現在の研究課題】 Nickel catalyzed hydroarylation of linear olefin【研究内容キーワード】 Nickel, Lewis Acid, linear olefin, NHC【学歴】 June 2011, Faculty of Chemistry, Northeast Normal University, P.R. China【学位】 Ph.D. in Physical Chemistry【略歴】 July 2011-Present, Faculty of Chemistry, Northeast Normal University, Changchun,
P.R. China.
August 2014-Present, Postdoctoral Fellow, Kyoto University.
【所属学会】 Chinese Chemical Society Membership【主な著書、学術論文】 1. Li Y.; Zhang, J.; Yang, F.; Liang, J.; Sun, H.; Tang, S.W.; Wang R. Phys. Chem.
Chem. Phys. 2014, 16, 24604-24609.
（過去 5 年以内）
2. Wang, F. D.; Wang, F.; Zhang, N.; Li, Y.; Tang, S.W.; Sun, H.; Chang, Y.; Wang, R.
Chem. Phys. Lett. 2013, 555, 212-216.
3. Tang, S.W.; Wang, F.D.; Zhang, N.; Chang, Y.; Sun, H.; Zhang, J.; Xie, H.; Qiu, Y.;
Wang, R. Phys. Chem. Chem. Phys. 2012, 14, 16476-16485.
4. Tang, S.W.; Feng, J.; Qiu, Y.; Sun, H.; Wang, F.; Su, Z.; Chang, Y.; Wang, R. J.
Comput. Chem. 2011, 32, 658-667.
5. Tang, S.W.; Feng, J.; Qiu, Y.; Sun, H.; Wang, F.; Chang, Y.; Wang, R. J. Comput.
Chem.; 2010, 31, 2650-2657.

－ 42 －

Ⅱ 博士研究員 (2014)【氏名（ふりがな）】 Hong Zheng【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】 zhenghong@fukui.kyoto-u.ac.jp【研究分野】 Computational chemistry【現在の研究課題】 Theoretical Study of Cross-coupling Reaction between Pd(II)-X and Co(I)-R
Complexes【研究内容キーワード】 Transition state and electronic property of cross-coupling reaction【学歴】 December 2012, School of Science, Xi’an Jiaotong University【学位】 Doctor of Materials Physics and Chemistry, Xi’an Jiaotong University【略歴】 July 2014, Postdoctoral Fellow, Kyoto University【主な著書、学術論文】 1. H. Zheng, X. Zhao, T. Ren, W. W. Wang, C 74 Endohedral metallofullerenes
violating the isolated pentagon rule: A density functional theory study, Nanoscale, 4,（過去 5 年以内）
4530-4536 (2012)
2. H. Zheng, X. Zhao, W. W. Wang, T. Yang, S. Nagase, Sc2@C70 rather than Sc2C2@
C68: Density functional theory characterization of metallofullerene Sc2C70, J. Chem.
Phys., 137, 014308 (2012)
3. H. Zheng, J. Li, X. Zhao, Regioselective Chlorine-Addition Reaction toward C54Cl8
and Role of Chlorine Atoms in Stone-Wales Rearrangement, Dalton Trans, 41,
14281-14287 (2012)
4. H. Zheng, X. Zhao, W. W. Wang, J. S. Dang, S. Nagase, Quantum Chemical Insight
into Metallofullerenes M2C98: M2C2@C96 or M2@C98, Which Will Survive? J. Phys.
Chem. C, 117, 25195-25204 (2013)
5. H. Zheng, J. Zheng, L. He, X. Zhao, Unique Configuration of A Nitrogen-doped
Graphene Nanoribbon: Potential Applications to Semiconductor and Hydrogen Fuel
Cell, J. Phys. Chem. C, 118, 24723-24729 (2014)
6. H. Zheng, X. Zhao, L. He, W. W. Wang, S. Nagase, Quantum Chemical
Determination of Novel C82 Monometallofullerenes Involving a HeterogeneousGroup, Inorg. Chem., 53, 12911-12917 (2014)－ 43 －

Ⅱ 博士研究員 (2014)

４. 共同研究員プロフィール【氏名（ふりがな）】 Maneeporn Puripat【職名】 Visiting Researcher【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 213【直通電話】 075-711-7631【電子メールアドレス】 puripat@fukui.kyoto-u.ac.jp【研究分野】 Computational Chemistry【現在の研究課題】 Computational and Theoretical Chemistry, Simulation of Physics Phenomena,
Acoustics Physics【研究内容キーワード】 Conversion of cellulose to Green energy, Biginelli reaction and Acoustic Analysis of
Speech【学歴】 May 2011, B.Sc. in Physics, Faculty of Science, Chulalongkorn University, Thailand
March 2013, LL.B, Faculty of Law, Sukhothai Thammathirat Open University,
ThailandMay 2016 (Expected), Ph.D. in Nanoscience and Techology, Graduate School,
Chulalongkorn University, Thailand【学位】 Ph.D. student in Nanoscience and Technology program, Chulalongkorn University【学術関係の受賞など】 Development and Promotion of Science and Technology talents project (DPST)
2004-present－ 44 －

Ⅲ 研究広報活動 (2014)

Ⅲ

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
第 12 回京都大学福井謙一記念研究センターシンポジウム

─ 諸熊奎治先生傘寿記念 ─日時2015 年（平成 27 年）1 月 23 日（金）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

北川

進（京都大学 物質―細胞統合システム拠点 教授）「多孔性金属錯体の化学と応用」
10:15 − 11:15
田中肇（東京大学 生産技術研究所 教授）「水の局所構造化と熱力学異常・結晶化におけるその役割 」
11:30 − 12:30
諸熊奎治（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）「Chemical Theory of Complex Molecular Systems: Discovery andInsights from Computational Studies of Chemical Reactions」
14:00 − 15:00
―

休

憩

―

ポスターセッション

15:30 − 17:20

お祝いの会・懇親会（１F 多目的ルーム）

17:30 − 19:00－ 45 －

Ⅲ 研究広報活動 (2014)

２．センターセミナー
第 12 回福井センターセミナー
日時2014 年（平成 26 年）4 月 8 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 ～ 15:00

14:00 − 17:30

Yuichi MASUBUCHI (Kyoto Univ.)“Modeling and Simulations of Polymer Dynamics”

15:15 ～ 16:15

Atsushi Ikeda (FIFC)“Statistical Mechanics of the Glass Transition: Insightsfrom Mean-Field Situations”

16:30 ～ 17:30

Gernot FRENKING (Philipps-Univ. Marburg)“Main Group Complexes with Unusual Donor-Acceptor Bonds”

３．国際交流当センター教員が海外の研究機関を訪問し、研究所の運営に関して意見交換を行った。
（資料編 を参照）

４．社会へのアウトリーチ活動
高等学校などへの出張講義（1） 畑中美穂

特定研究員

兵庫県立北摂三田高等学校

2014 年（平成 26 年）10 月 2 日〃

2015 年（平成 27 年）1 月 15 日

（2） 榊

茂好

リサーチリーダー

京都府立南陽高等学校

2014 年（平成 26 年）11 月 6 日－ 46 －

Ⅲ 研究広報活動 (2014)（3） 諸熊奎治

シニアリサーチフェロー

畑中

美穂

他

特定研究員

京都大学アカデミックディ

2014 年（平成 26 年）9 月 28 日

メディアなどへの出演（1） 池田昌司

准教授

エフエム京都 Kyoto University Academic Talk 2014 年（平成 26 年）12 月 24 日

５．その他（報告）諸熊奎治シニアリサーチフェローについては、2014 年 10 月 21 ～ 22 日に日経産

業新聞「日本のイノベーター」欄でその研究活動などの紹介がされている。
（資料編 を参照）－ 47 －

Ⅳ 研究業績 (2014)

Ⅳ

研究業績

１．専任教員Atsushi Ikeda
Associate Professor

1. Summary of the research of the year (3-5 pages, includes appropriate figures and tables)
Thinning or thickening? Multiple rheological regimes in dense suspensions of soft particles
Understanding the shear rheology of dense
colloidal and granular suspensions remains a central
challenge at the crossroad between nonequilibrium
statistical mechanics and soft matter physics, with aclear technological relevance. Simple liquids display
simple rheological properties characterized by linear
Newtonian behavior. However, in dense particle
suspensions such as emulsions, colloidal assemblies, or
granular materials, the viscosity is usually not a single
number, but a nonlinear function of the applied flow rate.
To characterize these materials, an entire flow curve isthus needed. When the viscosity varies with the applied
shear rate, the system can either flow more easily as theshear rate increases (shear-thinning), or offer increasing
resistance to flow (shear-thickening).
In order to understand the origin of thisnonlinearity, we numerically study the rheology of asimple model of soft repulsive particles at large
densities, and show that nonlinear flow curves
reminiscent of experiments on real suspensions can beobtained (Fig 1). By using dimensional analysis andbasic elements of kinetic theory, we rationalize theseFig. 1 Flow curves obtained in two
experiments (a. Latex dispersion and b.
Oil-in-water

emulsion),

and

our

simulation (c).

multiple rheological regimes and disentangle the relative
impact of thermal fluctuations, glass and jamming transitions, inertia and particle softness on the flow curves.
We characterize more specifically the shear-thickening regime and show that both particle softness and theemergence of a yield stress at the jamming transition compete with the inertial effects responsible for theobserved thickening behaviour. This allows us to construct a dynamic state diagram, which can be used toanalyze experiments.

Diverging viscosity and soft granular rheology in non-Brownian suspensions－ 48 －

Ⅳ 研究業績 (2014)

The jamming transition is widely studied in dense disordered systems such as granular materials,
emulsions, and suspensions of large colloids. Below the jamming packing density, the system flows with afinite viscosity when an external force if applied. On approaching the jamming transition from below, theviscosity increases dramatically and the system eventually develops a solid like behavior with a finite yieldstress.
We use large scale computer simulations and finite
size scaling analysis to study the shear rheology of dense
three-dimensional

suspensionsoffrictionless

non-Brownian particles in the vicinity of the jamming
transition. We perform simulations of soft repulsive
particles at constant shear rate, constant pressure, andfinite system size, and study carefully the asymptotic
limits of large system sizes and infinitely hard particle
repulsion. Extending earlier analysis by about two ordersof magnitude, we first study the asymptotic behavior of theshear viscosity in the hard particle limit. We confirm its
asymptotic power law divergence at the jamming
transition, but show that a precise determination of theFig. 2 Divergence of the shear viscosity

critical density and critical exponent is difficult due to thenear the jamming transition is controlled`multiscaling'by two exponents.

behavioroftheviscosity

(Fig.

2).

Additionally, finite-size scaling analysis suggests that thisdivergence is accompanied by a growing correlation length scale, which also diverges algebraically. We thenstudy the effect of soft repulsion, and propose a natural extension of the standard granular rheology toaccount for softness effects, which we validate from simulations. Close to the jamming transition, this `soft
granular rheology' offers a detailed description of the non-linear rheology of soft particles, which differsfrom earlier empirical scaling forms.

Replica theory analysis of the glass transitions of Network-formers
When the crystallization is avoided, the dynamics of liquids slows drastically with decreasing
temperature, ending up with the formation of amorphous solids. This glass transition is a highly common
phenomenon. Many complicated systems present the glass transition and the associated slow dynamics,
everyday examples include window glass, various plastics, optical fibers, etc, which are formed through theglass transitions of molecular liquids, colloidal suspensions, polymeric liquids, and so on. In experimental
studies, the wide varieties of the systems have been studied, and their glass transitions are revealed to haverich phenomenologies. On the other hand in theoretical studies, in order to keep the analysis tractable, thesimplified models, such as hard spheres and Lennard-Jones particles, have been focused. An extreme
example is the hard spheres in infinite dimensions. Though never exist in reality, this system is the simplest
glass former and is playing a great role for the construction of the mean-field theory of the glass transition－ 49 －

Ⅳ 研究業績 (2014)

and the understanding of the universal feature of the glass transition.

We are attempting to bridge these

theoretical and experimental efforts, by applying or extending the microscopic mean-field theory of the glasstransition to more complicated systems. In particular we focus on the replica theory, which is the theory to
calculate the structures and thermodynamics of supercooled liquids and glasses through a replication ofsystems and liquid state theory calculations of the replicated systems.
In this work, we especially focus on the problem of fragility. Experiments have showed that theincrease of the viscosity is strongly dependent on the nature of liquids. The liquids which show a steeper
increase of the viscosity are called ``fragile'', and the others ``strong''. Experimentally liquids tend to become``strong'' when the molecules tend to form a network structure in their liquid states, however the theoreticallevel of understanding on this tendency is stilllacking. This is the fragility problem. We apply
the replica theory (small cage expansion with thehyper-netted chain theory) to the standard binary
mixture of Lennard-Jones particles (KALJ),
which is a typical fragile glass former, and thesimple network-forming fluid model (NTW) thatwas introduced by Coslovich and Pastore. The
theory is found to predict that the temperaturedependence of the configurational entropy of
NTW is much milder than that of usual
Lennard-Jones particles (Fig. 3). This result with

Fig. 3 Configurational entropy of NTW model andAdam-Gibbs argument on the relaxation time

KALJ model calculated by the replica theory.

explain well the difference between strong andfragile liquids.

Correlation of Local Order with Particle Mobility in Supercooled Liquids is Highly System
Dependent
Supercooled liquids display markedly heterogeneous dynamics, despite possessing structuralproperties that appear nearly unchanged from those of normal liquids from which they are prepared.
Simulations of model supercooled liquids are useful for understanding the connections between structure anddynamics because particle locations may be followed precisely for all times. Recently, focus has turned tothe study of specific structural motifs and their putative connection with the dynamics of supercooled liquids.
The notion that the frustration of local order incommensurate with bulk crystalline periodicity may be related
to glass formation is an old one. New evidence for the growth of domains associated with local packing
motifs has been presented for several simple and realistic model systems, where particles tend to be found incertain "locally preferred structures" (LPS) with increased supercooling. As a general rule, more fragile
systems display a more rapid increase in LPS concentration and domain extent.

－ 50 －

Ⅳ 研究業績 (2014)

In this study, we use extensive numerical simulation to investigate the connection between local
structure and dynamical heterogeneity in supercooled liquids. Through the study of four different models weshow that the correlation between a particle's mobility and the degree of local order in nearby regions ishighly system dependent (Fig. 4). Our results suggest that the correlation between local structure anddynamics is weak or absent in systems that conform well to the mean-field picture of glassy dynamics andstrong in those that deviate from this paradigm. Finally, we investigate the role of order-agnostic point-to-set
correlations and reveal that they provide similar information content to local structure measures, at least in
the system where local order is most pronounced.

Fig. 4 Time dependence of the correlation between the dynamics and local structural motif.

2. Original papers(1) Takeshi Kawasaki, Daniele Coslovich, Atsushi Ikeda and Ludovic Berthier“Diverging viscosity and soft granular rheology in non-Brownian suspensions”
Phys. Rev. E 91, 012203 (2015). (This article was selected as “Editors' Suggestion”)(2) Glen M. Hocky, Daniele Coslovich, Atsushi Ikeda and David R. Reichman“Correlation of Local Order with Particle Mobility in Supercooled Liquids is Highly
System Dependent”
Phys. Rev. Lett. 113, 157801 (2014). [arXiv:1402.6709](3) Takeshi Kawasaki, Atsushi Ikeda and Ludovic Berthier“Thinning or thickening? Multiple rheological regimes in dense suspensions of soft
particles”
EPL 107, 28009 (2014).
3. Presentation at academic conferences(1) Atsushi Ikeda－ 51 －

Ⅳ 研究業績 (2014)“Disentangling glass and jamming physics: a rheological study”
Gordon Research Conference on Granular and Granular Fluid Flows, Massachusetts (USA),
July 20-25, 2014. (Invited)(2) 池田昌司「ガラス転移とジャミング転移の統一的研究：力学物性とレオロジー」
第 4 回ソフトマター研究会、名古屋、2015 年 1 月 6 日-8 日(招待講演)(3) Atsushi Ikeda“A replica theory study of the glass and jamming transitions of hard ellipsoids”
日本物理学会第70回年次大会、東京、2015年3月21日-24日(4) Harukuni Ikeda, Atsushi Ikeda“Correlation length for the high dimensional hard sphere model near the glass and jamming
transition point”
日本物理学会第70回年次大会、東京、2015年3月21日-24日(5) Misaki Ozawa, Walter Kob, Atsushi Ikeda, Kunimasa Miyazaki“Numerical Study of Ideal Glass Transition by Random Pinning”
日本物理学会第70回年次大会、東京、2015年3月21日-24日(6) 枡井 基典, 佐藤 啓文, 池田 昌司「ガラス転移における構造とフラジリティの関係：レプリカ理論によるアプロー
チ」
日本物理学会第70回年次大会、東京、2015年3月21日-24日(7) 池田 晴國, 池田 昌司「高次元剛体球のガラス・ジャミング転移における相関長」
第四回ソフトマター研究会、名古屋、2015年1月6日-8日(8) 枡井 基典, 佐藤 啓文, 池田 昌司「ガラス転移における構造とフラジリティの関係：レプリカ理論によるアプロー
チ」
第四回ソフトマター研究会、名古屋、2015年1月6日-8日(9) 池田 昌司, Ludovic Berthier「ランダム最密充填近傍での静的構造と振動」
日本物理学会2014年秋季大会、春日井、2014年9月7日-10日
4. Others(1) Atsushi Ikeda“Statistical mechanics of the glass transition: Insights from mean-field situations”
The 12th Fukui Center Seminar, Kyoto, 2014/4/8.
(2) 池田昌司「高密度分散系のレオロジー：ガラス転移とジャミング転移とその間」
関西レオロジー研究会第66回例会, 京都, 2014年6月16日－ 52 －

Ⅳ 研究業績 (2014)(3) 池田昌司「粒子のランダム最密充填における臨界性」
8th Mini-Symposium on Liquids, 岡山, 2014年7月5日(4) 池田昌司「高密度分散系のレオロジー：ガラス転移とジャミング転移」
計算粉体力学研究会, 京都, 2014年12月2日－ 53 －

Ⅳ 研究業績 (2014)

２．シニアリサーチフェロー

Shigeru
NagaseShigeru
NagaseSeniorResearch
Fellow
FIFC
SeniorResearch
Fellowof of
FIFC
1. Summary of the Research of the Year(a) Widely Believed Metallofullerene Sc2@C66 Revised
Fullerenes consists of pentagonal and hexagonal carbon rings, and have closed cage structures.
The isolated pentagon rule (IPR) has been established in fullerenes chemistry, which states that there
is no adjacent pentagon for stable fullerenes. The first example of IPR-violation was reported for
endohedral metallofullerene Sc2@C66. The 13C NMR spectrum showed that Sc2@C66 has C2v
symmetry. It was determined fromMEM

(maximummethod)/Rietveld

entropy

analysisthat

two Sc atoms were encaged as adimmer inside the C2v isomer(coded

#4348

in

the

spiralalgorithm) of C66.
However, we pointed out that
the C2v structure of Sc2@C66(#4348) shown in Fig. 1 does not correspond to an energy minimum; it has two imaginary frequencies
that destroy C2v symmetry. This is explained by the fact that the two Sc atoms located in a narrow
space on the upper side of the C66 cage undergo large electrostatic repulsion between the positively
charged Sc atoms. Therefore, the two Sc atoms move down toward the central area of the C66 cagewith a larger space, and then the Sc-Sc unit rotates in the way that each Sc atom points to the top andbottom of the C66 cage, so that the electrostatic repulsion between the positively charged Sc atoms is
most reduced because of the increasein the Sc-Sc distance. The resultant C1
structure becomes 62 kcal mol-1 morestablethandetermined

the
from

C2v

structure

MEM/Rietveld

analysis. However, the C1 structure
does not fit the observed 13C NMR
spectrum.
Among the 4,478 isomers of C66, 8 isomers have C2v symmetry.
Detailed calculations revealed that encapsulation of two Sc atoms
inside the C2v isomer coded #4059 are the most favorable. The C2v
structure of Sc2@C66 (#4059) with a larger separation of two Sc atoms,
which is shown in Fig. 2, is 95 kcal mol-1 more stable than that of－ 54 －

Ⅳ 研究業績 (2014)

Sc2@C66 (#4348) determined by MEM/Rietveld analysis. It is noteworthy that the discrepancy
between theoretical calculations and MEM/Rietveld analysis has been dissolved by 2D NMR
spectroscopic and single-crystal X-ray structure analyses showing that the theoretically predicted
Sc2@C66 (#4059) is correct, while the widely believed Sc2@C66 (#4348) is wrong. It is interesting thatthe carbon cage of Sc2@C66 (#4059) has two pairs of three adjacent pentagons, this fusion of threepentagons being the first example in the chemistry of endohedral metallofullerenes. As well known,
fused pentagons are antiaromatic. However, they become aromatic by accepting electrons from the Sc
atom coordinated to the fused pentagons, as indicated by the negative NICS (nuclear-independentchemical shift) values shown in Fig. 3.

(b) Structural Prediction of Endohedral Metallofullerenes
The smallest sulfide clusterfullerene Sc2S@C68 has been detected by mass spectrometry.
However, it has been determined yet what is the endoheral structure of Sc2S@C68. Therefore, density
functional theory (DFT) calculations were performed for a large number of possible isomers of C68. It
is found that the Sc2S cluster is encapsulated inside the IPR-violating C2v-C68 (#6078) isomer of C68
that has two pairs of fused pentagons, each Sc atom being coordinated to the fussed pentagons with an
obtuse Sc–S–Sc angle of 151°. The 13C NMR, UV-vis-NIR, and IR spectra of Sc2S@C2v-C68 (#6078)
are calculated, which are useful for future experimental characterization. DFT calculations were also
performed for Sc2S@C76, because its structure has not been experimentally determined. It is foundthat the Sc2S cluster is encapsulated inside the IPR-satisfying Td-C76 (#19151) isomer of C76. In
addition, it is suggested that the Sc2S cluster can be encapsulated also inside the IPR-violating isomersof C76 at high temperatures. The 13C NMR, UV-vis-NIR, and IR spectra are calculated to confirm thestructures of Sc2S@C76 in future experimental characterization.
For the Gd2C94 species, it is an interesting subject which is abundantly produced,
dimetallofullerene Gd2@C94 or carbide
clusterfullerene
energyGd2C2@C92.

calculations

show

DFT
that

Gd2@C2-C94 (#153480) is the moststable. However, relative concentrations(mole fractions) calculated via freeenergies as a function of temperatures
reveal that Gd2C2@D3-C92 (#126408) is
the most abundant, and Gd2C2@C1-C92(#126390) and Gd2C2@C2-C92(#126387)
are the second and third most abundant,
respectively, for the temperatures atwhich endohedral metallofullerenes are
generally produced, as shown in Fig. 4.
This suggests that dimetallofullerenes－ 55 －

Ⅳ 研究業績 (2014)(encapsulation of two pure metals) are much less abundantly produced than carbide cluster fullerenes.
In this context, it is interesting that Gd2C2@D3-C92 (#126408) has been characterized experimentallyas the example of the largest carbide clusterfullerene.

(c) Reactions of Endohedral Metallofullerenes
The DFT calculations were performed for the Diels–Alder reactions of the IPR-violating C68 andthe corresponding Sc3N@C68 to investigate the effects of endohedrtal doping on the reactivities. For
the empty C68, the addition of dienes to the [5,6] bond is kinetically favorable, while the addition to
the [5,5] bond is thermodynamically favorable. Upon encapsulation of the Sc3N cluster, the addition
to the [5,5] bond becomes favorable both kinetically and thermodynamically, though the reactivities
are considerably reduced because of electron transfer from Sc3N to C68. It is found that the bonds
around the adjacent pentagons are most reactive. This suggests that adjacent pentagons play animportant role in the reactivities.
Synthesizing unprecedented diamagnetic adducts of an endohedral metallofullerene wasachieved by using 1,3-dipolar cycloaddition
reaction of paramagnetic La@Cs-C82 with asimultaneoushydrogenaddition.

The

selective formation of two main products,
La@Cs-C82HCMe2NMeCHPh (2a and 2b),
was first detected by HPLC analysis and
MALDI-TOF mass spectrometry, as shownin Fig. 5. 2a and 2b-O, which was readily
formed by the oxidation of 2b, were isolated
by multistep HPLC separation and were fully characterized by spectroscopic methods, including
1D-NMR, 2D-NMR, and UV−vis-NIR measurements and electrochemistry. The hydrogen atom wasfound to be connected to the fullerene cage directly in the case of 2a, and the redox behavior indicatedthat the C−H bond can still be readily oxidized. The reaction mechanism as well as the structures of
2a and 2b were well disclosed by the close interplay between experimental observations and DFT
calculations. The feasible order of the reaction process would involve a 1,3-dipolar cycloaddition
followed by the hydrogen addition through a radical pathway. It was concluded that the characteristic
electronic properties and structure of La@Cs-C82 result in a site-selective reaction, which afford aunique chemical derivative of an endohedral metallofullerene in high yields. Derivative 2a constitutes
the first endohedral metallofullerene where the direct linking of a hydrogen atom has been structurally
proven.

(d) Interesting Bonds Provided by Heavier Main Group Elements
Recent insightful reports have proposed that carbodiphosphoranes should be classified as a newclass of carbone rather than a heteroallene. Carbones consist of two ligands (L) coordinated to its
central zero-valent carbon atom, which maintains its four valence electrons as two orthogonal lone

－ 56 －

Ⅳ 研究業績 (2014)

pairs, and therefore, is also described carbon complex of the general type LCL. Electronic effects
on the central carbon atom of carbone, generated by the replacement of the SIV ligand ofcarbodisulfane (CDS) withotherchalcogenligands(Ph2E, E = S or Se), were
investigated.
shows,

As

the

Fig.

6

carbones

Ph2ECSPh2(NMe) (E =S (a) or Se (b)) weresynthesized

from

the

corresponding salts, and their electronic properties as well as structures were characterized by DFT
calculations. The carbone b is the first carbone containing selenium as the coordinated atom. DFT
calculations revealed the electronic structures of carbones a and b, which have two lone pairs ofelectrons at the carbon center. The trend in HOMO energy levels, also estimated by cyclic
voltammetry measurements as well as DET calculations, for the carbones and CDS follows the orderof b > a > CDS. Analysis of a doubly protonated dication and trication complex revealed that thecentral carbon atom of b behaves as a four-electron donor.
The linkage of hypercoordinated atoms is of considerable interest in the chemistry of group 14
elements. As Fig. 7 shows, the first dianioniccompounds

bearingabond

betweentwo

pentacoordinated Ge atoms have been synthesized
in a stable form. X-ray crystallographic analysis as
well as DFT calculations indicated that the two
pentacoordinated Ge atoms are linked by a clear
single bond. The dianionic compounds arereversibly converted to the anionic and neutral
Ge−Ge bonded compounds while maintaining thecoordination number of the germanium atoms. Theinterconversion features changes in electronic properties and structures around the germanium atoms.
These new structures composed of such Ge-Ge bonds will be useful for the construction of functional
materials that respond to acid-base reactions.

(e) Other Research Subjects(1) "Enhancement of Stannylene Character in Stannole Dianion Equivalents Evidenced by NMR
and Mössbauer Spectroscopy and Theoretical Studies of Newly Synthesized Silyl-Substituted
Dilithiostannoles", (2) "Photochemical Behavior of Single-Walled Carbon Nanotubes in the Presenceof Propylamine", (3) "Regioselective Benzyl Radical Addition to an Open-Shell Cluster
Metallofullerene. Crystallographic Studies of Cocrystallized Sc3C2@Ih-C80 and Its Singly Bonded
Derivative", (4) "Regioselective Synthesis and Molecular Structure of the First Derivative of－ 57 －

Ⅳ 研究業績 (2014)

Praseodymium-Containing

Metallofullerenes",(5)"Isolation

andCharacterizationof[5,6]-Pyrrolidino-Sc3N@Ih-C80 Diastereomers", (6) "Synthesis, Structures, and Electronic Properties
of Triple- and Double-Decker Ruthenocenes Incorporated by a Group 14 Metallole Dianion Ligand",(7) "Magnetic Alignments of Endohedral Metallofullerene Nanorods under Magnetic Fields", (8)"Partial

ChargeTransferintheShortest

Possible

Metallofullerene

Peapod,La@C82[11]Cycloparaphenylene", (9) "Quantum Chemical Determination of Novel C82
Monometallofullerenes Involving a Heterogeneous Group", (10) "Hiding and Recovering Electrons in
a Dimetallic Endohedral Fullerene: Air-Stable Products from Radical Additions",(11)"Regioselective Cage Opening of La2@D2(10611)-C72 with 5,6-Diphenyl-3-(2-pyridyl)-1,2,4-triazine",and (12) "Water-Dimer Stability and Its Fullerene Encapsulations".

2. Original papers(1) 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).
(2) Y. –J. Guo, T. Yang, S. Nagase, X. Zhao, "Carbide Clusterfullerene Gd2C2@C92 vs
Dimetallofullerene Gd2@C94: A Quantum Chemistry Survey", Inorg. Chem., 53, 2012-2021(2014).
(3) M. Yamada, H. Kurihara, M. Suzuki, J. –D. Guo, M. Waelchli, M. M. Olmstead, A. L. Balch, S.
Nagase, Y. Maeda, T. Hasegawa, X. Lu, and T. Akasaka, "Sc2@C66 Revised: An Endohedral
Fullerene with Scandium Ions Nestled within Two Unsaturated Linear Triquinanes", J. Am.
Chem. Soc., 136, 7611-7614 (2014).
(4) T. Kuwabara, J. –D. Guo, S. Nagase, M. Minoura, R. H. Herber, and M. Saito, "Enhancementof Stannylene Character in Stannole Dianion Equivalents Evidenced by NMR and Mössbauer
Spectroscopy

andTheoretical

Studiesof

Newly

Synthesized

Silyl-Substituted

Dilithiostannoles", Organometallics, 33, 2910-2913 (2014).
(5) Y. Maeda, Y. Hasuike, K. Ohkubo, A. Tashiro, S. Kaneko, M. Kikuta, M. Yamada, T.
Hasegawa, T. Akasaka, J. Zhou, J. Lu, S. Nagase, and S. Fukuzumi, "Photochemical Behaviorof Single-Walled Carbon Nanotubes in the Presence of Propylamine", ChemPhysChem, 15,
1821-1826 (2014).
(6) Y. -J. Guo, B. – C. Gao, T. Yang, S. Nagase, and X. Zhao, "Sc2S@C68: An Obtuse
Di-Scandium Sulfide Cluster Trapped in a C2v Fullerene Cage", Phys. Chem. Chem. Phys, 16,
15994-16002 (2014).
(7) P. Zhao, T. Yang, Y. –J. Guo, J. –S. Dang, X. Zhao, and S. Nagase, "Dimetallic Sulfide
Endohedral Metallofullerene Sc2S@C76: Density Functional Theory Characterization", J.
Comput. Chem., 35, 1657-1663 (2014).
(8) H. Fang, H. Cong, M. Suzuki, L. Bao, B. Yu, Y. Xie, N. Mizorogi, M. M. Olmstead, A. L.
Balch, S. Nagase, T. Akasaka, and X. Lu, "Regioselective Benzyl Radical Addition to an－ 58 －

Ⅳ 研究業績 (2014)

Open-Shell Cluster Metallofullerene. Crystallographic Studies of Cocrystallized Sc3C2@Ih-C80
and Its Singly Bonded Derivative", J. Am. Chem. Soc., 136, 10534-10540 (2014).
(9) Q. Zhou, H. Li, Y. Lian, M. Suzuki, L. Bao, W. Cai, W. –W. Wang, S. Nagase, X. Lu, and T.
Akasaka, "Regioselective Synthesis and Molecular Structure of the First Derivative ofPraseodymium-Containing Metallofullerenes", Chem. Commun., 50, 9876-9878 (2014).
(10) T. Yang, X. Zhao, S. Nagase, and T. Akasaka, "Diels-Alder Reaction on Free C68 Fullerene andEndohedral Sc3N@C68 Fullerene Violating the Isolated Pentagon Rule: Importance ofPentagon Adjacency", Chem. Asian J., 9, 2604-2611 (2014).
(11) T. Morosaki, T. Suzuki, W. –W. Wang, S. Nagase, and T. Fujii, "Syntheses, Structures, andReactivities of Two Chalcogen-Stabilized Carbones", Angew. Chem. Int. Ed., 53, 9569-9571(2014).
(12) Y. Maeda, M. Kimura, C. Ueda, M. Yamada, T. Kikuchi, M. Suzuki, W. –W. Wang, N.
Mizorogi, N. Karousis, N. Tagmatarchis, T. Hasegawa, M. M. Olmstead, A. L. Balch, S.
Nagase, and T. Akasaka, "Isolation and Characterization of [5,6]-Pyrrolidino-Sc3N@Ih-C80
Diastereomers", Chem. Commun., 50, 12552-12555 (2014).
(13) T. Kuwabara, J. –D. Guo, S. Nagase, T. Sasamori, N. Tokitoh, and M. Saito, "Synthesis,
Structures, and Electronic Properties of Triple- and Double-Decker Ruthenocenes Incorporated
by a Group 14 Metallole Dianion Ligand", J. Am. Chem. Soc., 136, 13059-13064 (2014).
(14) M. O. Ishitsuka, H. Nikawa, N. Mizorogi, F. Kimura, T. Kimura, T. Kato, S. Nagase, and T.
Akasaka, "Magnetic Alignments of Endohedral Metallofullerene Nanorods under Magnetic
Fields", Fullerenes, Nanotubes, Carbon Nanostruct., 23, 35-39 (2014).
(15) T. Iwamoto, Z. Slanina, N. Mizorogi, J. –D. Guo, T. Akasaka, S. Nagase, H. Takaya, N. Yasuda,
T. Kato, and S. Yamagao, "Partial Charge Transfer in the Shortest Possible Metallofullerene
Peapod, La@C82[11]Cycloparaphenylene", Chem. Eur. J., 20, 14403-14409 (2014).
(16) X. Lu, L. Bao, T. Akasaka, and S. Nagase, "Recent Progress in the Chemistry of Endohedral
Metallofullerenes", Chem. Commun. (Feature Article), 50, 14701-14715 (2014).
(17) Y. Takano, Z. Slanina, J. Mateos, T. Tsuchiya, H. Kurihara, F. Uhlik, M. A. Herranz, N.
Mart ín, S. Nagase, and T. Akasaka, "Unprecedented Chemical Reactivity of a Paramagnetic
Endohedral Metallofullerene La@Cs-C82 that Leads Hydrogen Addition in the 1,3-Dipolar
Cycloaddition Reaction", J. Am. Chem. Soc., 136, 17537-17546 (2014).
(18) H. Zheng, X. Zhao, L. He, W. –W. Wang, and S. Nagase, "Quantum Chemical Determination ofNovel C82 Monometallofullerenes Involving a Heterogeneous Group", Inorg. Chem., 53,
12911-12917 (2014).
(19) N. Kano, S. Tsukada, Y. Shibata, T. Kawashima, H. Sato, J. –D. Guo, and S. Nagase,"Interconversion among Dianionic, Anionic, and Neutral Compounds Bearing a Bond between
Two Pentacoordinated Germanium Atoms", Organometallics, 34, 56-62 (2015).
(20) M. Yamada, H. Kurihara, M. Suzuki, M. Saito, Z. Slanina, F. Uhlik, T. Aizawa, T. Kato, M. M.
Olmstead, A. L. Balch, Y. Maeda, S. Nagase, X. Lu, and T. Akasaka, "Hiding and Recovering－ 59 －

Ⅳ 研究業績 (2014)

Electrons in a Dimetallic Endohedral Fullerene: Air-Stable Products from Radical Additions", J.
Am. Chem. Soc., 137, 232-238 (2015).
(21) M. Yamada, Y. Muto, H. Kurihara, Z. Slanina, M. Suzuki, Y. Maeda, Y. Rubin, M. M. Olmstead,
A. L. Balch, S. Nagase, X. Lu, and T. Akasaka, "Regioselective Cage Opening of
La2@D2(10611)-C72 with 5,6-Diphenyl-3-(2-pyridyl)-1,2,4-triazine", Angew. Chem. Int. Ed., 54,
2232-2235 (2015).
(22) F. Uhlík, Z. Slanina, S.-L. Lee, B. Wang, L. Adamowicz, and S. Nagase, "Water-Dimer Stability
and Its Fullerene Encapsulations", J. Comput. Theor. Nanosci., 12, 959-964 (2015).

3. Review articles(1) 山田道夫、赤阪健、永瀬茂、「新しいフラーレン構造の発見—実験と理論のインタープレイ」、化学、69, 70-71 (2014).
(2) 前田 優、赤阪健、永瀬茂、「金属内包フラーレン研究の進展」、現代化学、2, 48-53(2015).

4. Books(1) 土屋敬広、溝呂木直美、永瀬 茂、赤阪 健、「 空間に閉じ込められた物質系の創製と機能」、赤阪 健、大須賀篤弘、福住俊一、神取秀樹 監修「高次π空間の創発と機能開発」、シーエムシー出版、pp. 5-9 (2013).
(2) M. Yamada, X. Lu, L. Feng, S. Sato, Y. Takano, S. Nagase, and T. Akasaka, "Fundamental andApplied Aspects of Endohedral Metallofullerenes as Promissing Carbon Nanomaterials", In
Organic Nanomaterials: Synthesis, Characterization, and Device Applications (Eds. T. Torres
and G. Bottari), John Wiley & Sons, Chapter 12, pp. 241-258 (2013).
(3) X. Ku, L. Echegoyen, A. L. Balch, S. Nagase, and T. Akasaka, Eds., Endohedral
Metallofullerenes: Basics and Applications, CRC Press, Taylor&Francis Group, New York(2015).

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Ⅳ 研究業績 (2014)

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. In 2013 and 2014
many veteran postdocs left FIFC to take up faculty positions in their respective countries. Dr. Miho Hatanaka,
Fukui Fellow for the last four years, became Assistant Professor at Kinki University in Osaka as of April 1, 2015.
Several new postdocs joined our group in 2014, and we had a total of 8 postdoctoral fellows (2 Fukui Fellows, 2
JSPS Postdoctoral Fellows and regular postdocs supported mainly by Kakenhi (grants from the Minister of
Education, Culture, Sports, Science and Technology)). One Visiting Foreign Researcher (PhD student fromThailand) spent a year in the group working on her thesis. In addition, three Visiting Foreign Researchers (onAssociate Professor on Sabbatical from US, and one Lecturer from Vietnam and two graduate students from US
and Spain stayed in the group. Since detailed description on individual projects at FIFC can be found in thereports of postdoctoral fellows, here only the areas of studies and titles of individual projects are summarized.
I.
Method Development
A. The ONIOM Method and Its Application
The ONIOM method, developed by Morokuma and collaborators since 1995, is a very powerful and robust
hybrid method, in which a molecule is divided into two or more parts and different levels of theoretical methods
are applied to different parts of the molecule, enabling calculation of large molecular systems with reasonableaccuracy and cost. More than 100 scientific papers that refer to the ONIOM method have been published every
year. Although some reviews of the method itself were published in the past, there were no comprehensive
reviews of both recent developments and variations of the method and its applications have not been published.
This was in part because applications cover very wide areas of chemistry, from organic, inorganic, catalysis tomaterials, solution, nano and bio. Some former and present members of the Morokuma group at FIFC decided toundertake such a review. It took over a year and resulted in a Chem. Rev. article with 13 authors and 119 printed
pages, entitled “The ONOIM Method and its Applications”. Chem. Rev. 115, 5678–5796 (2015).
B. Development of the GRRM Strategy
In the last several years, in collaboration with Profs. Koichi Ohno and Satoshi Maeda, we have developed the
Global Reaction Route Mapping (GRRM) strategy, combining the two methods of automatic potential energy
search, the ADDF (adiabatic downward distortion following) method and the AFIR (artificial force-induced
reaction (AFIR) method. These methods allow determination of important reaction pathways, includingintermediates and transition states as well as minimum energy conical intersections and seam of crossing, ofcomplex reaction systems without any guess or prejudice. The strategy can be applied to complex molecularsystems by also combining with micro-iteration techniques. The GRRM strategy has been actively applied tohomogenous catalysis systems such as transition metal catalysts and metal-free organocatalysts. The GRRM
strategy has also been particularly powerful in finding reaction pathways of photo-activated molecules, in which1－ 61 －

Ⅳ 研究業績 (2014)

multiple pathways involving various electronically excited states and crossings can efficiently be located. The
GRRM14 program has been released to public in October 2014 and is available throughhttp://grrm.chem.tohoku.ac.jp/GRRM/index_e.html.
a. Anharmonic Downward Distortion Following for Automated Exploration of Quantum Chemical Potential
Energy Surfaces. (See Original Paper #9).
b. Intrinsic Reaction Coordinate: Calculation, Bifurcation, and Automated Search. (See Original Paper #8).
c. Systematic Exploration of Minimum Energy Conical Intersection Structures near the Franck-Condon Region.
(See Original Paper #7).
d. From Roaming Atoms to Hopping Surfaces: Mapping out Global Reaction Routes in Photochemistry. (See J.
Am. Chem. Soc. 137, 3433–3445 (2015).)
II. Theoretical Studies of Reactions of Complex Molecular 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 catalysis, 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 to find reaction pathways.
GRRM turned out to be a very powerful tool for finding many important transition states and intermediates ofcomplex multistep multipathway reactions. In some stereochemistry-determining steps of asymmetric catalytic
reactions, sometimes more than 100 different pathways exist and the GRRM strategy allowed to properly sample
all these. GRRM studies have shown that some organic multicomponent reactions, such as Passerini, Biginelli
and Ugi reactions, are in fact organocatalytic reactions in which some component acts as catalyst in more than
one step of multistep reactions.
A. The Mechanism of Metal-Free C-H Activation of Branched Aldehydes and Acylation of Alkenes Using
Hypervalent Iodine Compound: A Theoretical Study (See research activities of J. Jiang)
B. The Biginelli reaction is a urea-catalyzed organocatalytic multicomponent reaction (see research activities ofM. Puripat)
C. R. Ramozzi, K. Morokuma, Revisiting the Passerini reaction mechanism: existence of the nitrilium,organocatalysis of its formation and solvent effect. (See research activities of R. Ramozzi)
D. Hydroboration Mechanism Revisited: Alkene Addition Partner Depends on Ligand and Substrate. (Seeresearch activities of T. Harris)
E. Theoretical investigation on the Pd-catalyzed C(sp3)-H activation in the synthesis of unnatural amino acids.
(See research activities of J. Jiang)
F. Rh(III)-Catalyzed C(sp3)-H Bond Activation via an External Base Metalation Deprotonation Mechanism: A
Theoretical Study. (See research activities of J. Jiang)
G. Mukaiyama aldol reactions catalyzed by a chiral Fe(II) complex (See research activities of W. M. C. Sameera)
H. Pd-catalysed borylation of 2-arylaziridines See research activities of W. M. C. Sameera)
I. G. P. Petrova, H.-B. Li, K. Maruoka and K. Morokuma, Asymmetric phase-transfer catalysis with homo- andheterochiral quaternary ammonium salts: a theoretical study (See Original Paper #13)
J. The origin of enantioselectivity for intramolecular Friedel-Crafts reaction catalyzed by the supramolecular Cu /DNA catalyst complex (See Original Paper #14)
K. A Theoretical Study on the UVR8 Photoreceptor: Sensing Ultraviolet-B by Tryptophan and Dissociation of
Homodimer. (See Original Paper #10).
III. Simulation of Nanomaterials
In the area of simulation of nanomaterials, we continued our research efforts on quantum chemical molecular2－ 62 －

Ⅳ 研究業績 (2014)

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 nanotubes(SWCNTs) and graphenes, for which the growth mechanism is still poorly understood. The chirality control in the
CNT growth is one of the most important pending issues. The nucleation and growth of graphenes on transition
metal surfaces have been studied using a variety of model systems. The research activity in this area is slowed
down, as we feel that we have accomplished what we can hope for using the present methodology and techniques.
A. Graphene Nucleation from Amorphous Nickel Carbides: QM/MD Studies on the Role of Subsurface Carbon
Density. (See Original Paper #16)
B. Graphene Nucleation on a Surface-Molten Copper Catalyst: Quantum Chemical Molecular Dynamics
Simulations. (See Original Paper #12)
C. Nearly Exclusive Growth of Small Diameter Semiconducting Single-Wall Carbon Nanotubes from Organic
Chemistry Synthetic End-Cap Molecules. (See Original Paper #3)
D. Insights into Carbon Nanotube and Graphene Formation Mechanisms from Molecular Simulations. (See
Review Article #2)
IV. Theoretical Studies of Photofunctional Molecular Systems
The functionality of photofunctional molecules, such as fluorescence probes, photoswitches andphotosensitizers, is often controlled by the energy and geometry of minimum energy conical intersections(MECIs) between the ground S0 and the first excited S1 electronic states. If an MECI can be reached easily fromthe Franck-Condon (FC) state of the first excited state, the excited molecule makes nonadiabatic transition from
S1 to S0 through this MECI and its emission is quenched. It is therefore very important to determine the S1/S0
MECI theoretically. The GRRM method (see section I) allows one to search and determine MECIs automaticallyand is a very essential tool for clarification of the origin of quenching of such molecules. We have recently used
the GRRM method in conjunction to inexpensive DFT methods for the quenching mechanism of large organicand inorganic molecules.
A. Exploring the reaction coordinates for f-f emission and quenching of lanthanide complexes –thermo-sensitivity of terbium(III) luminescence. (See research activities of M. Hatanaka)
B. Reason of the low quantum yield (QY) of Eu(III) helical ligand complexes and computational molecular
design for higher QY. (See research activities of M. Hatanaka)
C. Photochemical Ring Opening and Closing of Three Isomers of Diarylethene: Spin-Flip Time Dependent
Density Functional Study (See research activities of M. Isegawa)
D. Exploration of quenching pathway of multiluminescent acenes using the GRRM strategy with the SF-TDDFT
method. (See research activities of S. Suzuki)
V. Theoretical Studies of Chemical Reactions of Small Radical Species
We have collaborated with a molecular beam experimental group to study the reaction of phenyl and tolyl
radicals with butadiene and vinyl acetylene to form naphthalene derivatives, the reaction that is considered to beimportant in terrestrial as well as combustion environments.
A. An Experimental and Theoretical Study on the Formation of 2-Methylnaphthalene (C11H10/C11H3D7) in theReactions of the Para-Tolyl (C7H7) and Para-Tolyl-d7 (C7D7) with Vinylacetylene (C4H4). (See Original
Paper #15)
B. Formation of 6-Methyl-1,4-Dihydronaphthalene in the Reaction of the Para-Tolyl Radical with
1,3-Butadiene under Single Collision Conditions, J. Phys. Chem. A 118, 12111-12119 (2014). (See Original
Paper #4)
3

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Ⅳ 研究業績 (2014)

C.

D.
E.

A Crossed Molecular Beam and Ab Initio Study on the Formation of 5- and6-Methyl-1,4-Dihydronaphthalene (C11H12) via the Reaction of Meta-Tolyl (C7H7) with 1,3-Butadiene(C4H6). (See Original Paper #1).
Complete active space second order perturbation theory (CASPT2) study of N(2D) + H2O reaction paths on
D1 and D0 potential energy surfaces: direct and roaming pathways. (See Original Paper #6)
Initial gas phase reactions between Al(CH3)3/AlH3 and ammonia: a theoretical study. (See Original Paper#2)

2. Original Papers
1. R. I. Kaiser, L. G. Muzangwa, T. Yang, D. S. N. Parker, A. M. Mebel, A. Jamal, and K. Morokuma, A Crossed
Molecular Beam and Ab Initio Study on the Formation of 5- and 6-Methyl-1,4-Dihydronaphthalene (C11H12)
via the Reaction of Meta-Tolyl (C7H7) with 1,3-Butadiene (C4H6). Phys. Chem. Chem. Phys. 17, 7699-7706(2015).
2. A. S. Lisovenko, K. Morokuma, A. Y. Timoshkin. Initial gas phase reactions between Al(CH3)3/AlH3 andammonia: a theoretical study, J. Phys. Chem. A 119, 744-51 (2015).
3. B. Liu, J. Liu, H.-B. Li, R. Bhola, E. A. Jackson, L. T. Scott, A. J. Page, S. Irle, K. Morokuma and C. Zhou,
Nearly Exclusive Growth of Small Diameter Semiconducting Single-Wall Carbon Nanotubes from Organic
Chemistry Synthetic End-Cap Molecules, Nano Lett. 15, 586-595 (2015).
4. D. S. N. Parker, B. B. Dangi, R . I. Kaiser, A. Jamal, M. Ryazantsev and K. Morokuma, Formation of
6-Methyl-1,4-Dihydronaphthalene in the Reaction of the Para-Tolyl Radical with 1,3-Butadiene under Single
Collision Conditions, J. Phys. Chem. A 118, 12111-12119 (2014).
5. M. Hatanaka and K. Morokuma, Exploring the reaction coordinates for f-f emission and quenching oflanthanide complexes – thermo-sensitivity of terbium(III) luminescence. J. Chem. Theo. Comp. 10,4184-4188 (2014).
6. M. Isegawa, F. Liu, S. Maeda and K. Morokuma, Complete active space second order perturbation theory(CASPT2) study of N(2D) + H2O reaction paths on D1 and D0 potential energy surfaces: direct and roaming
pathways, J. Chem. Phys. 141, 154303/1-9 (2014).
7. S. Maeda, Y. Harabuchi, T. Taketsugu, and K.Morokuma, Systematic Exploration of Minimum Energy ConicalIntersection Structures near the Franck-Condon Region, J. Phys. Chem. A 118, 12050-12058 (2014).
8. S. Maeda, Y. Harabuchi, Y. Ono, T. Taketsugu, and K. Morokuma, Intrinsic Reaction Coordinate: Calculation,
Bifurcation, and Automated Search, Int. J. Quant. Chem. 115, 258-269 (2015).
9. S. Maeda, T. Taketsugu, K. Morokuma, and K. Ohno. Anharmonic Downward Distortion Following for
Automated Exploration of Quantum Chemical Potential Energy Surfaces, Bull. Chem. Soc. Jpn. 87,
1315-1334 (2014).
10. X. Li, L. W. Chung, K. Morokuma and G. Li, A Theoretical Study on the UVR8 Photoreceptor: Sensing
Ultraviolet-B by Tryptophan and Dissociation of Homodimer, J. Chem. Theo. Comp. 10, 3319–3330 (2014).
11. M. Isegawa, F. Liu, S. Maeda, and K. Morokuma, Ab initio reaction pathways for photodissociation andisomerization of nitromethane on four singlet potential energy surfaces with three roaming paths J. Chem.
Phys. 140, 244310/1-11 (2014).
12. H-B. Li, A. J. Page, C. Hettich, B. Aradi, C. Köhler, T. Frauenheim, S. Irle and K. Morokuma, Graphene
Nucleation on a Surface-Molten Copper Catalyst: Quantum Chemical Molecular Dynamics Simulations,Chem. Sci. 5, 3493-3500 (2014).
13. G. P. Petrova, H.-B. Li, K. Maruoka and K. Morokuma, Asymmetric phase-transfer catalysis with homo- andheterochiral quaternary ammonium salts: a theoretical study, J. Phys. Chem. B, 118, 5154–5167 (2014).
4－ 64 －

Ⅳ 研究業績 (2014)

14. G. P. Petrova, Z. Ke, S. Park, H. Sugiyama and K. Morokuma, The origin of enantioselectivity for
intramolecular Friedel-Crafts reaction catalyzed the supramolecular Cu / DNA catalyst complex, Chem.
Phys. Lett. 600, 87-95 (2014).
15. D. S. N. Parker, B. B. Dangi, R. I. Kaiser, A. Jamal, M. N. Ryzantsev, K. Morokuma, A. Korte and W. Sander,
An Experimental and Theoretical Study on the Formation of 2-Methylnaphthalene (C11H10/C11H3D7) in theReactions of the Para-Tolyl (C7H7) and Para-Tolyl-d7 (C7D7) with Vinylacetylene (C4H4), J. Phys. Chem. A
118, pp 2709–2718 (2014).
16. M. Jiao, H. Qian, A. Page, K. Li, Y. Wang, Z. Wu, S. Irle, and K. Morokuma, Graphene Nucleation from
Amorphous Nickel Carbides: QM/MD Studies on the Role of Subsurface Carbon Density, J. Phys. Chem. C
118, 11078–11084 (2014).
3. Review Articles.
1. L. W. Chung, W. M. C. Sameera, R. Ramozzi, A. J. Page, M. Hatanaka, G. P. Petrova, T. V. Harris, X. Li, Z. Ke,
F. Liu, H.-B. Li, L. Ding, and K. Morokuma, The ONOIM Method and its Applications. Chem. Rev. 115,
5678–5796 (2015).
2. A. J. Page, F. Ding, S. Irle and K. Morokuma, Insights into Carbon Nanotube and Graphene Formation
Mechanisms from Molecular Simulations: A Review. Rep. Prog. Phys. 78, 036501/1-38 (2015).
4. Invited Presentation at Academic Conferences and Universities
1. Keiji Morokuma, Exploring potential energy surfaces with GRRM automatic search strategy, Theory andComputation Provide Insights and Discovery on Chemical Reactions of Complex Molecular Systems. the2014 AATACC Seminar, University of New Castle, Canberra, Australia, April 28, 2014
2. Theory and Computation Provide Insights and Discovery on Chemical Reactions of Complex Molecular
Systems, the 2014 AATACC Seminar, University of Sydney, Sydney, Australia, April 29, 2014
3. Theory and Computation Provide Insights and Discovery on Chemical Reactions of Complex Molecular
Systems, the 2014 AATACC Seminar, Australian National University, Canberra, Australia, May 1, 2014
4. Exciting World of Theoretical Studies of Chemical Reactions − From Gas Phase Reactions to Catalysts, andEnzymatic Reactions, Swiss Chemical Society Lecture, University of Basel, Basel, Switzerland, May 19, 2014
5. Chemical Theory of Complex Molecular Systems: Discovery and Insights from Computational Studies ofChemical Reactions, Swiss Chemical Society Lecture, University of Fribourg, Fribourg, Switzerland, May 20,
2014
6. Theoretical Studies of Complex Molecular Systems. Methods and Applications, Swiss Chemical Society
Lecture, University of Basel, Basel, Switzerland, May 21, 2014
7. Complex Chemical Reaction Pathways Explored by Automatic Search Strategy, Swiss Chemical Society
Lecture, ETH, Zurich, Switzerland, May 22, 2014
8. Exciting World of Theoretical Studies of Chemical Reactions − From Gas Phase Reactions to Catalysts, andEnzymatic Reactions, Swiss Chemical Society Lecture, EPFL, Lausanne, Switzerland, May 23, 2014
9. Multiscale Computational Approaches And Applications in Biochemistry And Biomaterials, Annual
Conference of Canadian Chemical Society, Vancouver, Canada, June 4, 2014
10. 複雑分子系のシミュレーション～生体分子の反応への応用とその周辺, 情報計算化学生物学会（CBI学会）講演会、東京、2014年7 月29 日
11. Quantum chemical molecular dynamics (QM/MD) simulations of nucleation, growth and healing processes offullerenes, carbon nanotubes and graphenes, the 17th International Symposium on Small Particles andInorganic Clusters (ISSPIC XVII), Fukuoka, September 7, 20145

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Ⅳ 研究業績 (2014)

12. Theory and Computation Provide Insights and Discovery on Chemical Reactions of Complex Molecular
Systems, International Conference "Molecular Complexity in Modern Chemistry” (MCMC-2014), Moscow,
Russia, September 16, 2014
13. Theory and Computation Provide Insights and Discovery on Chemical Reactions of Complex Molecular
Systems, Japan-Russia Joint-Symposium on Chemical Theory for Complex Systems, St. Petersburg State
University, Russia, September 19, 2014
14. Chemical Theory of Complex Molecular Systems: Discovery and Insights from Computational Studies ofChemical Reactions CRC-SU Joint International Symposium on Chemical Theory of Complex Systems:“Interplay between Theory and Experiments; New Trends in Catalysis”, Stockholm University, Stockholm,
Sweden, October 31, 2014
15. Theory and Computation Provide Insights and Discovery on Chemical Reactions of Complex Molecular
Systems, Advanced Molecular Transformations by Organocatalysts, 2nd International Conference and 7th
Symposium on Organocatalysis, Tokyo, November 21, 2014
16. GRRM法を用いた複雑分子系の反応機構、GRRM誕生十周年・GRRM14発表記念講演会「GRRMで拓く化学のニューフロンティア」、東京、2014年11月30日
17. Fascinating World of Theoretical Studies of Chemical Reaction--From Gas Phase Reactions to Catalysts, andEnzymatic Reactions, Hiroshima University, December 3, 2014
18. Chemical Reactions of Complex Molecular Systems -- Discovery and Insights from Computational Studies,
12th Fukui Institute Symposium, Fukui Institute for Fundamental Chemistry, Kyoto University, January 23,
2015
19. Exciting World of Theoretical Studies of Chemical Reactions − From Gas Phase Reactions to Catalysts, andEnzymatic Reactions, Argonne National Laboratory, USA, March 17, 2015
20. Gas-Phase Photochemical and Homogenous Catalytic Reactions Explored Using the Automated Reaction
Route Mapping (GRRM) Method, American Chemical Society Spring Meeting, Denver, USA, March 23,
2015
5. Other Activities.
1. The Morokuma group (Satoshi Suzuki, Miho Hatanaka, Julong Jiang, W.M.C. Sameera, Romain Ramozzi and
Keiji Morokuma) participated in the 2014 Kyoto University Academic Day, at the Kyoto University Centennial
Clock Tower on September 28, 2014, in the Section “Conversation with Researchers” by presenting a poster“Exploring the World of Chemistry by Computer.”6－ 66 －

Ⅳ 研究業績 (2014)

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 2014
The d electron complex systems which consist of transition metal element(s), organic moiety, main groupelement(s), and hypervalent species are attractive research targets in wide areas of modern chemistry.
Actually, the d electron complex systems play important roles as metal enzymes, molecular catalysts,
photo-sensitizer, molecular switch, luminescence material and so on. Also, they exhibit a variety ofgeometry, molecular property, bonding nature, reactivity and catalysis which attract a lot of interest intheoretical and 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 is indispensable infurther development of chemistry.
Also, those d-electron complex systems are interesting and challenging research targets from the point ofview 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. Our group is theoretically investigating those d-electroncomplex systems bearing complicated electronic structure.
This year, we theoretically investigated (i) electronic structure and absorption spectra of mixed-valence
Mn(III)- and Ni(II)-salen radical complexes, (ii) CASPT2 study of inverse dinitrogen complexes ofdinuclear metal complexes of the first row transition metal element, (iii) catalysis of Mo-Mo
quintuple bond in benzene synthesis from acetylelene, (iv) generation of dihydrogen molecule andhydrosilylation of carbon dioxide catalyzed by zinc hydride complex, and (v) efficient catalyst for
acceptorless alcohol dehydrogenation: interplay of theoretical and experimental studies, (vi) catalytic transferhydrogenation by at trivalent phosphorus compound, (vii) the crucial roles of MgCl2 as a non-innocent
additive in the Ni-catalyzed carboxylation of benzyl halide with CO2 and (viii) the crucial role of a Ni(I)intermediate in Ni-catalyzed carboxylation of aryl chloride with CO2.
. We wish to report summaries of them.
(i) Theoretical Study of One-Electron Oxidized Mn(III)− and Ni(II)−Salen Complexes: Localized vs
Delocalized Ground and Excited States in Solution:
The mixed-valence complexes are classified into three
categories by Robin and Day, as shown in Scheme 1. The
classification is of considerable importance in both offundamental chemistry and applied chemistry, because it
deeply relates to the electronic structure and also switching
function. Though one can expect that the classification Scheme
1.
Classificationofsignificantly depends on solvation, such dependency has not Mixed-Valence complexes by Robin andDaybeen theoretically investigated well.
One-electron oxidized Mn(III)− and Ni(II)−salen complexes exhibit unique mixed-valence electronic
structures and charge transfer (CT) absorption spectra. We theoretically investigated them to elucidate thereason why the Mn(III)−salen complex takes a localized electronic structure (class II mixed valencecompound by Robin−Day classification) and the Ni(II)-analogue has a delocalized one (class III) in solution,
where solvation effect was taken into consideration either by the three-dimensional reference interaction sitemodel self-consistent field (3D-RISM-SCF) method or by the mean-field (MF) QM/MMMD simulation. The－ 67 －

Ⅳ 研究業績 (2014)

geometries of these complexes were optimized by
the 3D-RISM-SCF-U-DFT/M06. The verticalexcitation energy and the oscillator strength of thefirst excited state were evaluated by the generalmulticonfigurationreferencequasidegenerate
perturbation theory (GMC-QDPT), including thesolvation effect based on either 3D-RISM-SCF- or
MF-QM/MMMD-optimized solvent distribution.
The computational results well agree with theexperimentally observed absorption spectra and theexperimentally proposed electronic structures. The
one-electron oxidized Mn(III)−salen complex with asymmetrical salen ligand belongs to the class II, as
Scheme 2. Ni(II) and Mn(III)-salen radical
experimentally reported, in which the excitation complexes and their electronic structure.
from the phenolate anion to the phenoxyl radical
moiety occurs. In contrast, the one-electron oxidized
Ni(II)−salen complex belongs to the class III, in which theexcitation occurs from the doubly occupied delocalized π1
orbital of the salen radical to the singly occupied delocalized
π2 orbital; the π1 is a bonding combination of the HOMOs of
two phenolate moieties and the π2 is an antibonding Figure 1. One-electron excitation in
Mn(III) and Ni(II) Complexes
combination. Solvation effect is indispensable for correctly
describing the mixed-valence character, the geometrical
distortion, and the intervalence CT absorption spectra of these complexes. The number of d electrons and the
d orbital energy level play crucial roles to provide the localization/delocalization character of thesecomplexes.
(ii) 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:
Dinuclear transition metal complexes exhibit complicated electronic structure and interesting
molecular properties. Inverse sandwich-type dinuclear complexes (ISTCs), (μ-C6H6 or N2)[M(AIP)]2 (AIPH= (Z)-1-amino-3-imino-prop-1-ene; M = Cr and Fe; Scheme 2), exhibit variety of spin multiplicity. This year,
the dinitrogen ISTCs of the first row transition metalelements were investigated with the CASPT2 method. In the
ISTC of Cr, the ground state takes a singlet spin multiplicity.
However, the singlet to nonet spin states are close in energy
to each other. The thermal average of effective magnetic
moments (μeff) of these spin multiplicities is close to theexperimental value. The η2-side-on coordination structure of
N2 is calculated to be more stable than the η1-end-on
Scheme 2. Benzene and dinitrogencoordination one. This is because the d-orbital of Cr forms a inverse sandwich dinuclear metalstrong dπ−π* bonding interaction with the π* orbital of N2 in complexes
molecular plane. The MO diagram and occupation number of－ 68 －

Ⅳ 研究業績 (2014)

MO (Scheme 3) provide us with consistent understanding of these features.
In the ISTC of Fe,
on the other hand, theground state takes aseptet spin multiplicity,which agrees well withtheexperimentally
reported μeff value. The
η1-end-on structure of N2
is more stable than theη2-side-on structure. In Scheme 3. Schematic orbital pictures of (μ-N2)[Cr(AIP)]2.
the η1-end-on structure,
two doubly occupied
d-orbitals of Fe can form two dπ−π* bonding interactions. The negative spin density is found on the bridging
N2 ligand in the Fe complex but is not in the Cr complex. All these interesting differences between ISTCs of
Cr and Fe are discussed on the basis of the electronic structure and bonding nature.
(iii) The important role of the Mo–Mo quintuple bond in catalytic synthesis of benzene from alkynes.
A theoretical study
Though the metal-metal multiple bond was foundvery old days by Cotton and his coworkers. Since then, its
interesting bonding nature has attracted many researchers intheoretical and experimental fields. However, its theoretical
study was not easy because of its complicated electronic
structure due to multi-reference nature. Also, the reaction of
metal-metal multiple bond has not been reported until
recent several pioneering works.
The Mo–Mo quintuple bond was recently applied tocatalytic synthesis of benzene from alkynes, which is thefirst example of the catalytic reaction of the metal–metal
multiple bond. This new reaction was studied using DFT Scheme 4. Catalytic Cycle theoreticallyand CASSCF/CASPT2 methods. The entire catalytic cycle elucidated.
consists of four steps: [2 + 2], [4 + 2], and [6 + 2]
cycloadditions, and reductive elimination of benzene. The symmetry-forbidden [2 + 2] cycloaddition andasymmetric [2 + 2] cycloaddition are two possible pathways for the reaction between an alkyne and the
Mo–Mo quintuple bond. Though the barrier of the former pathway is moderate because of the presence ofthe multi-reference character of the Mo–Mo quintuple bond, the asymmetric pathway is much morefavorable because of its symmetry-allowed feature.
The C–C bond formation in the next [4 + 2] cycloaddition occurs through charge transfer (CT) fromthe π orbital of the incoming alkyne to the π* orbital of another alkyne coordinating with the Mo center toafford a novel dimolybdenacyclic species 3. In 3, the δdxz and δdxz* orbitals of the Mo–Mo moiety and four πorbitals of the [C4H4] moiety construct the π and π* orbitals in the six-membered ring. The next [6 + 2]
cycloaddition between 3 and one more alkyne affords an eight-membered ring compound 4 which has a
Mo–Mo quadruple bond. This is the rate-determining step of the entire catalytic cycle, the ΔG0‡ value of－ 69 －

Ⅳ 研究業績 (2014)

which is 22.4 kcal mol−1. The
subsequent
reductive
elimination of benzene easily
occurs
to
yield
a
2
2 2
μ –η :η -benzene dinuclear Mo
complex with a Mo–Mo
quintuple bond. On the other
hand, further [8 + 2]
cycloaddition between 4 andone more alkyne is much more
unfavorable than the reductive
elimination of benzene. The
similar [4 + 2] process between
alkyne and a Cr–Cr quadruple
bond is calculated to be Figure 2. Energy changes in the first 4+2 coupling process leading to thedifficult, which is consistent formation of unusual six-member intermediate 3 .
with the experimental resultthat only the Mo–Mo quintuple bond was successfully applied to this reaction. It is likely that the crowded
coordination environment and the much more stable πdyz orbital in the Cr–Cr quadruple bond are
responsible for the difficulty in the reaction.
(iv) Generation of Dihydrogen Molecule and Hydrosilylation of CarbonDioxide Catalyzed by Zinc
Hydride Complex: Theoretical Understanding and Prediction
The H2 production from water and alcohol becomes
important nowadays. Also, the CO2 fixation is another important
reaction for sustainable society. Though many catalytic systems
have been proposed successfully for these reactions, the valuable
metals are used in those catalysts. That is also one of the problem.
We need to use cheap and abundant metal for catalysts because of
the limit of such metals in the earth.
In this work, the generation of H2 from methanol/water andScheme 5. Catalytic cycle of H2hydrosilylation of CO2 catalyzed by [tris(2-pyridylthio)methyl]zinc production from water or alcohol
hydride [κ3-Tptm]ZnH 1 were investigated with DFT and MP2 and CO2 fixation by Zn-H complex
methods. The hydrosilylation of CO2 occurs via the CO2 insertion 1
into the Zn−H bond of 1 followed by the metathesis of aZn−(η1-OCOH) bond with hydrosilane to yield silyl formate and regenerate 1. The CO2 insertion easily
occurs, but the metathesis is difficult because of the formation of a very stable Zn−(η2-O2CH) species before
the metathesis. The ΔG°⧧ value of the metathesis with triethoxysilane is much smaller than that withphenylsilane because electronegative methoxy groups stabilize the transition state bearing hypervalent Si
center, which is consistent with the experimental result that triethoxysilane is used in the hydrosilylation of
CO2. It is theoretically predicted here that hydrosilane with two electronegative OEt groups or one to three F
groups can be applied to this reaction. In the generation of H2 from methanol/water by 1, the first step is themetathesis of 1 with the O−H bond of methanol/water to produce [κ3-Tptm]Zn(OMe)/[k3-Tptm]Zn(OH) anddihydrogen molecule. The next step is the metathesis of the Zn−OMe/Zn−OH bond with hydrosilane to yield－ 70 －

Ⅳ 研究業績 (2014)

silyl ether and regenerate 1. The first metathesis is rate-determining but the second one occurs with verysmall activation energy, indicating that various hydrosilanes can be applied to this reaction.
(v) Efficient Catalyst for Acceptorless Alcohol Dehydrogenation: Interplay of Theoretical andExperimental Studies
As mentioned above, the H2
production from alcohol is one ofimportant catalytic reactions now.
Recently, Fujita and Yamaguchi
reported excellent catalyst with Ircomplex to perform this reaction under
mild conditions without any acceptor.
Such reaction is of considerable
Scheme 6. Reaction scheme of acceptorless alcoholinterest and theoretical knowledge is dehydrogenation reaction and excellent Ir catalyst
necessary to understand well thecatalytic mechanism and the prediction.
In this work, the promoterless AAD (acceptorless alcohol dehydrogenation) reaction mediated by an
iridium catalyst Cp*Ir(bpyO) 1−Ir (Cp* = pentamethylcyclopentadienyl, bpyO = α,α′-bipyridonate) has beentheoretically investigated with the density functional theory. The reaction occurs through three steps,
including alcohol dehydrogenation, formation of dihydrogen complex, and H2 elimination from the iridium
center. In the first two steps, the metal center and the bpyO ligand work cooperatively via thearomatization/dearomatization process of the bpyO ligand. The second step is ratedetermining, where the
ΔG0≠ and ΔG0 values are 23.9 and 13.9 kcal/mol, respectively. Our calculations demonstrate that thearomatization of the bpyO ligand as well as the charge transfer (CT) from the Cp* ligand to the iridium
center plays important roles in stabilizing the transition state of the rate-determining step. We havetheoretically and experimentally examined the 4d rhodium analogue Cp*Rh(bpyO) 1−Rh and found that itexhibits similar activity to that of 1−Ir. On the basis of those results, a new catalyst (HMB)Ru(bpyO) 1−Ru
(HMB = hexamethylbenzene) is designed both theoretically and experimentally, where a cheaper and moreabundant 4d ruthenium element is employed with the HMB and bpyO ligands. Theoretical calculations
certainly show that 1−Ru is active for the promoterless AAD reaction via the same reaction mechanism asthat of the reaction by 1−Ir. The experiments also demonstrate that 1−Ru is as efficient as 1−Ir for the AAD
reaction.
(vi) Catalytic Transfer Hydrogenation by a Trivalent Phosphorus Compound: Phosphorus-Ligand
Cooperation Pathway or P(III)/P(V) Redox Pathway?
Main-group-element catalysts are a desirable alternative to transition-metal catalysts because of naturalabundance and cost. However, the examples are very limited. Catalytic cycles involving a redox process
and E-ligand cooperation (E=main-group element), which are often found in catalytic cycles oftransition-metal catalysts, have not been reported.
Herein theoretical investigations of a catalytic hydrogenation of azobenzene with ammonia–borane
using a trivalent phosphorus compound, which was experimentally proposed to occur through PIII/PV redox
processes via an unusual pentavalent dihydridophosphorane, were performed. The geometry was optimizedby the DFT and the energy change was evaluated by the ONIOM(CCSD(T):MP2) method. These
calculations disclosed that this catalytic reaction occurs through a P-O cooperation mechanism, which－ 71 －

Ⅳ 研究業績 (2014)

resembles the metal-ligand cooperation mechanism of transition-metal catalysts. As summarized in Scheme
7: 1) the catalytic cycle occurs through a new concerted P-O cooperation mechanism, 2) the active species of
the transfer hydrogenation is 4OP, which is produced from 1P through the dehydrogenation ofammonia–borane, 3) this PO cooperative reaction resembles the metal-ligand cooperation reaction by thetransition-metal complex with a pincer ligand, 4) the PIII/PV redox reaction certainly occurs in the mutual
conversions between 4OP and 4PP, but it is not involved in the catalytic cycle, and 5) the substitution of theelectron-withdrawing CF3 group for tBu improves the catalytic activity of the trivalent phosphorus compound

Scheme 7. Transfer hydrogenation of azobenzene with ammonia-borane by 1P via aP(III) compound 4OP which further isomerizes to 4PP with a stepwise reaction
h i(vii) The crucial roles of MgCl2 as a non-innocent additive in the Ni-catalyzed carboxylation of benzyl
halide with CO2
The transformation of CO2 into useful chemicals has
been one of the important topics in the last decade.1 In thisregard, various attempts have been made usingtransition-metal complexes as catalysts for the CO2transformation. Among those efforts, direct carboxylation oforganic halide with CO2 is in particular attractive because of
the importance of carboxylic acid in various applications.3
However, the reports of such direct carboxylation have been
elusive except for several pioneering studies of the Martingroup4 and the Tsuji group.5 Interestingly, Martin and Scheme 8. Experimentally proposed
co-workers succeeded in the transformation of the C(sp3)–Cl and theoretically evidenced reaction
mechanismbond of benzyl halide to phenylacetic acid with CO2 using a Ni
catalyst, very recently. This Ni-catalytic system contains the Zn powder and MgCl2. If the Zn powder isabsent, no catalytic conversion occurs. If MgCl2 is not added, the yield is very low. The experimentally
proposed reaction mechanism suggests that a Ni(I) intermediate might be crucial in the catalytic cycle, as
shown in Scheme 8. However, mysterious is the role of MgCl2; it is not clear at all what roles MgCl2 plays inthis catalytic carboxylation to provide good yield of the product.
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Ⅳ 研究業績 (2014)

Herein, we theoretically investigated this Ni-catalyzed carboxylation of benzyl chloride tophenylacetic acid in the presence of MgCl2. The Gibbs free energy profile for the total catalytic cycle clearly
indicates that MgCl2 promotes the carboxylation of benzyl chloride with CO2. Based on the computational
results, we disclosed here that MgCl2 stabilizes the Ni(I)-CO2 adduct and accelerates the CO2 insertion as a
non-innocent additive and one-electron reduction as one reagent. To the best of our knowledge, this is thefirst report that shows the unprecedented roles of MgCl2. The knowledge of the interplay between the metal
catalysis and non-innocent additive is crucial for new development in catalytic reactions by transition metal
complexes.
Original Papers(1) Yuh Hijikata and Shigeyoshi Sakaki,“Interaction of Various Gas Molecules with Paddle-Wheel-Type Open Metal Sites of Porous
Coordination Polymers: Theoretical Investigation”
Inorg. Chem., 53, 2417−2426 (2014).
(2) Masayuki Nakagaki and Shigeyoshi Sakaki,"CASPT2 Study of Inverse Sandwich-Type Dinuclear Cr(I) and Fe(I) Complexes of the
Dini-trogen Molecule: Significant Differences in Spin Multiplicity and Coordination Structure
between These Two Complexes”
J. Phys. Chem. A, 118, 1247−1257 (2014).
(3) Shinji Aono, Masayuki Nakagaki, Takuya Kurahashi, Hiroshi Fujii, and Shigeyoshi Sakaki, J.
Chem. Theory Comput. 2014, 10, 1062−1073“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).
(4) Hiroshi Sato, Wataru Kosaka, Ryotaro Matsuda, Akihiro Hori, Yuh Hijikata,Rodion V. Belosludov,
Shigeyoshi Sakaki, Masaki Takata, Susumu Kitagawa,“Self-Accelerating CO Sorption in a Soft Nanoporous Crystal”
Science, 343, 167-170 (2014).
(5) Guixiang Zeng, Shigeyoshi Sakaki, Ken-ichi Fujita, Hayato Sano, and Ryohei Yamaguchi,“Efficient Catalyst for Acceptorless Alcohol Dehydrogenation: Interplay of Theoretical andExperimental Studies”
ACS Catal., 4, 1010−1020 (2014).
(6) Guixiang Zeng, Satoshi Maeda, Tetsuya Taketsugu, and Shigeyoshi Sakaki,“Catalytic Transfer Hydrogenation by Trivalent Phosphorus Compound: Phosphorus-Ligand
Cooperation Pathway or PIII/PV Redox Pathway?”
Angew. Chem. Int. Ed., 128, 4721-4725 (2014).
(7) Yue Chen and Shigeyoshi Sakaki,“The important role of the Mo–Mo quintuple bond in catalytic synthesis of benzene from alkynes.
A theoretical study”
Dalton Trans., 43, 11478-11492 (2014).
(8) Farreed Basha Sayyed and Shigeyoshi Sakaki,“The Crucial Roles of MgCl2 as a Non-innocent Additive in the Ni-Catalyzed Carboxylation of
Benzyl Halide with CO2”
Chem. Commun., 50, 13026 – 13029 (2014).
(9) Masayuki Wakioka, Yuki Nakamura, Yoshihiro Hihara, Fumiyuki Ozawa, and Shigeyoshi Sakaki,“Effects of PAr3 Ligands on Direct Arylation of Heteroarenes with Isolated [Pd(2,6-Me2C6H3)(μ‑O2CMe)(PAr3)]4 Complexes”
Organometallics, 33, 6247–6252 (2014).
(10) Keisuke Kishida, Yumiko Watanabe, Horike Satoshi, Yoshihiro Watanabe, Yoshikuni Oku-mura,Yuh Hijikata, Shigeyoshi Sakaki, and Susumu Kitagawa,“DRIFT and Theoretical Studies of Ethylene/Ethane Separation on Flexible Microporosity of[Cu2(2,3-pyrazinedicarboxylate)2(pyrazine)]n”
Eur. J. Inorg. Chem., 2747–2752 (2014).
－ 73 －

Ⅳ 研究業績 (2014)(11) Tetsuaki Fujihara, Yuichiro Horimoto, Taiga Mizoe, Fareed Bhasha Sayyed, Yosuke Tani, Jun Terao,
Shigeyoshi Sakaki, and Yasushi Tsuji“Nickel-Catalyzed Double Carboxylation of Alkynes Employing Carbon Dioxide”
Org. Lett., 16, 4960−4963 (2014).
(12) Milind Madhusudan Deshmukh and Shigeyoshi Sakaki,“Generation of Dihydrogen Molecule and Hydrosilylation of Carbon Dioxide Catalyzed by Zinc
Hydride Complex: Theoretical Understanding and Prediction”
Inorg. Chem., 53, 8485−8493 (2014).
(13) Hajime Kameo, Tatsuya Kawamoto, Shigeyoshi Sakaki, and Hiroshi Nakazawa,“Can One σ*-Antibonding Orbital Interact with Six Electrons of Lewis Bases? Analysis of aMultiply Interacting σ* Orbital”,
Organometallics, 33, 5960−5963 (2014).
(14) Hajime Kameo, Tatsuya Kawamoto, Shigeyoshi Sakaki, Didier Bourissou, and Hiroshi Nakazawa“Synthesis, Geometry, and Bonding Nature of Heptacoordinate Compounds of Silicon andGermanium Featuring Three Phosphine Donors”
Organometallics, 33, 6557−6567 (2014).
3. Presentation at academic conferences(1) Shigeyoshi Sakaki,“Reaction Behavior of Main-Group Element Compound in Comparison with Transition-Metal
Complex. Theoretical Understanding and Prediction
The International Symposium on Reactive Intermediates and Unusual Molecules (ISRIUM) 2014,
April, 1-6, 2014, Hiroshima (Invited)(2) Shigeyoshi Sakaki“Catalytic Reactions by Transition Metal Complexes with Unusual Valence: Theoretical Study
XXVI International Conference on Organometallic Chemistry, July 13 – 18, 2014, Sapporo, Japan.
(Invited)(3) Shigeyoshi Sakaki“Spin-Multiplicity Issues of Transition Metal Complexes: Theoretical Understanding”,
41th International Conference on Coordination Chemistry (41 ICCC), July 21 – 25, 2014, Singapole(Invited)(4) Shigeyoshi Sakaki“-Bond Activation Reaction by Transition Metal and Main-Group Element Compounds andCatalytic Reaction Including It, International Conference”. Molecular Complexity in Modern
Chemistry (MCMC2014)”, Sept, 13 – 19, Moscow, Russia (Invited)(5) Shigeyoshi Sakaki“Flexibility in Spin-Multiplicity of Transition Metal Complex”
CRC-SU (Catalysis Research Center-Stockholm Univeristy) Joint Symposium for Chemical Theory
for Complex Systems, Oct. 30-31, 2014, Stockholm University, Stockholm, Sweden, (Plenary)(6) Shigeyoshi Sakaki“Flexible Electronic Structures of Inverse Sandwich-type Dinuclear Metal Complex and Metal
Salen Complex”
QSCP XIX (XIXth International Workshop on Quantum Systems in Chemistry, Physics andBiology), Nov. 11-17, 2014, Tamsui, Taiwan, (Invited)(7) Shigeyoshi Sakaki“Theoretical Study of Complex System Consisting of Transition Metal Element
From
Mononuclear Metal Complex to Multinuclear Metal Complex and Metal Complex System in
Surrounding Atmosphere”
Lead-Lecture, Eurasia-13 Conference on Chemical Sciences, Dec. 15 – 18. 2014, Bangalore, India(Invited./Lead Lecture)(8) Shigeyoshi Sakaki“Molecular Property and Reactivity of Transition Metal Complex: Theoretical Understanding andPrediction”, The 4th Modeling of Chemical and Biological (Re)Activity, Feb. 23-25, 2015.
Heiderberg, Germany (Invited)－ 74 －

Ⅳ 研究業績 (2014)

4. Others(1) σ‑Bond Activation of Small Molecules and Reactions Catalyzed by Transition-Metal Complexes:
Theoretical Understanding of Electronic Processes
Wei Guan, Fareed Bhasha Sayyed, Guixiang Zeng, and Shigeyoshi Sakaki, Inorg. Chem. 2014,
53, 6444−6457.

(2) 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春
季年会、３月26-29日, 1S2-02 名古屋大学(3) 金属錯体の量子・計算化学、山口兆、榊 茂好、増田秀樹編、三共出版 ２０１４年
3-3 多核金属錯体の理論化学 中谷直輝、榊 茂好 pp250-268
5-5-2 理論化学･計算化学分野から見た錯体化学の理論的研究の将来展望と今後への期待
榊 茂好 pp500-518.
(4) 日本化学会編 化学便覧 応用編 10. 榊 茂好、山下晃一；計算機シミュレーションと情報科学－ 75 －

Ⅳ 研究業績 (2014)

４．博士研究員

嶺澤
嶺澤

範行
範行

センターフェロー

センターフェロー
1. 今年度の研究の要約
今年度は、(1)時間依存密度汎関数法 (TDDFT) のプログラム開発と(2)溶液内における光化学反応の解析を行った。後者は、昨年度から引き続きの研究課題である。
【Non-collinear SF-TDDFT 法のプログラム開発】
スピン反転励起をもとに電子励起状態を記述する SF-TDDFT 法は、ポテンシャル面の交差を同定することができることを過去の研究において報告した[1-2]。したがって、光化学における反応機構を解明する上で非常に有用な方法である。SF-TDDFT 法は３重項を参照系として、スピン反転励起を考える:

AX   X(1)

Aia , jb  a   i   ij ab  cx  ij | ab 

(2)

もっとも単純な collinear (C) 型の場合[3]、で表される。ここで、 i, j , はアルファスピンをもつ占有軌道、 a , b , はベータスピンをもつ非占有軌道、{・} は軌道エネルギー、そして係数 cx は Hartree-Fock (HF) 交換項の割合を示す。上式から明らかなように、適用可能な汎関数は HF 項をもったものに限られ、計算では cx � 0.5 のものが用いられる。

今年度の研究では、適用可能な汎関数の幅を増やすため、いわゆる non-collinear (NC) 型の
SF-TDDFT 法[4,5]を実装した。NC-SF-TDDFT 法は、NC
Aia , jb  a   i   ij ab  cx  ij | ab   fijab(3) En (r )  En (r )  dr  i (r ) j (r ) a (r ) b (r )
(
r
)

(
r
)
n
n




(4)

で付加項が現れる。
xc

f

NC
ijab

xc

この付加項が存在することで、HF 交換項がない汎関数でも SF-TDDFT 法で計算を行うことができる。

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Ⅳ 研究業績 (2014)

本研究ではテスト計算として、シアニン色素のモデル分
子の系列を選んだ (図 1)。
計算結果の一部を表 1 に示した (詳しい結果および解析
図 1: シアニン分子については文献[7]を参照)。従来の C-SF-TDDFT 法でcx

0.5 の汎関数 (BHHLYP) を用いることで、精度よく記述できた。今回導入した NC-SF-TDDFT

法で cx  0 の汎関数 (SVWN, BLYP) を試したが、~1 eV の過小評価をしてしまうことがわかった。
したがって、この分子系では HF 交換項が重要であることが示唆される。実際、NC-SF-TDDFT 法
でも cx が大きな汎関数では精度がよいことを確認した。

今後、NC-SF-TDDFT 法をポテンシャル面の交差に応用し、汎関数の依存性について研究する予定である。
表 1: シアニンの励起エネルギー (単位: eV)
CN5

CN7

CN9

CN11

MSEa

C-BHHLYP

5.18

4.00

3.32

2.87

+0.20

NC-BHHLYP

5.15

3.87

3.19

2.76

+0.10

NC-SVWN

3.95

2.80

2.17

1.77

−0.97

NC-BLYP

3.85

2.73

2.12

1.74

−1.03

DMCba

5.03

3.83

3.34

2.88

a

Mean signed error w.r.t. DMC.

b

Diffusion Monte Carlo.

【水和チミン分子における自由エネルギー面交差の解析】
生体内に存在する DNA は有害な紫外線により損傷を受ける可能性がある。
遺伝情報が適切に保存されないことは、生物にとって致命的である。しかし、DNA 塩基では非常に速い緩和過程が存在し、有害な副次的反応を抑制する。本研究では、チミン分子 (図 2) の水溶液における非断熱緩和過程を、自由エネルギーの交差の観点から解析する。
図 2: チミン分子
自由エネルギーの交差点を求める方法は、昨年度の研究で確立した。すなわち、非平衡自由エネル
ギー F (R, V ) を定義し、2 つのエネルギー面の交差を考える。ここで、 V は溶媒和座標を表しており、核座標 R と同時に最適化を行う。

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Ⅳ 研究業績 (2014)

本研究では３つの自由エネルギー交差点が同定された。分子構造を図 3 に示す。いずれの構造においても６員環の炭素原子に結合した (a)メチル基、(b)水素原子、あるいは (c)酸素原子の面外振動の寄与がある。特に(c)の構造では、水素結合の生成によって酸素原子の面外角が強調されている。
酸素原子と水との相互作用による安定化は、表 2 からも明らかである。水和により(c)の構造が特に大きく安定化している。これは、最近報告された水和チミンの非断熱分子動力学シミュレーション
で現れた分子構造を再現している[9]。

図 3: チミン分子の円錐交差における分子構造 (灰色: 気相、黒: 水溶液)(a) MEX(C5), (b) MEX(C6), and (c) MEX(C4).

表 2: チミン分子の相対エネルギーa (単位: eV)aFranck-Condon

MEX (C5)

MEX (C6)

MEX (C4)

Gas

5.92

4.54

5.52

5.60

Water

5.79

4.48

5.53

4.94

エネルギーの原点は基底状態の再安定構造

【文献】
1.

N. Minezawa and M. S. Gordon, “Optimizing conical intersections by spin-flip density functional
theory”, J. Phys. Chem. A 113, 12749 (2009).

2.

N. Minezawa and M. S. Gordon, “Photoisomerization of stilbene: A spin-flip density functional
theory”, J. Phys. Chem. A 115, 7901 (2011).

3.

Y. Harabuchi, S. Maeda, T. Taketsugu, N. Minezawa, and K. Morokuma, “Automated search forminimum 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 (2013).

4.

Y. Shao, M. Head-Gordon, and A. I. Krylov, “The spin–flip approach within time-dependent
density functional theory: Theory and applications to diradicals”, J. Chem. Phys. 118, 4807 (2003).

5.

F. Wang and T. Ziegler, “Time-dependent density functional theory based on a noncollinear
formulation of the exact-exchange potential”, J. Chem. Phys. 121, 12191 (2004).
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Ⅳ 研究業績 (2014)

6.

Y. A. Bernard, Y. Shao, and A. I. Krylov, “General formulation of spin-flip time-dependent density
functional theory using non-collinear kernels: Theory, implementation, and benchmarks”, J. Chem.
Phys. 136, 204103 (2012).

7.

N. Minezawa, “Vertical excitation energies of linear cyanine dyes by spin-flip time-dependent
density functional theory”, Chem. Phys. Lett. 622, 115 (2015).

8.

N. Minezawa, “Optimizing minimum free-energy crossing points in solution: Linear-response freeenergy/spin-flip density functional theory approach”, J. Chem. Phys. 141, 164118 (2014).

9.

A. Nakayama, G. Arai, S. Yamazaki, and T. Taketsugu, J. Chem. Phys. 139, 214304 (2013).

2. 論文
1.

N. Minezawa, “Vertical excitation energies of linear cyanine dyes by spin-flip time-dependent
density functional theory”, Chem. Phys. Lett. 622, 115-119 (2015).

2.

N. Minezawa, “State-specific solvation effect on the intramolecular charge transfer reaction insolution: A linear-response free energy TDDFT method”, Chem. Phys. Lett. 608, 140-144 (2014).

3.

N. Minezawa, “Optimizing minimum free-energy crossing points in solution: Linear-response freeenergy/spin-flip density functional theory approach”, J. Chem. Phys. 141, article No. 164118(2014).

3.学会発表(1) 嶺澤 範行「GFP 発色団分子の水溶液における円錐交差の理解: SF-TDDFT/LRFE 法」
第１７回理論化学討論会 名古屋大学 2014/05/23 2P20(2) 嶺澤 範行「溶液における分子内電荷移動: 状態固有の溶媒和効果」
第８回分子科学討論会 広島大学 2014/09/21 1P108

4. その他(1) 嶺澤 範行「分子内電荷移動反応における状態固有の溶媒和効果」
第１２回京都大学福井謙一記念研究センターシンポジウム
京都大学

2015/01/23 P20－ 79 －

Ⅳ 研究業績 (2014)

Takuya Saito
Takuya Saito
FIFC Fellow
FIFC Fellow
1. Summary of the research of the year
Driven anomalous diffusion in polymer stretching
Small particles or soft matters in solutions exhibit diffusive motion due to thermal agitation. One of theway to approach the diffusion characteristics is to examine the time evolution of the position variance<(x(t)-x(0))2>-<(x(t)-x(0))>2 ~ t. While the diffusion of the simple particle is normal with the exponents
being ~1, viscoelastic conditions such as soft matter or cells make the dynamics anomalous. For example, if
a monomer of polymer is tracked, the diffusion is usually characterized by the smaller exponent <1, i.e.,
subdiffusion because of the chain connectivity.
There are various underlying mechanisms generating the anomalous diffusion. In our study, wenarrowed down a target to a tagged monomer dynamics of a driven single polymer. The polymer initiallyrelaxes, but the chain end starts to be pulled with constant force at time t=0. We then track the stochastic
motion of the tagged monomer, where the other connected monomers create the colored noise against it. So
far, the fluctuation has been discussed on the basis of the generalized Langevin equation (GLE) with thepower-law memory kernel and the previous studies reported that some polymer model retains thefluctuation-dissipation like normal diffusion in a simple colloid. Indeed, we can confirm it under weak
driving force (or the Rouse model). This relates the variance to the average drift;f<(x(t)-x(0))2>/<x(t)>=2kBT.

(1)Here question arise: does it hold beyond the near equilibrium? Our study addressed the issue and pointed outthat it does not necessarily hold under strong driving force and what deviates eq. (1).
(a)

(b)

t=0

f

t=0

Hereafter, we will describe ourfinvestigation on the anomalous dynamics ofpolymer stretching under strong driving
force by combining different approaches.

ff(i) We first discussed it at the scalinglevel in (a) weak and (b) strong force

x
x(0)
Fig.

1.

x(t)

Schematicxx(0) x(t)representationofpolymerstretching.

regimes (see Fig. 1). In both, the tension
propagation mechanism is a key word tointerpret the dynamics. The tension gets
transmitted along the polymeric chain fromthe forced monomer. On the other hand, thedominant－ 80 －

factors

aredifferent.

TheⅣ 研究業績 (2014)fluctuations dominate in the weak force regime compared with the drift, while the drift has a major
contribution in the strong force regime. From eq. (1), we can estimate the drift or fluctuation in weak orstrong force, respectively, but we have to stress out that it does not necessarily hold in strong force as will bementioned below. Except ideal chains, the memory kernel or spring constant depends on the force magnitude
due to the self-avoiding (SA) effects, which eventually deviates normalized ratio eq.(1).

Fig. 2 MD simulation results in 3D (left) and 2D (right). Time evolutions of average drift andvariance in the displacement are plotted. All axes are double logarithmic scale.

(ii) To numerically verify it, we carried out molecular dynamics simulation of the self-avoiding chain(free-drraining). We calculated the average drift and the variance in the displacement (Fig.2). There are two
regimes in the time evolutions; first, anomalous dynamics is observed, and later the center of mass modeshows up.
We then plotted the normalized ratio, i.e., left hand side of eq (1) (see Fig. 3). The 3D results are in agood agreement with the prediction by eq. (1), but the deviations are clearly seen in 2D.

Fig. 3. Normalized Ratio.
(iii) To construct the microscopic model to analyze the results of (ii), we first reviewed the Rousechain known as the simple polymer model idealized by not considering the self-avoidance (SA) andhydrodynamic interactions (HIs). The Rouse model was reported to be described by the GLE. We there
discussed the connection between real and mode spaces for the response and correlation.
Next we again reviewed the near equilibrium fluctuation with the SA and/or HIs, which are generally－ 81 －

Ⅳ 研究業績 (2014)

non-linear effects. The dynamics is described in the mode space by using friction and spring constants
pre-averaged over the equilibrium distribution. From this, we investigated the non-linear force dependence,and the relation of the response with the velocity autocorrelation was discussed.
(iv) Mono-block picture was found to be available to describe the fluctuation in the transient process
as well as around the steady stretching state used in the previous work. Indeed, the average dynamics isequivalent to that obtained by the scaling theory (two state approximation). Developing this approach, weinvestigated the normalized rate and then we found eq. (1) is not satisfied in the self-avoiding chain, since
the restoring force is essentially changed from the initial equilibrium to stretching. The theoreticalpredictions qualitatively meet with MD results (Fig. 3).

Rate in template-directed polymer synthesis
Genomic DNAs are synthesized by DNA polymerase through driven process. Synthesizing time andaccuracy are expected to be important in this process. However, how to simultaneously weigh those has
been an issue. In this study, we proposed the template-directed polymer synthesis rate to weigh the timeand accuracy through the same unit. The rates in several models were discussed.

2. Original papers(1) Takuya Saito,“Rate in template-directed polymer synthesis”
Phys. Rev. E 89, 062716(2014).
3. Presentation at academic conferences(1) 齋藤拓也, 坂上貴洋
“伸張した高分子鎖の揺らぎと応答”
日本物理学会 2014 秋季大会, 中部大学 春日井キャンパス, Sep 8, 2014(2) 齋藤拓也、坂上貴洋“引き伸ばされていく過渡的過程の高分子の揺らぎと移動距離”
日本物理学会第 70 回年次大会, 早稲田大学 早稲田キャンパス, Mar 22, 2015
4. Others(1) Takuya Saito and Takahiro Sakaue“引き伸ばされていく過渡的過程の高分子の揺らぎ”
The 12th symposium of Fukui Institute for Fundamental Chemistry, Kyoto, Jan. 23, 2015.

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John Jairo Molina
John Jairo Molina
FIFC Fellow
FIFC fellow
1. Summary of the research of the year
Dynamics of passive and active particles
Colloidal dispersions make up most of the materials we use in our everyday life, such as foams, emulsions,or gels. Specific examples include blood, pigmented ink, milk, and gelatin. Understanding the properties ofsuch dispersions is crucial to control many industrial and engineering processes. Additionally, recent
experiments have shown the possibility of creating active colloidal particles, which are able to extract local
energy from their environment to perform work. Unfortunately, accurately simulating such systems requiresthat one be able to solve for the fluid and particle motions over large scales with a very fine resolution (forHere, we have contributed to the development of a direct numericalsimulation method that can be used to study dense dispersions ofcomplex particles (both passive and active) with fully resolvedhydrodynamics, called the Smooth Profile Method (SPM). We have

Swimmerexample, to accurately resolve turbulent motion).

studied the collective behavior of swimming particles under confinement,

pusherpullerReynolds number, and the frequency dependent polarizability of charged
particles in oscillating electric fields. In addition, we have also worked toextend the SPM to handle rheological measurements of complex particle

Squirmeras well as the dynamics of sedimenting colloidal particles at highdispersions (i.e. non-spherical particles).
In our study of active or swimming particles, we have adopted the simple“squirmer” model, in which the swimmers are modeled as sphericalparticles with modified stick boundary conditions at their surface. Bychanging the velocity profile of the fluid at the particle/fluid interface,swimming dir.
fluid flow
surface flow

Figure 1. Schematic representation of
the squirmer model.

one can easily represent the two basic types of swimming motion: “pusher” and “pullers” (see Figure 1). As afirst approximation, the fluid velocity at the surface is given by

where U 0 is the swimming velocity of an isolated particle,  is the polar angle, and ˆ the tangential
unit vector. If   0 (   0 ) we the flow profile generated by the particle is that of a puller (pusher). For
the special case when   0 we have a neutral or potential squirmer. The value of  is crucial when
determining the hydrodynamic interactions between pairs of particles, as they will be pushed/pulled in－ 83 －

Ⅳ 研究業績 (2014)

different directions, depending on their relative
position an orientation. In addition, the strength of thehydrodynamic interactions also depends strongly on : if  is zero, the flow field disturbance is more
localized, decaying as 1 / r 3 (where r is the distance
between the swimmers), otherwise it will decay as

1 / r 2 . Such differences have important consequences
when one considers the collective behavior ofswimming

dispersions.

In

particular,consideredpseudo-2D

geometries

we

that

have
mimic

experiments on active Janus particles, in which Figure 3. Time evolution of the order parameter for different
particles are placed between two flat parallel walls, types of swimmers.
and constrained to move in two dimensions. We have foundthat only neutral particles (   0 ) are able to exhibit aflocking state (all particles moving in the same direction).
Furthermore, we have seen that this collective behavior can be
attributed to the short-range hydrodynamic interactions, since
introducing an additional short-range repulsive forceF

between the particles makes the flocking state unstable. Figure
2 shows the order parameter e as a function of time ( e isone for an ordered system, zero for completely disorderedsystem), obtained from simulations for different values of  .
The instability of the flocking state for   0 is also due tothe hydrodynamic interactions, as the long-range disturbances
generated by the swimming motion give rise to fluctuations in
the fluid, which themselves cause a diffusive type of motion
for the particles (even in the absence of any thermal
fluctuations). These fluctuation are enough to hinder any
global flocking, particularly for   1, where strong vortices
are generated at the front/back of the pushers/pullers. To
measure the strength of these fluctuations, we have computed~

an effective hydrodynamic diffusion coefficient DT for theparticles (which considers only the fluctuating motion around Figure 2. (top) Enstrophy and (bottom) effective
the inherent swimming), as well as the enstrophy in the fluid diffusion coefficient as a function of swimming(which is directly related to the energy dissipation). As seen in mode for two concentrations. All quantities are
Figure 3, both quantities present the same overall behavior: A scaled with respect to the corresponding value
minimum for   0 , and a rapid increase as  increases. at   0 .
In addition, we see a clear asymmetry between pushers and－ 84 －

Ⅳ 研究業績 (2014)

pullers, with the latter showing stronger diffusion/energy dissipation. Understanding this asymmetry between
pushers and pullers, and how it affects the physical properties of the dispersion is still a work in progress.
Finally, in order to overcome the effect of these fluctuations on the stability of the flocking state, we are now
considering additional alignment mechanisms which can make such flocking stable, even for   0 ; forexample, by considering patchy or dipolar interactions between the particles. In this way, we will also beable to make a more direct comparison with experiments on Janus particles.

2. Original papers(1) Tanh-Nghi Nguyen, Magali Duvail, Arnaud Villard, John J. Molina, Philippe Guilbaud, andJean-François Dufrêche
“Multi-scale modeling of uranyl chloride solutions”
J. Chem. Phys. 142(2), 024501 (2014).
(2) Adnan Hamid, John J. Molina, and Ryoichi Yamamoto“Direct numerical simulations of sedimenting spherical particles at non-zero Reynolds
number”
RSC Advances, 4(96), 53681 – 53693 (2014)(3) Adnan Hamid, John J. Molina, and Ryoichi Yamamoto“Simulation studies of microstructure of colloids in sedimentation”
Mol. Sim., Proceedings of the 3d International Conference on Molecular Simulation,
DOI:10.1080/00268976.2015.1059510 (2015)(4) Chunyu Shih, John J. Molina, and Ryoichi Yamamoto“Dynamic polarization of a charged colloid in an oscillating electric field”
Mol. Phys., DOI:10.1080/00268976.2015.1059510 (2015)
3. Presentation at academic conferences(1) John J. Molina, Jean-Baptiste Delfau, Masaki Sano, and Ryoichi Yamamoto“Emergence of Collective Dynamics in Active Particle Suspensions” [poster]
Physics of Structural and Dynamical Hierarchy in Soft Matter, Tokyo, March 16-18, 2015
4. Others
1) John J. Molina“Dynamics of Swimming Particles: A DNS approach”
YITP Seminar (Hayakawa Lab), Kyoto, June 25, 2014
2) John J. Molina“Computational Modeling of Active Matter: Collective Dynamics in Swimming－ 85 －

Ⅳ 研究業績 (2014)

Suspensions”
ISSP Seminar (Noguchi Lab), Tokyo, November 21, 2014
3) John J. Molina, Jean-Baptiste Delfau, Masaki Sano, and Ryoichi Yamamoto“Emergence of Collective Dynamics in Active Particle Suspensions” [poster]
Kyoto Winter School for Statistical Mechanics, Kyoto
February 4-17, 20154) John J. Molina, Norihiro Oyama, Ryoichi Yamamoto“Computational Modeling of Active Matter”
Curie Institute Seminar (J.-F. Joanny Lab), Paris, February 26, 2015

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Ⅳ 研究業績 (2014)

Jing-Dong Guo
Research Fellow

Jing-Dong Guo
Research Fellow
1.

Summary of the research of the year
Dispersion Force Effects on the Dissociation of “Jack-in-the-Box” Diphosphanes
and Diarsanes
The earlier EPR experiments showed that the reduction of the sterically crowded dialkyl or diamido

phosphorus or arsenic halides ClER2 (E = P or As; R = −CH(SiMe3)2 or −N(SiMe3)2) yielded solutions
containing the persistent radicals :Ė{CH(SiMe3)2}2 or : Ė{N(SiMe3)2}2. The V-shaped monomeric
structures of the alkyl substituted radicals :Ė{CH(SiMe3)2}2 (E = P or As) were further confirmed by gas
electron diffraction (GED). However, in the solid, crystalline state they were shown to be dimerized withrelatively long P−P (2.3103(7) Å) and As−As (2.5384(16) Å) bonds. The attractive dispersion forces
between the hydrocarbon-substituted sterically bulky dialkyl or diamido groups may play important role
for the dimerization under ambient conditions..
With hybrid density functional theory (DFT) at the B3PW91 and B3PW91-D3 levels, we explored
the attractive dispersion forces on the present P and As compounds. Here we only present the calculated
results for alkyl substituted compounds shown in Scheme 1.
Scheme 1. The Dissociation of the [:E{CH(SiMe3)2}2]2 (E = P or As) Dimers with syn,anti Arrangementof -CH(SiMe3)2 Substituents to Two :Ė{CH(SiMe3)2}2 in the syn,syn Conformation.

§1. Comparison in geometry between theoretical and experimental results.

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Ⅳ 研究業績 (2014)

It can be seen in Table 1 that there is close agreement between the calculated and experimental
distances in the case of the tetraalkyls. But the calculated CAsAsC torsion angles show deviations in therange 8.4−11.5° from the experimentally measured values when the D3 dispersion term is included. To
estimate the effect of the angular deviations in the calculated diarsane angles on the dispersion energy, an
additional calculation was carried out in which the real system model was fully optimized but with thedihedral angles fixed at the experimentally measured positions. The very small dissociation energy
difference, 37.1 vs 36.5 kcal mol−1, indicates little effect on the dispersion energy upon changing thetorsion angle.
Table 1. Calculated Structural Parameters and Dissociation Energies of [E{CH(SiMe3)2}2]2 (E = P, As) at
the B3PW91 and B3PW91−D3 Levels of Optimization§2. The attractive dispersion forces play important role in the P and As alkyl dimers.

As shown in Table 1, the calculated dissociation energies without the inclusion of dispersion force

effects are negative: −10.3 (P) and −6.5 (As) kcal mol−1. In contrast, the incorporation of dispersion force
effects changes in these numbers to +37.6 (P) and +37.1 (As) kcal mol−1. In other words, without thedispersion forces the monomeric radical form is preferred over the dimeric structure, presumably becauseof steric repulsion between the substituents and the accumulated strain energies. However, the attractive
dispersion force between the ligands overcomes these dissociation tendencies to favor the diphosphaneand diarsane structures.
§3. Dimeric structure is favored under ambient conditions, while dissociation is favored at hightemperature.

The data in Table 2 show that the inclusion of the dispersion correction (−D3) has a very large effect on
the ΔH and ΔG energies, and a smaller but significant effect on the ΔS values. Without the dispersion－ 88 －

Ⅳ 研究業績 (2014)

optimization, dissociation is strongly favored at all temperatures, whereas with the dispersion correction
the dimeric structure is favored at −20 and 25 °C, while dissociation is favored at high temperatures near
150 °C. For phosphorus, the ΔG(−D3) value is slightly positive, having a value of 2.2 kcal mol−1 at
147 °C (the temperature of the GED studies) and at 1 atm pressure. Upon lowering of the pressure to 1
Torr, this becomes −5.3 kcal mol−1, showing that dissociation to radicals is favored, consistent with theobserved structure in the gas phase. At lower temperatures (i.e., −20 and 25 °C) the associated structure isfavored (ΔG = 14.2 and 10.9 kcal mol−1), consistent with the dimeric structure observed in the crystalline
phase. For the arsenic derivative, the dissociated structure is energetically favored at 152 °C (GED studies
temperature) at both 760 and 1 Torr pressure, consistent with the experimental data, whereas at 25 and−20 °C, the dimeric structure is favored, consistent with the crystal structure observedfor :As{CH(SiMe3)2}2]2.
Table 2. Thermodynamic Data (kcal/mol) for the Dissociation of [Ë{CH(SiMe3)2}2]2 into
Two :Ė{CH(SiMe3)2}2 Radicals.

In conclusion, the DFT calculations using different methods on the dipnictane tetraalkyl species withinclusion of attractive dispersion forces show that the dimeric structures are favored over the radicalmonomers under ambient conditions. The attractive forces exceed those that stabilize the radicals throughrelaxation and conformational changes. The results underline the general necessity of incorporating thedispersion force effects in calculations on sterically crowded molecules. Calculations for themonomer−dimer equilibrium in the tetraalkyl species indicate that they are governed mainly by dispersion
force attraction and entropic factors.

2.

Original papers:
Jing-Dong Guo, Shigeru Nagase, and Philip P. Power,"Dispersion Force Effects on the Dissociation of “Jack-in-the-Box” Diphosphanes andDiarsanes"
Organometallics 34, 2028-2033 (2015).

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Ⅳ 研究業績 (2014)

Wei-Wei Wang
Wei-Wei Wang

SPR Fellow
SPR Fellow

1. Summary of the research of the year
Multistep Reconstructions of Half-saturated Zigzag Carbon Nanotubes
Since the first discovery in 1991, carbon nanotubes (CNTs) have drawn much attention
as promising functionalized materials in nanoelectronics and spintronics. Similar to the 1Dgraphene nanoribbon (GNR), the edge states, and in particular of two primary edge structures(armchair and zigzag edges) of CNTs are considered to play a prominent role on theelectronic, magnetic and mechanical properties. In the field of CNT chemistry, hitherto
studies on the armchair edge, i.e. the bottom-up cycloaddition growth mechanisms of CNTs,
have been well-developed in both theory and experiments. However, investigations on thecase of zigzag edge of CNTs are still limited. In the present work, a novel multistep
reconstruction mechanism of the open-ended zigzag CNTs were introduced by using DFT
calculations. We aim to uncover the kinetic process of edge deformation and to elucidate theimpact of deformed edge on the stability and electronic properties of CNTs.

Figure 1. Structure and spin density distribution of half-capped (6,0)CNT
A finite C3v symmetric (6,0)CNT was selected as the CNT model. As shown in Figure 1,
one side of the tube is terminated by the carbonic cap and the other side is open-ended. It
should be mentioned that (6,0)CNT can be capped by only one type of carbonic hemisphere intheory and the hydrogen-terminated model is not used to avoid the impact of hydrogen atoms.
All computations were performed with the HSEH1PBE density functional in conjunction withthe basis sets of 6-311G(d) by using the Gaussian 09 program.
First, we optimized the pristine (6,0) CNT under different electronic spin states and aheptet state was proved as the ground state. The calculated spin distribution (Figure 1)
suggests that the high-spin state of this CNT structure results from the bared carbon atoms at
the open edge, which contribute six unpaired σ electrons. The kinetic process of the firstreconstruction step is depicted in Figure 2. By overcoming a concerted 10-membered cyclic
transition state (TS1), the fused two hexagons at edge transform into a pentagon-heptagon(5-7) pair. This process is similar to the reconstruction of GNR at edge and an edge cut of theclassical Stone-Wales transformation (SWT) of fullerenes. Energetically, this process is－ 90 －

Ⅳ 研究業績 (2014)

exothermic with the reaction energy (Er = Eproduct - Ereactant) of -31.4 kcal/mol, indicating aself-stabilization character of the reconstruction from the zigzag edge to the deformed 5-7
edge. Kinetically, the reaction barrier E‡ is 41.4 kcal/mol which is significantly lower thanthat of the SWT on the sidewall network of CNTs. Furthermore, the total spin of CNT wasfound to reduce by one after the rearrangement and the electronic ground state was quintet forthe deformed product P1. As elucidated in Figure 2, after the unsaturated zigzag fragment in
the reactant transforms to the 5-7 edge, a triple C-C bond was formed in the heptagonal ring,which eliminate two pristine unpaired electrons and lead to the decrease of the total spin by
one.

Figure 2. The first step reconstruction of half-capped (6,0)CNT
Subsequently, since the symmetry of CNT is broken after the first step, theregioselectivity of second step rearrangement on P1 was taken into account. As shown in
Figure 3, all the six possible SWT reactions were calculated and the reconstruction takes
place on the site that next to the heptagon was proved to exhibit the lowest E‡ (34.3 kcal/mol)as well as the most negative Er (-33.3 kcal/mol), implying that the multistep reconstruction of
zigzag edge is a sequential rather than a random process. Moreover, it should be mentionedthat the second step is spontaneous because it is thermodynamically exothermic and thebarrier is 7.1 kcal/mol lower that that of the first step kinetically. The spin density diagram of
P2 is exhibited in Figure 3. In accord with the initial step, the total spin after reconstruction is
reduced by one and the ground state of P2 is triplet.

Figure 3. The regioselective second step reconstruction of half-capped (6,0)CNT
In the final step, two hexagons are surviving at the open edge of P2 and therefore only
two deformed structures are available after reaction: the alternating 5-7 edge or the edge withfused 5-5 and 7-7 fragments. Calculations demonstrate that formation of the former one with
the E‡ of 33.9 kcal/mol and the Er of -32.1 kcal/mol is more favored both thermodynamicallyand kinetically, whereas the latter one is unfavorable in energy because of the much higher
molecule strain caused by the pentagon-pentagon and heptagon-heptagon fragments. From theviewpoint of molecular spintronics, interestingly, we found the ground state of final productP3 is closed-shell singlet with a large singlet-triplet splitting energy of 10.7 kcal/mol. The－ 91 －

Ⅳ 研究業績 (2014)

total spin of half-saturated (6,0)CNT dramatically transforms from a high-spin state (heptet)
to an unpolarized singlet after three steps of reconstructions, indicating the structuraldeformation of zigzag edge not only enhances the stability but also significantly modifies themagnetic property of materials.

Figure 4. The regioselective third step reconstruction of half-capped (6,0)CNT

Figure 5. Relative energies of (6,0)CNT and reconstructed products (left) and
Energy barriers of multistep reconstructions (right)

Figure 6. Spin density distributions of (6,0)CNT and reconstructed products
Overall, the multistep reconstructions of the open edge of zigzag (6,0) CNT have been
explored by quantum chemistry calculations. Thermodynamically, the deformation fromunsaturated zigzag edge to deformed 5-7 edge was demonstrated as a stabilization process andthe stability enhanced linearly with the increase of 5-7 pairs. Kinetically, Because of thereactive dangling bonds at edge, the barriers of rearrangements (<50.0 kcal/mol) are much
lower than those of reactions on the sidewall network of CNTs or fullerenes (100.0 ~ 200.0
kcal/mol). As drawn in Figure 5, the first step exhibits the largest energy barrier, suggestingthat the initial transformation from two hexagons is the rate-determining step and thefollowing steps can take place spontaneously like an unzipping process. Moreover, the－ 92 －

Ⅳ 研究業績 (2014)

regioselectivity of the multistep reactions were studied. We proposed that the reconstructions
prefer occur in a sequence because successive transformation next to the already existing 5-7
pair is much more feasible in energy. Furthermore, our calculations indicate that thereconstruction is a special process in which the total spin decreased gradually in each step,
revealing that the half-saturated zigzag CNT can be utilized to design novel intramolecularspin-transfer materials.
2. Original papers
1. T. Morosaki, T. Suzuki, W. W. Wang, S. Nagase, and T. Fujii, “Syntheses, Structures, andReactivities of Two Chalcogen-Stabilized Carbones” Angew. Chem. Int. Ed. 2014, 53, 9569.
2. Q. Zhou, H. Li, Y. Lian, M. Suzuki, L. Bao, W. Cai, W. W. Wang, S. Nagase, X. Lu and T.
Akasaka, “Regioselective synthesis and molecular structure of the first derivative ofpraseodymium-containing metallofullerenes” Chem. Commun., 2014, 50, 9876.
3. Y. Maeda, M. Kimura, C. Ueda, M. Yamada, T. Kikuchi, M. Suzuki, W. W. Wang, N. Mizorogi,
N. Karousis, N. Tagmatarchis, T. Hasegawa, M. M. Olmstead, A. L. Balch, S. Nagase and T.
Akasaka “Isolation and characterization of [5,6]-pyrrolidino-Sc3N@Ih-C80 diastereomers” Chem.
Commun., 2014, 50, 12552.
4. H. Zheng, X. Zhao, L. He, W. W. Wang, and S. Nagase “Quantum Chemical Determination ofNovel C82 Monometallofullerenes Involving a Heterogeneous Group” Inorg. Chem., 2014, 53,
12911.

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Ⅳ 研究業績 (2014)

Miho Hatanaka
FIFC Fellow
1. Summary of the research of the year
1.1. Theoretical study of the thermo-sensitive luminescence of Ln(III) compounds
Lanthanide (Ln) compounds have been widely used for luminescence materials, such as in vivo
probes, lasers, optical fibers etc. Some of the advantages of Ln(III) compounds are that theshapes of the emission spectra are very sharp (like isolated cations), the emission wavelengths
are independent of the surrounding environment, and only the emission intensities depend
heavily on the surroundings. These characters can be explained by the inner-core 4f electrons.
Ln(III) have distinct electronic configurations, such as 1s22s2…4fN5s25p6, in which open-shell
4f electrons are shielded by closed-shell 5s and 5p electrons from outside. Therefore, theproperties caused by 4f electrons, such as the excitation energies of 4fN excited states, and theshapes of potential energy surfaces (PESs) of 4fN states, are not affected by the change ofsurrounding environment.
One of the interesting applications of Ln
luminescence is thermo-sensitive luminescentprobes that use Eu(III) and Tb(III). Eu(III) andTb(III) show red and green emissions causedby the f-f transitions (5DJ → 7FJ’), respectively.
With appropriate ligands, the intensity of the

Figure 2. Energy shift approximation

f-f emission decreases (or sometimes increases)
astemperature

increases,

enabling

these

complexes to be used as temperature sensors.
The mechanism of Ln(III) luminescence has

Figure 1. Possible mechanism of Tb(III)luminescence and quenching

been explained by five steps shown in Figure 1. The process starts from (1) ligand-centeredexcitation from the singlet ground state (S0) to a singlet excited states (Sn), followed by (2)intersystem crossing (ISC) from the excited state Sn to the lowest triplet state (T1), (3)excitation energy transfer (EET) from the ligand T1 to Ln-centered 4fN excited state(s), (4)internal conversion (IC) from the 5DJ” state to the lowest quintet state 5DJ, and (5a) f-f emission
from 5DJ to 5FJ’. The quenching process also can be explained based on Figure 1. The lifetime of
Ln-centered excited state (5DJ) is rather long because the f-f transitions from 5DJ to 5FJ’ areparity-forbidden as well as spin-forbidden transitions. Thus, the quenching process, such as (5b)the backward EET and (5c) the ISC on the ligand, can take place when the crossing pointes
shown as (5b) and (5c) in Figure 1 are enough low. To control the quenching process, which
directory affects the intensity of the f-f emission, we need to control the energy levels of the twocrossing points.
How can we compute the energy levels and structures of these two crossing points as well as
LM on the ligand-centered T1 and Ln-centered excited states? The ab initio calculations of such
94 －excited states in Ln compounds are highly－demanding
because relativistic effects, electron

correlation need to be considered explicitly. Here, we change the view point. As mentioned

the backward EET and (5c) the ISC on the ligand, can take place when the crossing pointes
shown as (5b) and (5c) in Figure 1 are enough low. To control the quenching process, which
directory affects the intensity of the f-f emission, we need to control the energy levels ofⅣthetwo (2014)
研究業績
crossing points.
How can we compute the energy levels and structures of these two crossing points as well as
LM on the ligand-centered T1 and Ln-centered excited states? The ab initio calculations of such
excited states in Ln compounds are highly demanding because relativistic effects, electron
correlation need to be considered explicitly. Here, we change the view point. As mentioned
above, the PESs of 4fN excited states have almost the identical shapes to that of the 4fN groundstate, and the excitation energies are independent of the surrounding environment. Thus, thePESs of 4fN excited states can be described by that of the 4fN ground state corrected by an“energy shift” that is unique for each excited state. We call this approximation, the “energy shiftmethod”. (See Figure 2)
 Case study 1: Tb(III) complexes
As the first case study, we apply this approximation to tree Tb(III) complexes containing
different ligands; hexafluoroacetylacetonato (hfa), acetylacetonate (acac), and nitrate ion (NO3−).
According to the experimental studies by Hasegawa group, as the temperature increases, thegreen emission intensities of -diketone ligand (hfa and acac) coordinated Tb(III) complexes
decrease, whereas that of NO3 coordinated Tb(III) complex increase a little. To explain thereason for the different behaviors of the three complexes, the critical points on and between the
PESs were determined for the three complexes, Tb(X)3(H2O)2 (X = hfa, acac, and NO3). The
full geometry optimizations of LM and minimum seams of crossing (MSXs) were performed
using the Global Reaction Route Mapping (GRRM) program with energies and energy
derivatives of S0 and T1 states computed at the B3LYP-D3 level by the Gaussian09 program.
As a result, the dependence of the thermo-sensitivity on the ligands can be understood by thedifferent rate-determining steps for emission or quenching. For -diketone coordinated Tb(III)complexes, the MSX for the ISC on the ligand (5c in Figure 1) is the highest point among theemission and quenching process. Thus, as the temperature increases, only the rate for thequenching increases, which results in the decrease of the emission intensity. For NO3
coordinated Tb(III) complex, the highest point is the MSX for the EET (3 and 5b in Figure 1).
Therefore, as the temperature increases, the rate for the forward EET increases, which results inthe slight increase of the emission intensity.
 Case study 2: Tb(III)/Eu(III) containing polymers
Next, we focus on another temperature sensor, called the Chameleon, whose emission color
changes from green, yellow, to red as the temperature increases. The Chameleon sensor is apolymer in which Tb(hfa)3 and Eu(hfa)3 are connected by a phosphoryl linkage ligand (dpbp:
4,4’-bis(diphenylphosphoryl) biphenyl). According to the experimental study, (i) the intensity of
red emission of the polymer including only Eu(III) was almost independent on the temperature.
(ii) The green emission intensity of the Chameleon sensor was more sensitive to the temperaturechange than that including only Tb(III). These experimental results mean that the excitationenergy on Tb(III) could transfer to Eu(III). In the conventional theoretical study based on the
crystal field theory, only the direct EET between two Ln(III) has been considered. However, in
this mechanism, the rate of the direct EET becomesquite slow with more than 10 Å distance－ 95 －
between two Ln(III), which is shorter than the Tb-Eu distance in the Chameleon. Thus, we4,4’-bis(diphenylphosphoryl) biphenyl). According to the experimental study, (i) the intensity of
red emission of the polymer including only Eu(III) was almost independent on the temperature.
Ⅳ 研究業績
(ii) (2014)
The green emission intensity of the Chameleon sensor was more sensitive to the temperaturechange than that including only Tb(III). These experimental results mean that the excitationenergy on Tb(III) could transfer to Eu(III). In the conventional theoretical study based on the
crystal field theory, only the direct EET between two Ln(III) has been considered. However, in
this mechanism, the rate of the direct EET becomes quite slow with more than 10 Å distance
between two Ln(III), which is shorter than the Tb-Eu distance in the Chameleon. Thus, we
focused on the T1 state of thelinkageligand(dpbp)

andconsidered that the EET fromTb(III) to Eu(III) takes placethrough the T1 state of thelinkage ligand. To examine thisidea, we searched the MEXs
where

the

EET

from

Tb-centered excited state to the

Figure 3. Energy levels of the LM and MSXs in the Chameleon(Energies in orange are calculated for Ln(tfa)3(H2O)2)

ligand T1 and from the ligand T1 to Eu-centered excited state by using the energy shift
approximation with the DFT-D3 method. Figure 3 shows the energy levels of the critical points
on and between PESs in the model molecule (Tb(hfa)3-dpbp-Eu(hfa)3). The critical points (LMand MSXs) relating to T1 on dpbp are lower than the MSXs on the hfa. Thus, we can say that
the T1 state of the linkage ligand mediates the EET from Tb(III) to Eu(III). In other words, we
can control the rate of the EET between two Ln(III) by changing the linkage ligand with thedifferent T1 energy levels. To explore the temperature sensors whose thermo-sensitivity isdifferent from the original Chameleon, we examined three compounds including different
phosphoryl linkage ligand (dpb, dppcz, and dpbt). The MSXs between ligand T1 and Tb- (orEu-) centered excited states as well as the LM on ligand T1 state is the highest for dpb, followedby dppcz, dpbp (in the original Chameleon), and dpbt. This result is consistent with theexperimental thermo-luminescence measured by Hasegawa group. As shown above, the newly
proposed energy shift method can be a reasonable approximation to explore the PESs and to
explain the mechanism of emission, quenching, and EET qualitatively.

1.2. Reason of the low quantum yield (QY) of Eu(III) helical ligand complexes andcomputational molecular design for higher QY
One of the recent topics for the luminescencematerials is the computational molecular design whichshows high quantum yield (QY). As mentioned above,
the rate for the quenching process is determined by theenergy levels of the crossing points. Thus, one way todesign the luminescence material with higher QY is tomake the energy levels of the ISC on the ligand (5c inFigure 4. The top and side views of thegeometry of EuL optimized on (S0, 7F0)

Figure 1) less stable. In this study, we focus on Eu(III) complex with a hexadentate ligand(abbreviated to EuL shown in Figure 4). The QY depends on the state and temperature: in thesolid state of EuL, the QYs of f-f emission are 64 % and 53 % at 77 K and room temperature,
respectively, while that in the solution is only 12 % (at r.t.). To understand the different QYs in
96 －solid and－ solution,
we searched the critical points on andbetween the PESs (shown in Figure 1). As the result indesign the luminescence material with higher QY is tomake the energy levels of the ISC on the ligand (5c inFigure 4. The top and side views of thegeometry of EuL optimized on (S0, 7F0)

研究業績 (2014)
Figure 1) less stable. In this study, we focus on Eu(III) complex with a hexadentateⅣ ligand(abbreviated to EuL shown in Figure 4). The QY depends on the state and temperature: in thesolid state of EuL, the QYs of f-f emission are 64 % and 53 % at 77 K and room temperature,
respectively, while that in the solution is only 12 % (at r.t.). To understand the different QYs insolid and solution, we searched the critical points on andbetween the PESs (shown in Figure 1). As the result in
vacuum, three critical points; LMs on the ligand S0 and T1,
and the MSX where the EET takes place (3 in Figure 1)
had quite similar structures. Only the structure of the MSX
Figure 5. Structures of criticalpoints. Blue, red, green, and yellow
are LMs on S0, T1, MSXs for EET
and ISC, respectively.

where the ISC on the ligand takes place (5c in Figure 1)
were quite different as shown in Figure 5. If we can find aligand in which the structural motions from T1 to MSX for
the ISC, such as twist the C2 unit in diamine part and bent

the C-H bond, are restrained, we could achieve a luminescence complex with a higher QY.
Several hexadentate ligands including different substituents were examined. The substituents on
the N atom shown in pink circle in Figure 5 affected the energy levels of T1 states changed. In
contrast, the substituents on the C2 unit in the diamine part affected the T1 level a little. Finally,
we found that the hexadentate ligand with 1,2-dimethylcyclohexane on the diamine part had thelow energy barrier for the forward EET and high barrier for the ISC process.
The reason of the higher QY in the solid state can also understood by the MSX for the ISC. In
the solid state, the motion of the two biphenyl parts were limited by the  interaction from thesurrounding biphenyl groups. Those of C2 unit and N-H bond were also limited by the ionicinteractions from surrounding acetonitrile molecules. As discussed above, the QY can beunderstood and controlled by the energy level and structure of the MSX where the ISC on theligand takes place. This study could be the first example in which a higher QY of Ln(III)compound is achieved by controlling the ISC process.

2. Original papers(1) M. Hatanaka, K. Morokuma, “Exploring the reaction coordinates for f-f emission andquenching of lanthanide complexes – thermosensitivity of terbium(III) luminescence”, J.
Chem. Theory Comput. 10, pp 4184-4188 (2014).
(2) L.W. Chung, W.M.C. Sameera, R. Ramozzi, A.J. Page, M. Hatanaka, G.P. Petrova, T. Harris,
X. Li, Z. Ke, F. Liu, H.-B. Li, L. Ding, K. Morokuma, “The ONIOM Method and its
Applications” Chem. Rev. in press.
(3) M. Hatanaka, K. Morokuma, “How Can Fluctional Chiral Lanthanide(III) Complexes
Achieve a High Stereoselectivity in Aqueous Mukaiyama-Aldol Reaction?” ACS. Catal. 5,
pp 3731-3739 (2015).
(4) M. Puripat, R. Ramozzi, M. Hatanaka, W. Parasuk, V. Parasuk, K. Morokuma, “TheBiginelli reaction is a urea-catalyzed organocatalytic multicomponent reaction”, J. Org.
Chem. in press.

－ 97 －

3. Presentations at academic conferences

Biginelli reaction is a urea-catalyzed organocatalytic multicomponent reaction”, J. Org.
Chem. in press.
Ⅳ 研究業績 (2014)

3. Presentations at academic conferences(1) ○M. Hatanaka, “Theoretical Study of Stereoselective C-C Bond Formations Catalyzed by
Lanthanide Complexes”, 錯体化学会第 64 回討論会, Tokyo, Japan, September, 2014
(Invited Talk)(2) ○畑中美穂, 諸熊奎治, “ランタノイドの発光を用いた感温センサーにおける励起エ
ネルギー移動に関する理論的研究”,第 8 回分子科学討論会 2014, 広島, 2014 年 9 月.
(Oral)(3) ○畑中美穂, 堀直也, 前田理, María Luisa Senent, Majdi Hochlaf, 諸熊奎治, “星間空間における炭化水素アニオンの生成機構に関する理論的研究”, 第 17 回理論化学討論会 2014, 福岡, 2014 年 5 月. (Poster)

4. Others (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, 2015 年 1 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”,理系インスパイアー講演会, 兵庫
県立北摂三田高等学校, 2014 年 10 月. (高校 2 年生(理系限定約 120 人)対象)(3) 諸熊グループ(畑中美穂, Julong Jiang, Romain Ramozzi, WMC Sameera, 鈴木聡), “コンピュータで化学反応の世界を探る”, 京都大学アカデミックディ 2014, 2014 年 9 月 「研(究者と立ち話」のコーナーでポスター発表)－ 98 －

Ⅳ 研究業績 (2014)

Romain Ramozzi
Research Fellow (JSPS and FIFC), Fukui Kenichi Memorial Research Group 1

Research Fellow (JSPS and FIFC), Fukui Kenichi Memorial Research Group 1

1. Summary of the research of the year
With atoms economy, easy practical set up, the multicomponent reactions have been particularly
popular during the past twenty years.[1] Among them, the Passerini reaction is known to be the first
isocyanide based multicomponent reaction. This reaction involves an aldehyde, an isocyanide and acarboxylic acid. Maeda et al. studied the mechanism in 2011 by using the AFIR method in
conjunction with DFT calculations in gas phase.[2] They found that in gas phase the acyl-imidate
formation step proceeds concertedly, as widely represented in organic textbooks and publications.
Remarkably, the next step, an acyl transfer step called a Mumm rearrangement, was found to becatalyzed by a second acid molecule and makes the Passerini reaction an organocatalytic reaction(see Scheme 1).

Scheme1: Proposed mechanism for the Passerini reaction by Maeda et al. in 2011.

In the present study, we decided to investigate the solvent effect of this reaction. Indeed, thisreaction is known to react better in an aprotic apolar solvents, like the dichloromethane, contrary to
the very close reaction the Ugi coupling, which is known to react better in a protic polar solvent like－ 99 －

Ⅳ 研究業績 (2014)

methanol.[3]Interestingly, the new calculations performed at the mPW2PLYP/6-311++G(d,p) level predicted thestability of a nitrilium species during the acyl-transfert formation step. This method and result wereconfirmed with various functionals (M06 familly, B2PLYP-D3, …), basis sets (from 6-31G(d) to
aug-cc-pVTZ) and the ab-initio level CCSD(T)//MP4(SDQ)/aug-cc-pVTZ was taken as a reference
to confirm the choice of this method.
Moreover, the initial step, which is the addition of the isocyanide on the aldehyde was found to be
activated, not by one (as previously observed), but by two carboxylic acid molecules despite theentropic contribution of the second carboxylic acid molecule. Therefore, a revised mechanism was
proposed as shown in scheme 2 involving the organocatalyst from the beginning of the reaction, as
well as the existence of the nitilium intermediate.

Scheme2: Revised mechanism for the Passerini reaction in 2015.
To understand the solvent effect, the PCM approach was found to be not good enough to reproduce
the experimental results and various microsolvated model systems were then investigated.
Surprisingly, the absence of hydrogen bonds was found to increase the reactivity of the aldehyde
and isocyanide during the rate determining step (the nitrilium formation step) and thus explains the－ 100 －

Ⅳ 研究業績 (2014)

experimental observations. Moreover, the analysis of these results permits to understand the true
solvent effect in the rate-determining step of the Passerini and Ugi couplings. While for the Ugi
coupling the polarity of the solvent is crucial, it is the absence of proticity in the Passerini reactionthat leads to better yields.
Bibliography:[1] J. Zhu and H. Bienaymé, Multicomponent Reactions ; Wiley-VCH, 2005
[2] S. Maeda, S. Komagawa, M. Uchiyama and K. Morokuma, Angew. Chem. Int. Ed. 2011, 50,644.
[3] a) L. El Kaïm, L. Grimaud, Tetrahedron, 2009, 65, 2153-2171; b) N. Chéron, R. Ramozzi, L. El
Kaïm, L. Grimaud and P. Fleurat-Lessard, J. Org. Chem., 2012, 77, 1361.

2. Original papers- R. Ramozzi, N.Chéron, L. El Kaïm, L. Grimaud, and P. Fleurat-Lessard, Chem. Eur. J.,
2014, 20 (29), 9094-9099.
- L. Wa Chung, W. M. C. Sameera, R. Ramozzi, A. J. Page, M. Hatanaka, G. P.
Petrova, T. V. Harris, X. Li, Z. Ke, F. Liu, H.B. Li, L. Ding, and K. Morokuma,
Chem. Rev., 2015, doi:10.1021/cr5004419, 120 pages.
- R. Ramozzi, K. Morokuma, J. Org. Chem., 2015, doi:10.1021/acs.joc.5b00594- J. Jiang, R. Ramozzi, K. Morokuma, Rh(III)-Catalyzed C(sp3)-H Bond
Activation via an External Base Metalation Deprotonation Mechanism, Chem.
Eur. J., accepted

3. Presentations at academic conferences
Oral communication: The Isocyanide Multicomponent Reactions: a never-ending source ofinnovation, 14th RCTF, Paris (France), July 2014.
Poster communication: The solvent effect in the Passerini reaction, 12th FIFC symposium,
Kyoto (Japan), 2015

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Ⅳ 研究業績 (2014)

4. Others
Poster presentation in "Conversation with Researchers" in the Academic
Day of Kyoto University
Title: Explore the world of chemistry reactions by computers
Authors: Morokuma Group (Miho Hatanaka, Julong Jian, Romain Ramozzi, W.M.C.
Sameera, and Satoshi Suzuki), Fukui Institute for Fundamental Chemistry,
Kyoto University
Date and Place: September 28 (Sunday), 2014. Clock Tower Centennial Hall,
Kyoto University－ 102 －

Ⅳ 研究業績 (2014)

Satoshi Suzuki
Satoshi Suzuki
Research Fellow
Research Fellow
1. Summary of the research of the year
Exploration of quenching pathway of multiluminescent acenes using the GRRM strategy with
the SF-TDDFT method
Owing to their optical and electronic properties, π-conjugated systems have attracted much attention as afunctional material. Recently a series of π systems that consists of a flexible cyclooctatetraene (COT) core andaceneimide wings with different conjugation lengths has been synthesized. A significant feature of this system is
to show environment dependent emission from single component fluorophore. The system shows a blue emission
from the V-shaped structure in a polymer matrix or in a frozen solution, a green emission from the planar
geometry in solution, and a red emission in the crystalline state. The molecule with anthraceneimide wings isemissive both in solution and in the solid state, while the molecule with phenyleneimide has no emission either insolution or in the solid state. For the molecule with naphthaleneimide moiety, although no fluorescence isobserved in the various common organic solvents at room temperature, the compound shows fluorescence in thesolid state.
In many photochemical processes such as photochemcial reactions and fluorescence quenching, the conicalintersections (CIs) plays an important role because nonadiabatic transitions from excited states to the ground statetake place very efficiently in the vicinity of the CI.
In order to explain the difference in emission behavior of the present molecules, we adopted the GRRM
(Global Reaction Route Mapping) strategy to explore and locate minimum energy conical intersections (MECI)
between S1 and S0 for the three aceneimide 1-3 in figure 1. and to determine possible quenching pathways, startingfrom the Franck-Condon region. The difference in quenching pathway among the three systems would lead to thedifference of emission behavior.

Figure 1. Chemical structure of aceneimide compound 1-3－ 103 －

Ⅳ 研究業績 (2014)

Figure 2 shows structure of important critical points and their energies for molecule 1. A local minimum LM
on S1 surface is found near the C2v FC point (the ground state minimum GM) with a planar symmetric D2hstructure. The optimized MECI CIF also has a planar symmetric D2h geometry. CIF is higher in energy thanLM only by 11.7kJ mol-1. We also found a different type of MECI, CIB. This CIB shows large out-of-planebending of two neighboring CH bond in COT. In molecule 1, after vertical excitation, the molecule can reach to
CIF easily. This quenching pathway should be most preferable in solution. In addition, there is another pathway
to reach CI. Moreover, transition between S1 and S0 is forbidden by symmetry at LM. This is why molecule 1
shows nonradiative decay rather than emission.
For molecule 3, different from 1 and 2, two C2v local minima for S1 state were found(Figure 3). There are
one local minimum that has shallow V shape (LMV) and the other local minimum with flat C2v geometry(LMF). At LMF, S1 state belongs to 1B2 and thus transition from S1 to S0 is allowed. MECI for 3 near local
minimum has twisted structure, which has higher energy than FC by 50kJ mol-1. For this molecule, barrier
toward CI is high enough. Thus, in this molecule, fluorescence is more likely to take place at LMF than internalconversion around CI.

Fig.2 Energy profile of molecule 1.
Solid lines mean connections between points are confirmed by IRC or geometry optimization.
Connection for dotted line is not confirmed.

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Ⅳ 研究業績 (2014)

Fig 3 Energy profile of molecule 3.
Solid lines mean connections between points are confirmed by IRC or geometry optimization.
Connection for dotted line is not confirmed.

－ 105 －

Ⅳ 研究業績 (2014)

2. Original papers(1) Satoshi Suzuki, Satoshi Maeda, and Keiji Morokuma,”Exploration of quenching pathway ofmultiluminescent acenes using the GRRM strategy with the SF-TDDFT method”(in prepartion)

3. Presentation at academic conferences(1) ◯鈴木聡,諸熊奎治, “環境依存発光を示すアセン類縁体の消光経路探索”,第八回分子科学討論会 2014,広島,2014 年 9 月
4. Others
4.1 presentations at symposiums(1) Poster presentation in "Conversation with Researchers" in the Academic
Day of Kyoto University
Title: Explore the world of chemistry reactions by computers
Authors: Morokuma Group (Miho Hatanaka, Julonh Jianb, Romain Romazzi, WMC
Sameera, and Satoshi Suzuki), Fukui Institute for Fundamental Chemistry,
Kyoto University
Date and Place:
September 28 (Sunday), 2014. Clock Tower Centennial Hall,
Kyoto University(2) ◯鈴木聡,諸熊奎治, “環境依存発光を示すアセン類縁体の消光経路探索”, 新学術領域「高次複合光応答分子システムの開拓と学理の構築」,大阪,2015 年 1 月－ 106 －

Ⅳ 研究業績 (2014)

Travis Harris
Travis HARRIS
Research Fellow, Fukui Kenichi Memorial Research Group 1
Research Fellow, Fukui Kenichi Memorial Research Group 1
1. Hydroboration Mechanism Revisited: Alkene Addition Partner Depends on Ligand andSubstrate
Rh(I)-catalyzed hydroboration of alkenes has become a widely used reaction, producing
boronate esters with good regio- and stereoselectivity. These organoboranes can then befunctionalized via such processes as oxidation, amination, and C-C bond formation, while retainingchirality. Depending on the nature of the catalyst, the conditions, and the substrate, vinyl boronates
can also be produced as the major or sole product. Thus, to reliably predict the products that will beobtained from new substrates, and to rationally design ligands that enable greater selectivity, it isimportant to understand the mechanism and the factors that control it in detail.
The hydroboration mechanism for Wilkinson’s catalyst (RhCl(PPh3)3) has been studied indetail, whereas fewer studies have examined catalysts with chelating ligands, which are commonly
employed for asymmetric hydroboration. In this work we calculate full hydroboration mechanismsof neutral Rh(I) catalysts with pinacolborane (HBPin) and a series of bidentate ligands:
1,2-bis(dimethylphosphino)ethane (dmpe), 1,2-bis(diisopropylphosphino)ethane (dippe), and1,2-bis(ditertbutylphosphino)ethane (dtbpe). There are two distinct mechanisms, shown by thecatalytic cycle in Figure 1.

Figure 1. Catalytic cycle for Rh(I)-catalyzed hydroboration.

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Ⅳ 研究業績 (2014)

After oxidative addition of HBPin, addition of the alkene yields intermediates 3b’ and 3h’, whichlead to migratory insertion into the Rh-H or Rh-B bond, respectively. The resulting pentacoordinate
compounds isomerize to the reactive intermediates 4f’ and 5g’, before undergoing C-B or C-H
reductive elimination, respectively.
This investigation was specifically prompted by an experimental finding that norbornene
reacts faster than 1-octene, both yielding alkyl boranes. We thus employed norbornene and thecomputationally efficient propene as substrates in the DFT calculations, using B3LYP-D3 with the
SDD effective core potential basis set for rhodium and 6-31G* for other atoms. The THF solvent
was modeled by PCM. Free energy profiles for the H migration and B migration mechanisms were
calculated for both substrates using the dippe ligand. For propene, the H migration step was rate
limiting with a 20.2 kcal/mol barrier. The alternative, B migration pathway was more hindered, witha B migration barrier of 23.3 kcal/mol followed by a rate-limiting reductive elimination step (27.1
kcal/mol). By contrast, 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,
propene (and likely 1-octene) and norbornene undergo hydroboration via distinct mechanisms; theaddition partner is the hydride for propene, and BPin for norbornene.
The free energy profiles for the least hindered hydroboration pathways for propene andnorbornene are compared in Figure 2.

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

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Ⅳ 研究業績 (2014)

Norbornene has a lower rate-limiting barrier (18.4 kcal/mol) than propene (20.2 kcal/mol), which isconsistent with the experimental results. The reason H migration is unfavorable for norbornene isthat intermediate 3b, which leads to H migration, is unstable (20.1 kcal/mol) due to stericinteraction between the methylene bridge of norbornene and the Cl ligand, causing norborene tobind with a weak, rotated orientation as shown in Figure 3a. The C-Rh bond distances are 2.37 Å
and 2.43 Å in 3b, compared to 2.22 Å and 2.25 Å in 3h, which leads to B migration.
In addition to the substrate dependence, the mechanisms are significantly affected byvarying the ligand. Calculations with dmpe showed that the addition partner is the hydride for bothsubstrates, whereas with dtbpe the addition partner is BPin for both. Figure 3b shows thatintermediate 3b, which leads to H migration, is sterically hindered with dippe compared to dmpe, as
BPin is sandwiched between two ligand substituents. On the other hand, BPin only interacts with
one ligand substituent in intermediate 3h, and is thus less affected by the bulky isopropyl group.
The result is that bulky ligands disfavor H migration relative to B migration. In summary, this study
shows how ligands and substrates both affect the mechanism of hydroboration and control the
relative rates of two competing pathways.
(A)

(B)

(3b)
2.35 Å
2.28 Å

Rh-olefin
distance(3b)2.37 Å
2.43 Å

(3h)2.26 Å
2.24 Å

(3h_dmpe)(3h)2.22 Å
2.25 Å

(3h_dippe)

Figure 3. Structural comparison of intermediates 3b and 3h. The substrates propene and norbornene
are compared in (A); the ligands dmpe and dippe are compared in (B).
2. Original papers(1) Chung, L.W.; Sameera, W.M.C.; Ramozzi, R.; Page, A.J.; Hatanaka, M.; Petrova, G.P.;
Harris, T.V.; Li, X.; Ke, Z.; Liu, F.; Li, H.B.; Ding, L.; Morokuma, K.
“The ONIOM Method and its Applications.”
Chem. Rev. [Online early access]. DOI: 10.1021/cr5004419. Published Online: Apr 8, 2015.

－ 109 －

Ⅳ 研究業績 (2014)

Miho Isegawa
Miho Isegawa
Research Fellow
Research Fellow
Photochemical Ring Opening and Closing of Three Isomers of Diarylethene: Spin-Flip Time
Dependent Density Functional Study
The reaction mechanism of photochemical ring opening and closing transformation was investigated fordiarylethene (DAE), which works as molecular switch and photo device. Spin-flip time dependent density
functional theory is employed to map the potential energy surfaces and to elucidate the photochemicalmechanism of three isomers (normal, inverse, and mixed types) of 1,2-dithienylethene, a model DAE.

Figure1.

Ringtransformation
motionfor

opening-closing

with
(a-1)

conrotatory

normal,(a-2)

inverse, and (a-3) mixed type of

1,2-dithienylethene, with atomic
labels and definition of R, Ф and Ф’.
(b). HOMO and LUMO of the open
normal form.

The potential energy characteristics including minimum energy conical intersection reveals the origin ofdifferent product preference of the three isomers.
(1) For the normal type, the Frank-Condon state excited from either open or closed form of the groundstate reaches the same minimum on the excited state and decays to the closed form of the ground statethough the same conical intersection.
N-S1-FC1 (Closed), N-S1-FC2 (Open)  N-S1-MIN4  N-S1/S0-CI1  N-S0-MIN1 (Closed),(2) For the inverse type, both forms of FC states reach the same excited state minimum and decay to theopen form of the ground state via the same conical intersection,
I-S1-FC1 (Closed), I-S1-FC2 (Open)  I-S1-MIN4  I-S1/S0-CI1  I-S0-MIN2 (Open)The above findings provide the reason why the experimentally observed quantum yield is large for theclosed from in the normal type, and for the open form in the inverse type.
1－ 110 －

Ⅳ 研究業績 (2014)(3) In the mixed type, the observation of both open and closed form in the product is due to the existenceof two distinctive conical intersections with different nature and rather easy interconversion between the twopathways.
M-S1-FC1 (Closed)  M-S1-MIN4  M-S1-MIN5  (a) M-S1/S0-CI1  M-S0-MIN1 (Closed)(b) M-S1-MIN6  M-S1/S0-CI2  M-S0-MIN2 (Open)(b) M-S1-FC2 (Open)  M-S1-MIN5  (a) M-S1/S0-CI2  M-S0-MIN1 (Closed)(b) M-S1-MIN6  M-S1/S0-CI2  M-S0-MIN2 (Open)(a) Normal type
N‐S1‐FC2
86.0 kcal/mol(3.18Å, 31.1°,30.6°)

60
48

I‐S1/S0‐MECI
63.7 kcal/mol(2.04Å, 6.1°, 13.9°)

48
36
2.5

2.9

24
12
0

2.1

3.3

1.3

1.7

2.1

2.5

2.9

3.3

I-T2-MIN3
47.8 kcal/mol(3.15Å, 6.7°, 6.6°)
60

I-S1/S0-MECI
63.7 kcal/mol(2.04Å, 6.1°, 13.9°)

M-S1-TS2
61.1 kcal/mol(1.83Å, 14.6°, 11.1°)
M-S1-MIN4
60.4 kcal/mol(1.66Å, 11.0°, 9.6°)

1224

M-S1/S0-MECI1
58.9 kcal/mol(2.03Å,14.6°, 11.0°)

1.3

1.7

2.1

2.5

2.9

3.3

M-T2/S0-RF2(2.04Å, 7.3°, 4.1°)

M-S0-MIN2
0.0 kcal/mol(3.23Å, 32.4°, 23.3°)

0

0

12

24

I-T2-MIN3
47.8 kcal/mol(1.58Å, 12.6°, 9.2°)

36
24

2.5

2.9

3.3

hν

I-S1-FC2
76.4 kcal/mol(3.26Å, 26.4°, 26.0° )

1.3

1.7

2.1

2.5

2.9

3.3

M-S1/S0-MECI2
62.0 kcal/mol(2.04Å, 7.0°, 3.9°)

I‐S1‐MIN5
63.9 kcal/mol(2.90Å, 13.0°, 13.0°)

I‐S1‐MIN4
63.4 kcal/mol(2.05Å, 7.2°,13.7°)
I‐S0‐MIN1
13.0 kcal/mol(1.53Å, 1.4°, 1.3° )CLOSED
1.3

1.7

2.1

2.5

2.9

3.3

I-S1-MIN5
63.9 kcal/mol(2.80Å, 13.0°, 13.0°)

I‐T2/S0‐RF(2.05Å, 7.4°,13.6°)
I‐S0‐MIN2
0.0 kcal/mol(3.26Å, 26.4°, 26.0° )OPEN

M-S1-MIN5
58.2 kcal/mol(1.98Å, 16.9°, 11.9°)(c) Mixed type
M‐S1‐FC1
74.1 kcal/mol( 1.52Å, 3.0°, 3.5° )M-S1-FC2
81.3 kcal/mol(3.23Å, 32.4°, 23.3°)

hν

36

48

60
36

48

M-T2/S0-RF1(1.95Å, 14.6°, 12.5°)

0

I-S1-FC1
89.1 kcal/mol(1.53Å, 1.4°, 1.3°)

2.1

48

I-S1-MIN4
63.4 kcal/mol(2.05Å, 7.2°,13.7°)

1.7

36

60

60
48
36
24
12

1.7

1.3

I-S1-TS2
65.3 kcal/mol(2.14Å, 12.9°, 11.3°)

24

3.3

12

2.9

0
60

2.5

60

2.1

48

1.7

I-T2/S0-RF(2.05Å, 7.4°,13.6°)

I‐S1‐FC2
76.4 kcal/mol(3.26Å, 26.4°, 26.0° )

hν

60
48
1.3

3.3

(c) Mixed type

M-S0-MIN1
5.5 kcal/mol(1.52Å, 3.0°, 3.5° )I‐S1‐FC1
89.1 kcal/mol(1.53Å, 1.4°, 1.3°)

36

2.9

I-S0-MIN2
0.0 kcal/mol(3.26Å, 26.4°,
26.0° )
1.3

M-S0-TS1
53.9 kcal/mol(1.91Å, 16.4°,
17.3° )

I‐S1‐TS2
65.3 kcal/mol(2.14Å, 12.9°, 11.3°)

M‐S1‐TS2
61.1 kcal/mol(1.83Å, 14.6°, 11.1°)

M‐S1‐MIN4
60.4 kcal/mol(1.66Å, 11.0°, 9.6°)

M‐S1/S0‐MECI1
58.9 kcal/mol(2.03Å, 14.6°, 11.0°)

24

2.5

OPEN

CLOSED(b) Inverse type

M‐T2/S0‐RF1(1.95Å, 14.6°, 12.5°)

12

2.1

N‐S0‐MIN2
0.0 kca/mol(3.18Å, 31.1°, 30.6°)

M‐S1/S0‐MECI2
62.0 kcal/mol(2.04Å, 7.0°, 3.9°)

M‐S1‐FC2
81.3 kcal/mol(3.23Å, 32.4°, 23.3°)

M‐S1‐MIN6
61.4 kcal/mol(2.01Å, 8.4°, 9.5°)
M‐S1‐MIN5
58.2 kcal/mol(1.98Å, 16.9°, 11.9°)
M‐T2/S0‐RF2(2.04Å, 7.3°, 4.1°)

0

1.7

0

I-S0-MIN1
13.0 kcal/mol(1.53Å, 1.4°,
1.3° )

N-S1-FC1
60.1 kcal/mol(1.51Å, 4.6°, 4.6° )N‐T2/S0‐RF(1.86Å, 11.4°, 16.7°)
N‐S0‐MIN1‐1.8 kcal/mol(1.51Å, 4.6°, 4.6°)

0

0
1.3

(b) Inverse type
I-S0-TS1
60.2 kcal/mol(2.05Å, 10.6°,
11.5° )

N-S1-MIN4
50.0 kcal/mol(1.58Å, 10.5°,10.8°)

1224

N-T2/S0-RF(1.86Å, 11.4°, 16.7°)

12

N-S0-MIN1-1.8 kcal/mol(1.51Å, 4.6°, 4.6°)

N-S1-FC2
86.0 kcal/mol(3.18Å, 31.1°,30.6°)

root3 (S1)

1236

N-T2-MIN3
33.7 kcal/mol(1.55Å, 11.7°, 12.1°)

N-S1/S0-MECI
57.6 kcal/mol(1.95Å, 11.1°, 10.2°)

root2 (T2)

36

48

60

N-S0-MIN2
0.0 kca/mol(3.18Å, 31.1°, 30.6°)

24

root1 (S0)N-S0-TS46.5 kcal/mol(1.82Å, 21.7°, 21.8°)hν(a) Normal type

N‐S1/S0‐MECI
57.6 kcal/mol(1.95Å, 11.1°, 10.2°)

N‐S1‐MIN4
50.0 kcal/mol(1.58Å, 10.5°,10.8°)hνhνN‐S1‐FC1
60.1 kcal/mol(1.51Å, 4.6°, 4.6° )

1.3

1.7

2.1

2.5

M-S1-FC1
74.1 kcal/mol( 1.52Å, 3.0°, 3.5° )

2.9

3.3

M-S1-MIN6
61.4 kcal/mol(2.01Å, 9.5°, 8.3°)

M‐S0‐MIN1
5.5 kcal/mol(1.52Å, 3.0°, 3.5° )

M‐S0‐MIN2
0.0 kcal/mol(3.23Å, 32.4°, 23.3°)

CLOSED

OPEN

Figure 2. 2D Contour map of potential surfaces of S0 (root 1, left),

Figure ３. Summary of

T2 (root 2, middle) and S1 (root 3, right). Position of critical points

ring open-closed

on this map is given with the energy and selected geometricalisomerization mechanism forparameters (R, Ф and Ф’).

(a) normal, (b) mixed, and (c)inverse type.

The present results should be considered qualitative due to the limited reliability of SF-TDDFT. The
SF-TDDFT, on the other hand, is applicable to large molecules that are typically used in experiments for
efficient photofunctional materials. To raise the accuracy, more reliable CASPT2 level of calculation with thelarge active-space is required as a future study. In addition, dynamic simulation including multiple potential
energy surfaces is required to obtain quantitatively branching ratio for nonadiabatic processes.
Original paper
Photochemical Ring Opening and Closing of Three Isomers of Diarylethene:

Spin-Flip Time Dependent

Density Functional Study, M. Isegawa and K. Morokuma, J. Phys. Chem. A. 119, 4191 (2015)2－ 111 －

Ⅳ 研究業績 (2014)

W. M. C. Sameera
W. M. C. Sameera
JSPS
Postdoctoral
Fellow,
FukuiKenichi
KenichiMemorial
Memorial Research
Research Group
JSPS Postdoctoral Fellow, Fukui
Group11
1. Summary of the research
Mukaiyama aldol reactions catalyzed by a chiral Fe(II) complex
I used density functional theory (DFT), combined with the artificial force-induced reaction (AFIR)
method, to establish the mechanism of the aqueous Mukaiyama aldol reactions catalyzed by a chiral
Fe(II) complex (Scheme 1). In this reaction, silicon enolates and aldehydes is catalysed by a chiral aFe(II) complex to afford the desired aldol product in a high yield and high diastereo- andenantioselectivity. This reaction proceeds in the presence of water at 0 0C.
Bolm's ligand L1 (9 mol%)

tBu

O
Ph

H

OSiMe3

+ Me

Ph
H

N
OH

N
HO

Fe(OTf) 2 (3 mol%)
DME/H 2O
0 oC, 24h

tBu

OH

O

Ph
Me
syn (S,S)

70% yield
Ph syn : anti = 97 : 3
75 % ee (syn)Scheme 1. Aqueous Mukaiyama aldol reaction of silyl enol ethers with aldehydes catalyzed by
Fe(II) with Bolm’s ligand (L1).

On the bases of the calculations, we identified several thermodynamically stable six- orseven-coordinate complexes in the solution, where the high-spin quintet state is the ground state.
Therefore, the overall mechanism operates on the quintet state (Scheme 2). Several complexes are
possible in the solution. Of these, seven-coordinate [(L1)Fe(II)(OTf)(DME)(H2O)]+ complex (2) isthe thermodynamically most stable complex, and [(L1)Fe(II)(OTf)(DME)(PhC(O)H)]+ (5) is themost stable active species for the carbon-carbon bond formation. In 5, a dangling OTf- ligand isfound, which is attached to the –OH group of L1 via hydrogen binding. This feature helps tostabilize 5 in solution and lower the barrier for the carbon-carbon bond formation. The
carbon-carbon bond formation is the selectivity-determining step of the reaction, while the protontransfer between solvent (H2O) and of the carbonyl group of aldehyde is the rate-determining step.
The remaining steps of the mechanism are relatively straightforward. The MC-AFIR results
identified important competing reaction pathways for the selectivity-determining carbon-carbon
bond formation. Calculated enantioselectivity and diastereoselectivity are in good agreement withthe experimental results. Overall, the proposed mechanism is consistent with the experiments. This
study will guide the design of transition metal catalysts for Mukaiyama aldol reactions in aqueous
media.

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－1－

Ⅳ 研究業績 (2014)

Scheme 2. Free energy profile (kcal mol-1) for the Mukaiyama aldol reaction of silicon enolateswith aldehydes catalyzed by a chiral Fe(II) complexes in aqueous media (ΔG values are in plane
text, ΔE values are in italics).

Pd-catalysed borylation of 2-arylaziridines
Pd-catalyzed borylation reactions are well-known in the literature. The Miyaura borylation is a
Pd-catalysed conversion of an aryl or alkenyl halide to the corresponding boronic ester. The
mechanism of this reaction is related to the Suzuki–Miyaura coupling, and undergoes thePd(0)/Pd(II) manifold: (a) oxidative addition of the organohalide, (b) reaction with base, (c)transmetalation with the diboron reagent, (d) reductive elimination.

－ 113 －

－2－

Ⅳ 研究業績 (2014)

Scheme 3. Pd-catalysed borylation of 2-arylaziridines shown in the scheme 3.
My interest is the Pd-catalysed borylation of 2-arylaziridines shown in scheme 3. This reaction
works without a base, and aziridine ring opening occurs at the less hindered carbon. It is important
to note that H2O is very important for this reaction. In the absence of H2O, reaction does not work.
We have used DFT combined with the MC-AFIR method to establish the mechanism of thisreaction (Scheme 3).

Scheme 4. Catalytic cycle from computational studies.
We have systematically studied the possible pre-reacted complexes in solution, and identified thethermodynamically most stable complex, which is PdL2(H2O). Starting from this complex, next stepis the rate determining aziridine ring-opening. We have performed MC-AFIR to rationalized the－3－－ 114 －

Ⅳ 研究業績 (2014)

possible transition states, and confirmed that the ring-opening at the less-hindered carbon centre isfavourable. The resulting intermediate reacts with water, giving rise to a PdL2-OH complex. This
species acts as the active species to react with [B(pin)]2, the transmetalation process. This step ishowever sensitive to the steric effects of the ligand, L. For instance, in the presence of a bulky –P(tBu)2Me ligand, transmetalation is difficult to start from PdL2-OH due to steric repulsions, andtherefore one of two –P(tBu)2Me (L) of PdL2-OH intermediate must be dissociated. After thetransmetalation step, cis/trans isomerisation lead to the reductive elimination, and the PdL2(H2O)
can be recovered for the next catalytic cycle.
2. List of original papers
1. L. W. Chung, W. M. C. Sameera, R. Ramozzi, A. J. Page, M. Hatanaka, G. P. Petrova, T. V.
Harris, X. Li, Z. Ke, F. Liu, H-B. Li, L. Ding and K. Morokuma, "The ONIOM Method and
its Applications", Chem. Rev. 2015, 115, 5678-5796.
2. W. M. C. Sameera, M. Hatanaka, T. Kitanosono, S. Kobayashi, K. Morokuma. "TheMechanism of Iron(II)-catalyzed Asymmetric Mukaiyama Aldol Reaction in Aqueous Media:
Density Functional Theory and Artificial Force-Induced Reaction Study". J. Am. Chem. Soc.
(Submitted)
3. M. Besora, A. A. C. Braga, W. M. C. Sameera, J. Urbano, M. R. Fructos, P. J. Pe_rez, F.
Maseras, "A computational view on the reactions of hydrocarbons with coinage metal
complexes", J. Organomet. Chem. 2015, 784, 2-12.
4. 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,
136, 14, 5342-5350.
5. 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, 43,11269-11276. [This article is part of themed collection: Synergy between Experiment andTheory]6. W. M. C. Sameera, Bethmini Senevirathne, Stefan Andersson, Feliu Maseras and Gunnar
Nyman, Binding energies and binding preference of OH, HCO, and CH3 radicals onhexagonal ice: an ONIOM(QM:AMOEBA09) study. J. Chem. Phy. (Submitted)
7. F. Castro-Gómez, W. M. C. Sameera, G. Nyman, A. W. Kleij and C. Bo, "DFT Studies on
the Al(III) Catalyzed Formation of Cyclic Carbonates from CO2 and Epoxides: Towards
Quantitative Evaluation of the Catalytic Activity". ACS Catal. (Submitted)
8. D. Sharma, W. M. C Sameera, S. Andersson, G. Nyman, M. J. Paterson, "Computational
study of the interactions between benzene and crystalline ice Ih: Ground and excitedstates". Phys. Chem. Chem. Phys. (Submitted)
3. List of presentations at meetings.
1. W. M. C. Sameera and Keiji Morokuma, Computational studies of transition metal catalyzed－4－－ 115 －

Ⅳ 研究業績 (2014)

2.

3.

4.
5.

6.

7.

8.

carbon-carbon bond formation reactions, the 15th ICQC meeting, China (Poster).
W. M. C. Sameera, Fengyi Liu, Satoshi Maeda, and Keiji Morokuma, Spin-flip time-dependent
density functional theory (SF-TDDFT) study of TokyoMagenta (TM) and TokyoGreen (TG), The
12th Kenichi Fukui Memorial Research Center Symposium, Kyoto University, Japan (Poster).
W. M. C. Sameera, Miho Hatanaka, Keiji Morokuma, On the mechanism of Fe(II) catalyzed
asymmetric Mukaiyama-Aldol reaction in aqueous media, The 2nd international symposium foryoung chemists, Osaka University, Japan. (Poster)W. M. C. Sameera and Keiji Morokuma, Computational studies of the carbon-carbon bondformation reactions, Conference on C-C bond cleavage, Kyoto University, Japan. (Poster)W. M. C. Sameera, Miho Hatanaka, Keiji Morokuma, A computational study of the asymmetric
Mukaiyama-Aldol reaction. Conference on the new aspects of reactive organometallic
complexes of transition metals, Osaka University, Japan. (Poster)
M. Hatanaka, J. Jian, R. Romazzi, W. M. C. Sameera, and S. Suzuki, Explore the world ofchemistry reactions by computers, Conversation with the researchers in the academic day of the
Kyoto University, Japan. (Poster)W. M. C. Sameera, Bethmini Senevirathne, Muhsen Al-Ibadi, Stefan Andersson, Gunnar
Nyman, Interstellar radical species binding on ices: a hybrid QM/MM approach, Icy Grain
Chemistry for Formation of Complex Organic Molecules: From Molecular Clouds toProtoplanetary Disks, Comets and Meteorites, Tokyo Institute and Technology, Japan (Talk).
W. M. C. Sameera, Stefan Andersson, Gunnar Nyman, Hybrid QM/MM Methods forInterstellar Chemistry, MOLEC 2014 meeting, University of Gothenburg, Sweden. (Poster)－5－－ 116 －

Ⅳ 研究業績 (2014)

Julong Jiang
Julong JIANGSPR Fellow(March 1st 2014 to February 28th 2015)

SPR Fellow (March 1st 2014 to February 28th 2015)
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
bond was through the transition metal catalyzed C-C coupling reactions. However, in mostcases, a specific substrate should be synthesized prior to the subsequent cross-coupling
reaction. It should be noted that these special substrates are not always easy to be prepared,
and sometimes suffer from the decomposition due to the instability. In recent years, people
turned their 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 directed C-H activation on
sp3 carbons. (Yu et al., Science, 2014, 343, 1216)

Scheme 1. Palladium-catalyzed C(sp3)-H activation and subsequent arylation
More interestingly, as shown in Scheme 2, the intermediates A and B generated throughC-H activation have been successfully isolated and characterized. 2-Methylpyridine(2-picoline) was found as an appropriate ligand for the primary C(sp3)-H activation, whereas
an electron-rich ligand (2-alkoxylquinoline) was used for the secondary C(sp3)-H bond. The
reaction conditions become much milder with the help of 2-alkoxylquinoline.

Scheme 2. Generation of intermediate A and intermediate B－ 117 －

Ⅳ 研究業績 (2014)

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 thedetailed mechanism of this one-pot C-H activation and arylation reaction. The calculations
were performed on DFT level of theory (B3LYP-GD3). Interestingly, as a result, we foundthat the conventional CMD mechanism (or AMLA mechanism), in which the base is acarboxylate ligand directly coordinating to the central metal atom, does not apply to thisreaction.
Enthalpy(Gibbs Energy)
kJ/molF3C

O

at equilibrium+10.3 kJ/mol(+16.0 kJ/mol)

O N
O Pd O
N O

CF3

N

F3C

1-transN
O Pd N
O O
O
CF3

0.0
(0.0)

O
O
1-cis
+10.3
(+16.0)

O
TFA
O
O
Cs
N
H O
H3C
O
N
Cs
F3C
H
O
O
H2C
N Ph
N Ph
O
Pd
Pd
O H
N
O
N
O
CF3 1-cis
O
F3C
+
F3C
Cs
N3-TS2aa_iAbs
N3-TS1
O+25.4
N(+44.0)O Sub_Ph_AnionN
O Pd N
O O
O

F3C

O
H3C
H

+10.3
(+16.0)N-60.4(-40.9)
O
N
H3C
H
FC
O

O
O

O H3C

O
O
N Ph

Pd
O

F3C

O

CH2 N Ph
Pd
N
O

N

Cs

O

+72.4
(+93.2)

F3C

Pd

N

F3C

F3C

H

O

O
OH

O

O

N

F3C

N3-IIIb+2.0(+16.0)
CsF
O

H

O

-37.5
(-23.3)
Cs

N

HF

H

O

O

Cs

N Ph
Pd
O

N Ph
Pd
O

Cs

N Ph
Pd
O

TFA O
HO

N3-I

TFAA

O

O

N

N3-II

F3C

O TFAAN

N Ph N3-TS2b_oAbs
O

TFA

F3C
N3-TS2a_iAbs+162.2(+181.0)+53.0(+64.7)
O TFA
Cs
H O
+113.4
N(+105.6)
O H2C H N Ph
+20.8
Pd(+31.5)
O
N
O
TFA
Cs
O
H O
F3C
N

N

3

H

TFA
Cs
H O

O

N

F3C

N
N3-IIIa-145.9(-156.7)

N3-IV

Reaction Coordinate

Scheme 3. Enthalpy profile for Pathway N3, in which both L2 and L3 positions areoccupied by TFA ligands
The H-abstraction in this reaction is actually conducted by an out-of-plane TFA which has nocovalent interaction with the Pd(II) atom. Inspection of the corresponding transition statesshows that the conformation of the sp3-C atom is distorted in the TS which follows the
traditional CMD mechanism. Based on our findings, the minimum energy pathway was
located as Pathway N7. Moreover, our calculations suggested that agostic interaction is
crucial in weakening the C-H bond based on the inspection of the pre-reaction complex.

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Ⅳ 研究業績 (2014)

Scheme 4. Agostic interaction and out-of-plane H-abstraction
The Origin of the stereoselectivity in the secondary C(sp3)-H bond functionalization was
found to be the energy gap between two transition states at the secondary C(sp3)-H activation
step. The steric repulsion between the phenyl group and the succinimide moiety is crucial to
the selectivity. The size of the aryl halide for the C-H bond functionalization is irrelevant tothe selectivity, since the stereochemistry of the final product is determined at the C-H
activation step rather than the oxidative addition step. More kinds of amino acids may be
prepared in this way. Some other aspects that affect the C-H activation, such as the solvent
effect and the ligand effect, were also studied by us. The details were discussed in the
published paper.
2. Rh(III)-Catalyzed C(sp3)-H Bond Activation via an External Base Metalation
Deprotonation Mechanism: A Theoretical Study
Recently, the Wang group from Nankai University reported a novel Rh(III)-catalyzed
C(sp3)-H activation of 8-methylquinoline followed by the insertion of an alkyne (see Scheme5) in DMF. (B. Liu, T. Zhou, B. Li, S. Xu, H. Song, B. Wang Angew. Chem. Int. Ed. 2014, 53,
4191-4195.) Since 8-methylquinoline is the parent moiety of a series of bioactive compounds,
this method has a potential application in future’s drug discovery.

Scheme 5. C-H activation and insertion reactions for 8-methylquinoline
The mechanism proposed by Wang et al. is shown in Scheme 6. After dissociation of therhodium dimer and exchange of ligand with the Cu(II) acetate, the first step is the C-H
activation, which results in the formation of the intermediate A. This intermediate bears a rare
Rh-C(sp3) bond, which can go through further functionalization. After dissociation of theheterocyclic moiety and chelation of the alkyne (intermediate Bneutral), the alkyne insertionis proposed to give the intermediate C. The final product is then generated with a protonsource. The intermediate A has been isolated and fully characterized experimentally using freeacetate anion in methanol.

－ 119 －

Ⅳ 研究業績 (2014)

Scheme 6. Proposed mechanism by Wang et al. via Bneutral (Pathway I) and alternative
mechanism Bcation (Pathway II).
Herein, we wish to shed new lights on the reaction mechanism based on DFT calculations.
What is the pre-reactive complex activating the C-H bond and more particularly what is therole of the copper acetate in the formation of the intermediate A? How does the alkyne
insertion to A occur? Why the reaction cannot proceed to the alkyne insertion product withfree acetate? To answer these questions, pathways involving free and complexed acetate
ligand will be considered. Finally, the insertion of the alkyne will be studied by consideringboth neutral and cationic pathways. All of the calculations were carried out at DFT level oftheory (B3LYP) with an empirical dispersion correction (GD3).
If free acetate anion is used as the base, the C-H bond activation step is irreversible andshould proceed in a rapid way, according to our calculation results. The traditional
intramolecular CMD mechanism, which is widely used for C-H bond activation reactions, isno longer valid in this case. Indeed, the excess of free acetate anions permits to deprotonate
easily the methyl of the reactant due to the better basicity of the free acetate than the ligatedone.
For the full catalytic process, the copper (II) acetate is used as the base. The presence ofcopper prohibits the release of free acetate and thus a traditional intramolecular CMD
mechanism involving an acetate ligand on the rhodium center is not possible. Therefore, theexternal base CMD mechanism involving the copper (II) acetate occurs. The deprotonation isfound reversible in these conditions as observed experimentally. According to our results, thecopper(II) center is not directly involved the C-H activation reaction since it is fully
coordinated by ligands, and one of the ligated acetate ligands activates the C-H bond. The
copper (II) complex with a protonated acetate, [Cu(HOAc)(OAc)(DMF)2]+, releases the
proton to solution. This fact makes the H-D exchange feasible so that deuterium can bedetected from the products. Moreover, the use of non-free acetate plays a critical role toensure the feasibility of the next step as the alkyne insertion. The original proposed pathway－ 120 －

Ⅳ 研究業績 (2014)(Pathway I) was found inconsistent with the experiments and was proved to be less favoredin energy than the newly suggested cationic mechanism (Pathway II). This new pathway
starts with a relatively easy Rh-Cl bond breaking to give a stable cationic complex after
coordination of the diphenylacetylene. The DMF promotes this process as a polar solvent,which could explain why the reaction is failing in less polar solvents. The 1,2-insertion
reaction can be treated as a nucleophilic attack from the methylene group on the quinoline
ring to the C-C triple bond of the diphenylacetylene. The insertion reaction is followed by ametathesis reaction to give the final product. The insertion and metathesis steps are extremelyexothermic and thus irreversible. By considering the overall reaction, the C(sp3)-H activationis the rate-determining step since it has the highest effective barrier of +110.6 kJ/mol.
Therefore, the kinetic isotope effect (KIE) can be observed if a deuterated substrate isemployed as showed by Wang et al. Based on our newly findings, we proposed a revisedmechanism for this reaction, which is shown in Scheme 7.

Scheme 7. Revised catalytic cycle based on our DFT calculations
3. The Mechanism of Metal-Free C-H Activation of Branched Aldehydes and Acylation of
Alkenes Using Hypervalent Iodine Compound: A Theoretical Study
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. Recently,
the Maruoka group reported a C-H activation reaction of the branched aldehydes under mild
conditions, in which a hypervalent iodine(III) reagent was proposed as the catalyst (seeScheme 8).17 This reaction led to the generation of acyl radical, which can be subsequently
trapped by an electron-deficient alkene without the common side-reaction of decarbonylation.
This kind of reaction has been called hydroacylation, which was usually assisted by atransition-metal as catalyst.

－ 121 －

Ⅳ 研究業績 (2014)

Scheme 8. The C-H activation of aldehydes catalyzed by the hypervalent iodine (III)reagent 4e
A variety of experimental studies have been carried out for clarification of the reaction
mechanism. The initiation step of this reaction is the photon-assisted homolytic cleavage of
the O-I bond in the iodine(III) reagent 4e, which generates a carboxyl radical and an iodonyl
radical accordingly. To test whether the carboxyl radical is responsible for abstractinghydrogen atom from the aldehyde, the deuterated carboxylic acid was added to the mixture as
an additive, given the fact that the deuterium should appear in the product if the carboxyl
radical is the H-atom carrier. However, only trace amount of deuterated product was detected
at the end of reaction. Therefore, a mechanism based on these experimental observations was
originally proposed, as shown in Scheme 9.

Scheme 9. Proposed mechanism in which an iodonyl radical acts as a catalyst
To fully understand this reaction mechanism and to improve the reaction systematically in thenear future, we decided to perform theoretical investigations on this hydroacylation reaction. With
the help of DFT calculations, we can confirm that the iodonyl radical 12_Me is impossible toabstract H atom from the aldehyde, as shown in Scheme 10.

－ 122 －

Ⅳ 研究業績 (2014)

Scheme 10. Energy change for the H-abstraction by the iodonyl radical 12_Me
This finding disagrees completely with the initially proposed iodonyl mechanism, andprompted us to re-examine the mechanism of this metal-free hydroacylation reaction. Our extra
calculations have shown that the hypervalent iodine reagent is actually an initiator rather than areactive catalyst. After initiation, the reaction proceeds via a chain propagation mechanism
through the addition reaction of an acyl radical to the electron-deficient alkene, followed by ahydrogen abstraction from the aldehyde by the resultant carbon-centered radical species. Our
theoretical investigations led to a completely new mechanism shown in Scheme 11.

Scheme 11. Mechanism of the C-H activation and acylation reaction based on our theoreticalstudiesPublications
1. Julong Jiang, Jin-Quan Yu, Keiji Morokuma, “Mechanism and Stereoselectivity of Directed
C(sp3)-H Activation and Arylation Catalyzed by Pd(II) with Pyridine Ligand and TFA. A
Computational Study”, ACS Catal. 2015, 5, 3648-3661.
2. Julong Jiang, Romain Ramozzi, Keiji Morokuma, “Rh(III)-Catalyzed C(sp3)-H Bond
Activation via an External Base Metalation/Deprotonation Mechanism: A Theoretical Study”,
Chem. Eur. J. 2015, Accepted.
3. Julong Jiang, Romain Ramozzi, Shin Moteki, Asuka Usui, Keiji Maruoka, Keiji Morokuma,“The Mechanism of Metal-Free C-H Activation of Branched Aldehydes and Acylation of
Alkenes Using Hypervalent Iodine Compound: A Theoretical Study”, J. Org. Chem.
Submitted.

－ 123 －

Ⅳ 研究業績 (2014)

OthersPoster presentation in "Conversation with Researchers" in the Academic
Day of Kyoto University
Title: Explore the world of chemistry reactions by computers
Authors: Morokuma Group (Miho Hatanaka, Julong Jiang, Romain Romazzi, WMC Sameera, andSatoshi Suzuki), Fukui Institute for Fundamental Chemistry, Kyoto University
Date and Place: September 28 (Sunday), 2014. Clock Tower Centennial Hall, Kyoto University－ 124 －

Ⅳ 研究業績 (2014)

Shinichi Yamabe
Shinichi

Yamabe

FIFC
Fellow, Kenichi
FIFC
Fellow,
KenichiFukui
FukuiMemorial
MemorialResearch
Researchgroup
group22
1. Summary of the research of the year(1-1) A DFT Study of Hydride Transfers to the Carbonyl Oxygen of DDQ
Hydride-transfer reactions between benzylic
substrates and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) were investigatedby DFT calculations. The lowest unoccupied molecular orbitals of DDQ has thelargest extension on two carbonyl oxygens, which comes from two-step mixing ofantisymmetric orbitals of fragment pi MOs.
Transition-state (TS) geometries and activation energies of reactions offour benzylic substrates R2-CH2-para-C6H4-R1 (R1,R2 = H and/or OCH3)
with DDQ were calculated.
B3LYP, BHandH, M06-2X and wB97xD B3LYP methods
were used. The basis sets employed were 6-31G(d), 6-311(+*)G(d), 6-311++G(d,p)
and 6311++G(3df,2pd), where "6-311(+*)G(d)" means that a diffuse and a polarization
functions are added only to the migrating hydrogen(hydride). This was found to be apractical computational method, giving energies and geometries similar to those of
M06-2X/6-311++G(3df,2pd) and wB97xD/6311++G(3df,2pd). For toluene(R1=R2=H), an initiation-propagation model was suggested, and the calculated
kinetic isotope effect k(H)/k(D) = 5.0 with the tunnel correction at the propagating
step is in good agreement with the experimental value 5.2.
A reaction of para-MeO-C6H4-CH2(OMe) + DDQ + (H2O)14-> para-MeO-C6H4-C(=O)H + HOMe + DDQH2 + (H2O)13 wasinvestigated by M06-2X/6-311(+)G*. TS1 is for the hydride transfer, leading
to the ion pair intermediate (Int1). From Int1, the hemiacetal intermediate (Int2) isgenerated via TS2. Int2 is hydrolyzed via TS3 into Int3 consisting ofpara-methoxybenzaldehyde and methanol. The change of Int3 → TS4→ product is the neutralization of DDQH- to DDQH2. Thus, four elementary
processes were found and the hydride transfer (TS1) is the rate-determining step.
The hydride transfer was promoted by association with the water cluster.
The size of the water cluster, (H2O)n, at TS1 was examined. Three models ofn = 14, 20, and 26 were found to give similar activation energies.
Metal-free neutral hydride transfers from activated benzylic substrates to DDQ
were proposed to be ready processes both kinetically and thermodynamically.

－ 125 －

Ⅳ 研究業績 (2014)(1-2) Frontier orbitals and transition states in theoxidation and degradation of L-ascorbic acid.
DFT calculations were carried out to investigate reaction paths of L-ascorbic acid(AAH2), hydroxyl radical and water clusters. Frontier-orbital analyses werealso made to examine the regioselectivity of the OH(.) addition. Transition states ofthe electrolytic dissociation of AAH2 and intermediate carboxylic acids were foundto have very small activation energies through proton transfers along hydrogen bonds.
The ionized species (anions) are subject to the electrophilic attack of OH(.).
The process of AAH2 -> AA.- -> dehydroascrobic acid -> diketogulonic acid ->theronic acid was discussed on thebasis of the calculated elementary processes.
These of dehydroascrobic acid -> a bicyclic hemiketal were also examined as aside-chain participating reaction. The oxidation and degradation of vitamin C up
to threonic acid were summarized to be a donor(AAH2)-acceptor(OH.) reaction.

2

Original Papers(1)"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.

(2)"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.,－ 126 －

Ⅳ 研究業績 (2014)

Canadian Chemical Transactions, 2014, vol.2, issue 2, 134-148.
(3)"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),(4)

vol.35, issue 15,

DOI: 10.1002/jcc.23607.

"A DFT Study on Proton Transfers in Hydrolysis Reactionsof Phosphate Di-Anion and Sulfate Mono-Anion",
Shinichi Yamabe, Guixiang Zeng, Wei Guan, Shigeyoshi Sakaki,
Journal of Computational Chemistry,
Volume 35, Issue 30, November 15, 2014, Pages: 2195-2204.

(5)"Atmospheric pressure chemical ionization (APCI) of explosives
using alternating current corona discharge ion source",
D. T. Usmanov, L. C. Chen, Z. Yu, S. Yamabe*, S. Sakaki
and K. Hiraoka*,
Journal of Mass Spectrometry (a cover story, Wiley),vol. 50, No. 4, page 651-710 (2015),
http://onlinelibrary.wiley.com/doi/10.1002/jms.3552/pdf(6)"Study of structures, energies and vibrational frequenciesof (O2)n+(n=2-5) clusters by GGA and meta-GGA density functional
methods",
Govinda P. Khanal, Rajendra Parajuli, Elangannan Arunan,
Shinichi Yamabe, Kenzo Hiraoka and Eiko Torikai,
Computational and Theoretical Chemistry (Elsevier),vol. 1056, page 24-36 (2015),
DOI information: 10.1016/j.comptc.2014.12.022(7)"Frontier orbitals and transition states in the oxidation anddegradation of L-ascorbic acid: a DFT study"
Shinichi Yamabe, Noriko Tsuchida, Shoko Yamazaki and
Shigeyoshi Sakaki
Org. Biomol. Chem., 2015, vol. 13, 4002-4015.
DOI: 10.1039/c5ob00035a(8)"Transition States of the 3MLCT to 3MC Conversion in－ 127 －

Ⅳ 研究業績 (2014)

Ru(bpy)2(phen derivative)2+ Complexes"
Naokazu Yoshikawa, Shinichi Yamabe, Shigeyoshi Sakaki,
Nobuko Kanehisa, Tsuyoshi Inoue,and Hiroshi Takashima,
Journal of Molecular Structure, vol.1094 (2015) 98-108.
DOI: 10.1016/j.molstruc.2015.04.011(9)"A DFT study of hydride transfers to the carbonyl oxygen of DDQ"
Shinichi Yamabe, Shoko Yamazaki and Shigeyoshi Sakaki,
International Journal of Quantum Chemistry,

in press.

2. Presentation at academic conference"Frontier orbitals and transition states in the oxidation anddegradation of L-ascorbic acid: a DFT study"

第１２回 福井謙一記念研究センター シンポジウム（２０１５年１月２３日）
At Fukui Institute for Fundamental Chemistry, Kyoto University－ 128 －

Ⅳ 研究業績 (2014)

土方
土方

優
優

FIFC フェロー

FIFC フェロー
1. 今年度（半期）の研究の要約
今年度は配位高分子における、骨格構造の安定性に関する研究を行った。
【始めに】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。これら新規材料としての応用を考えた際に重要となるのが、水の存在、
つまり PCP の耐水性であり、近年では耐水性に関する実験研究も多く報告されている。特に通常の単核錯体と異なり、三次元骨格を組んだ場合は金属−配位子館結合だけでなく、骨格を崩壊させるためのエネルギーも考慮する必要があると考えられる。そこで骨格中における水との反応からその安定性についての知見を得ることを目的とした。
【計算、結果、考察】
図１に示した Zr406 クラスターから な る UiO-66 と 呼 ば れ る 骨 格[Zr406(OH)4(L)]n (L=OOC-Ph-COO)と配位子の異なる類似の構造（L=
OOC-(Ph)2-COO, OOC-(Ph)3-COO, ,OOC-bpy-COO）について、水付加による不安定化の評価を行った。３次元骨格構造内における水付加を想定し model における Zr クラスター部
分の距離は固定して行った。得られた結果を表１にまとめる。

（図 1）UiO-66 の細孔構造と model 構造（表１）H2O 付加による不安定化と各寄与(kcal/mol)
L の種類

H2O 付加Lframework のみの

OOC-Ph-COO

0.9

3.3

32.1

OOC-(Ph)2-COO

-4.6

3.2

29.8

OOC-bpy-COO

-3.2

3.9

30.5

OOC-(Ph)3-COO

-2.8

5.2

32.8

L = OOC-Ph-COO の方が L = OOC-(Ph)2-COO に比べ水付加による不安定化が小さい、つまり耐水性が高いという結果が得られた。これは実験結果とも一致している。一方で、L =OOC-(Ph)3-COO は L = OOC-(Ph)2-COO に比べ安定性が高いという結果となり、これは実験結果に一致していない。この理由については現在検討中である。

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2. 論文(1) Keisuke Kishida, Yumiko Watanabe, Satoshi Horike, Yoshihiro Watanabe, Yoshikuni
Okumura, Yuh Hijikata, Shigeyoshi Sakaki, and Susumu Kitagawa“DRIFT and theoretical studies of ethylene/ethane separation on flexible microporosity of[Cu2(2,3-pyrazinedicarboxylate)2(pyrazine)]n”
European Journal of Inorganic Chemistry, 2014, 2747-2752(2) Ryo Ohtani, Munehiro Inukai, Yuh Hijikata, Tetsuya Ogawa, Mikihito Takenaka, Masaaki
Ohba, and Susumu Kitagawa“Sequential synthesis of coordination polymersomes”
Angewandte Chemie International Edition, 2015, 54, 1139-1143(3) Shin-ichro Noro, Junya Mizutani, Yuh Hijikata, Ryotaro Matsuda, Hiroshi Sato, Susumu
Kitagawa, Kunihisa Sugimoto, Yasutaka Inubushi, Kazuya Kubo, and Takayoshi Nakamura“Porous coordination polymers with ubiquitous and biocompatible metals and a neutral
bridging ligand”
Nature Communications, 2015, 6, 5851
3. 学会発表(1) Yuh Hijikata and Shigeyoshi Sakaki“Theoretical study of the interaction between carbon dioxide and hexafluorosilicate in PCP
framework”
The 64th Conference of Japan Society of Coordination Chemistry, Tokyo, September 19,
2014(2) Yuh Hijikata and Shigeyoshi Sakaki“Theoretical study of binding energies and frequency shifts of various small gas moleculesinteracting with open metal site of Cu paddle-wheel”
4th International Conference on Metal-Organic Frameworks and Open Framework
Compounds, Hyogo, September 30, 2014(3) Shin-ichiro Noro, Junya Mizutani, Yuh Hijikata, kazuya kubo, and Takayoshi Nakamura“Porous light metal coordination polymers with charge-polarized neutral ligand”
4th International Conference on Metal-Organic Frameworks and Open Framework
Compounds, Hyogo, September 30, 2014
4. 書籍
1.

錯体化学選書 10「金属錯体の量子・計算化学」
4.4 章
土方

PCPs/MOFs の構造と機能発現（4－4－1 から 4－4－6 担当）
優 三共出版

2014 年 10 月 10 日

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青野
信治
青野 信治
センターフェロー（榊研）

センターフェロー（榊研）
1. 今年度の研究の要約【序】 d6 金属の Ru(II)と SO2 により構成される八面体型 Ru(II)-SO2 錯体 [RuII (NH3)4(SO2)X]Y は、基底状態において SO2 の S 原子が Ru(II)に配位した1 型の安定構造（GS 構造）を持つ。この結晶に低温中で可視光を照射すると光異性化反応が起こり、GS 構造から O と S 原子が Ru(II)に配位した2 型の準安定構造（MS2 構造）および O 原子が配位した1 型の準安定構造（MS1 構造）へ変化する。光反応後に温度を上昇させ、逆に MS1 構造から MS2 構造へ、MS2 構造から GS 構造へ戻す事が可能であり、この錯体は分子デバイスとしての利用が期待されている（Scheme 1）[1]。
光異性化反応後の GS、MS1、MS2 の存在比は Ru(II)-SO2 錯体のトランス位の配位子 X の種類のみならず対イオン Y の種類や温度により大きく異なる事が実験で観測されている。従って、この異性化反応に対する周囲の分子からの影響を明らかにする事は分子デバイスの設計・制御の上でも重要である。

Scheme 1: Ru(II)-SO2 の異性化反応
本研究では光異性化反応後の熱異性化過程について注目し、まず単分子レベルでのトランス位の配位子効果を調べる為に配位子 X が Cl-、H2O、pyridine の場合に対して遷移状態構造を最適化し、そのエネルギー変化を求め、気相中と水中での周囲の環境の違いについて比較・検討した。また
X=pyridine、Y=2Cl-・H2O の場合に対して QM/MM 法を用いて遷移状態構造とポテンシャルエネル
ギー変化を求め、Ru(II)-SO2 錯体の異性化反応への結晶効果とその温度依存性を検討した。
【方法】 構造最適化およびエネルギー計算には B3PW91 汎関数による DFT 法を用いた。Ru の原
子価電子には(311111/22111/411)基底を用い、内殻電子は Stuttgart グループの ECP で置き換えた。また O、S、Cl 原子には 6-311G++(2df, 2pd)基底、C、N 原子には 6-311++G**基底、H 原子には 6-31++G**
基底を用いた。水中の溶媒効果は PCM 法により考慮し、結晶効果は周期境界条件に基づく QM/MM法により取り入れた [2]。
本研究での QM/MM 法に基づく結晶中の構造決定は、次のような二段階で構築されている（Scheme 2）。反応中心以外の部分は MM 領域として点電荷と LJ 変数によるモデル化を行う。ここでは対称操作と格子ベクトルによる並進操作を用いる事で全結晶部分を再構成できる最小限の領域（参照領域）を QM 領域として選び、計算された RESP 電荷を MM 領域に再分布させる事で自己無撞着に MM 領域の構造と点電荷を決定した [2]。 得られた MM 領域を固定した条件下で、式(1)のエネルギー Ecrystal が最少となるように反応中心部分の構造最適化を行った。

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Ⅳ 研究業績 (2014)

Scheme 2: QM/MM 法による結晶中の構造決定

E crystal 
E QM  E QM/MM  QM Hˆ gas  QM  E ES  E LJ 式(1)

ここで MM 領域を固定した条件下では MM 分子の内部エネルギーと MM-MM 間の相互作用エネル
ギーが一定であると見做すと、変化量Ecrystal は反応中心（QM 領域）の構造変化に伴う全結晶のポテンシャルエネルギーの変化量に相当する事になる。
[RuII(NH3)4(SO2)(pyridine)] (2Cl-・H2O)の場合、単量体を QM 領域に選び、MM 領域は全て GS 構造、全て MS1 構造、全て MS2 構造であると仮定した３通りの MM モデルを構築した。特に MS2構造において SO2 分子がすべて同じ向きとなる結晶構造を仮定したが、それに加えて１層ごとに逆の向きとなる晶構造も MS2’構造として考えた。その後、QM 領域には異性化反応を起こす単量体とそれに隣接する２分子からなる合計３分子を選び、MM 領域の構造と電荷分布を固定して、結晶中での構造変化とエネルギー変化Ecrystal を計算した。構造最適化の際、着目する単量体の Ru 原子の位置は固定した。また本研究では、温度の違いは格子ベクトルの違いとしてエネルギー変化に反映されており、格子ベクトルは実験結果から引用した。
【結果】 気相中の GS→MS1 の異性化反応の構造変化では GS 構造と MS1 構造の間に MS2 構造が存在し、Ru と結合を作らない O 原子（Ofree）が面外に回り込むように移動する（図 1）。Ru と結合を作る O 原子（Obond）との距離 r(Ru-Obond)が短くなり、S との距離 r(Ru-S)が長くなるが、それらは複雑な変化を示す事から、１次元の反応座標としては距離の差

q = r(Ru-Ofree) r(Ru-S)

が有用である。この特徴は気相中のみならず溶液中、結晶中でも共通である。

図 1: 気相中での異性化反応の構造変化 (配位子 X = Cl)
配位子 X が Cl-、H2O、pyridine の場合について、気相中でのエネルギー Egas および水中での自由－ 132 －

Ⅳ 研究業績 (2014)

エネルギーA の変化には、大きな配位子効果と溶媒効果が確認された（図 2）。特に気相中ではトランス位の配位子 X が中性の H2O や pyridine の場合は MS1 構造と GS 構造のエネルギー差は僅かであるのに対し、アニオン性の Cl-の場合は MS1 構造が 10 kcal/mol 以上も不安定となる。この相違
は配位子 X の種類による Ru-SO2 結合エネルギーの変化や X の電子供与・逆供与性や電荷の違いによると考えられ、検討する必要がある。また水中では配位子 X の種類による自由エネルギー変化の違いは小さくなるが、X=H2O、pyridine の場合でさえ MS1 構造が GS 構造よりも 20 kcal/mol も不安定となり、エネルギー変化は気相中と大きく異なる。これは異性化反応に伴う内部エネルギーの変化だけでなく、反応中心と周囲分子との相互作用エネルギーの変化も重要である事を示唆する。
結晶中でも同様のエネルギー差がみられる。

図 2: 気相中での Egas および水中でのA の変化
反応中心以外の結晶分子が全て GS 構造である場合、全て MS1 構造である場合、全て MS2 構造である場合のいずれにおいても、水中の場合と同様に MS1 構造が GS 構造よりも大きく不安定化される事を示している（図 3）。ポテンシャルエネルギーの変化の形状は、MS1→MS2 の構造変化における障壁より MS2→GS の構造変化における障壁の方が高く、低温中では MS1 からの構造緩和がGS まで戻らず、MS2 で長時間存在する事を示唆する。特に MS2 構造と MS1 構造の間のポテンシャルエネルギー変化は周囲分子や温度に依存しており、MS1→MS2 の構造変化の障壁は周囲分子がGS 構造である場合よりも MS2 構造である場合の方が低く、また温度の上昇に伴い低くなる点も示唆している。この結果は、実験において熱を加える事で MS1 からの構造緩和が生じる点や、100K→140K 程度の温度上昇では MS2 の存在比が増加するものの GS の存在比は変化しない点などの傾向に一致している。

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Ⅳ 研究業績 (2014)

図 3:
3: 結晶中での結晶中での E
Ecrystalの変化
crystal の変化
図
crystal
図 3: 結晶中での Ecrystal の変化[1] (a)(a) A.
A. Y.
Y. Kovalevsky,
Kovalevsky, K.
K. A.
A. Bagley,
Bagley, andand P.
P. Coppens,
Coppens, J.
J. Am.
Am. Chem.
Chem. Soc.
Soc. 2002,
2002, 124,
124, 9241;
9241; (b)(b) A.
A. Y.
Y. Kovalevsky,
Kovalevsky, K.
K. A.
A.
[1]
Bagley, J.
J. M.
M. Cole,Cole, andand P.
P. Coppens,
Coppens, Inorg
Inorg Chem.
Chem. 2003,
2003, 42,42, 140;140; (c)(c) S.
S. O.
O. Sylvester, J.
J. M. Cole,
Cole, and P.
P. G.
G. Waddell,Waddell, J.
J. Am.
Am.
Bagley,[1](a) A. Y.
Kovalevsky,
K. A. Bagley,and P. Coppens,
J. Am. Chem.
Soc.Sylvester,
2002, 124, M.
9241; (b)and
A. Y. Kovalevsky,
K. A.
Chem. Soc.
Soc. 2012,2012, 134, 11860;
11860; (d)(d) A.
A. E.
E. Phillips,
Phillips, J.
J. M.
M. Cole,Cole, T.
T. d’ Almeida,
Almeida, andand K.
K. S.
S. Low,
Low, Inorg.
Inorg. Chem.
Chem. 2012, 51,
51, 1204.
Chem.
Bagley,J. M. Cole,134,
and P. Coppens,
Inorg
Chem. 2003,
42, 140;d’(c)S. O. Sylvester,J. M. Cole,and P. G.2012,
Waddell, 1204.
J. Am.
[2] S.
S. AonoAono
and S.
S.134,
Sakaki,Chem.
Phys.
Lett. 2012,
2012,
544,
77. T. d’ Almeida, and K. S. Low, Inorg. Chem. 2012, 51, 1204.
[2]
and
Sakaki,
Chem.
Phys.
Lett.
544,
77.
Chem.
Soc. 2012,
11860;(d) A.
E. Phillips,
J. M.
Cole,
[2] S. Aono and S. Sakaki, Chem. Phys. Lett. 2012, 544, 77.

2. 論文
論文
2.
2. 論文
(1) Taichi
Taichi Inagaki,
Inagaki, Shinji
Shinji Aono,
Aono, Hiroshi
Hiroshi Nakano,
Nakano, andand Takeshi
Takeshi Yamamoto,
Yamamoto,(1)“Like-Charge Attraction ofof Molecular
Molecular Cations
Cations in Water:
Water: Subtle
Subtle Balance
Balance(1) “Like-Charge
Taichi Inagaki,Attraction
Shinji Aono, Hiroshi
Nakano, and in
Takeshi Yamamoto,between InterionicInterionic Interactions
Interactions andand Ionic
Ionic Solvation
Solvation Effect”
Effect”
between“Like-Charge
Attraction of Molecular
Cations in Water:
Subtle Balance
J.
Phys.
Chem.
B
118,
5499-5508(2014).
J.
Phys.InterionicChem. B 118,
5499-5508 (2014).
betweenInteractions
and Ionic Solvation Effect”
J. Phys. Chem. B 118, 5499-5508 (2014).
3.
学会発表
3. 学会発表
3. 学会発表(1) 青野信治、榊茂好
青野信治、榊茂好(1)「結晶中におけるRu(II)-SO2錯体の異性化反応：配位子および結晶効果」(1) 「結晶中におけるRu(II)-SO2錯体の異性化反応：配位子および結晶効果」
青野信治、榊茂好
第8回分子科学討論会 広島
広島 2014/9/21
2014/9/21 1P122
1P122
第8回分子科学討論会「結晶中におけるRu(II)-SO2錯体の異性化反応：配位子および結晶効果」
第8回分子科学討論会
4.
その他
4. その他

広島

2014/9/21

1P122

4. その他(1) 「結晶中におけるRu(II)-SO2錯体の異性化反応：配位子および結晶効果」福井謙一
京都大学第12回京都大学福井謙一記念研究センターシンポジウム
2015/1/23 P46－ 134 －

京都

Ⅳ 研究業績 (2014)

Guixiang ZENG（曾GuixiangZeng（會 桂香）
桂香）

SPR
SAKAKIGroupGroup
SPRFellow,
Fellow, SAKAKI
1. Summary of the research of the year
Catalytic Transfer Hydrogenation by Trivalent Phosphorus Compound: Electronic Process, Ligand
Influence, and Prediction [1]Due to the desire for cheaper and environmentally friendly catalysis, main-group element catalysts attract
increasing interest in the past decade for their excellent reactivities similar to those of transition metal
complexes. However, catalytic cycles performed by main-group element compounds are limited.
Constructing catalytic cycles in the chemistry of main group element compounds are interesting, which
would provide new possibilities in the catalyses.

The reaction mode of the E−ligand (E=main groupelement) cooperation has not been reported for the main-group element compound until recently.

In 2012, a

trivalent phosphorus compound ADPO (1P) was reported to be able to catalyze the transfer hydrogenation
reaction of azobenzene with NH3BH3; see Eq. 1.

We found that the reaction occurs through an unprecedented phosphorus−ligand cooperation pathway,
which resembles the metal−ligand cooperation; see Scheme 1. In the reaction, the structure around thephosphorus atom dramatically changes from a planar T-shaped geometry to a tetrahedral one. However, theelectronic processes along such significant geometry changes are still ambiguous. Such information bodes
well for our deeper understanding of the E-ligand cooperation reaction. Constructing new and more efficient
main group element compounds is also of great importance for the development of the non-metal catalysis.

Scheme 1. Reaction Mechanism of the Reaction Shown in Eq. 1.
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Ⅳ 研究業績 (2014)

Here, we examined the substituent effect, framework effect and electronic processes of the reaction to
explain these two effects. The catalysts examined in this work are shown in Scheme 2.

Scheme 2. Catalysts examined in this work.
First, the substituent influence on the reactivity of 1P was examined. As shown in Figure 1, the Gibbs
energy barriers (∆G0≠) of the NH3BH3 dehydrogenation step decreases in the order 27.1 kcal/mol (R=tBu) >26.6 kcal/mol (R=Me) > 20.9 kcal/mol (R=CF3), indicating that the electron withdrawing (EWD) substituent
is favorable for the dehydrogenation step. The EWD substituent (R=CF3) also significantly stabilizes theintermediate 4OP by 8.3 kcal/mol as compared with the R=tBu case. For the transfer hydrogenation step,when 4OP was taken as the reference, the ∆G0≠ increases in the order 14.6 kcal/mol (R=tBu) < 18.0 kcal/mol(R=Me) < 18.3 kcal/mol (R=CF3). It indicates that the EWD substituent is unfavorable for this reaction step.
However, if we take the initial reactants, that is more stable than 4OP, as the energy reference, the ∆G0≠
decreases in the order 30.1 kcal/mol (R= Me) > 28.1 kcal/mol (R=tBu) > 23.5 kcal/mol (R=CF3). It indicatesthat the EWD substituent facilitates the transfer hydrogenation step through its large stabilization of 4OP.

Figure 1. Reaction profile for the transfer hydrogenation reaction by 1P with the substituents of tBu,
Me, and CF3.
2
－ 136 －

Ⅳ 研究業績 (2014)

Second, we explored the framework effect on the reactivity of 1P. As shown in Figure 2, the larger
conjugate framework significantly enhances the activity of 1P, where the ∆G0≠ values considerably
decrease from 26.6 and 30.1 kcal/mol (1P−Me) to 19.1 and 22.9 kcal/mol (diB−1P), respectively. Moreinteresting thing is that the dehydrogenation step is exothermic by -4.7 kcal/mol whereas it isendothermic by 12.1 kcal/mol in the 1P−Me catalyzed reaction. We will explain why 4OP was stabilized
by the dibenzo-ONO ligand so much below. Furthermore, when the benzene ringing in diB−1P wasconnected with a CH2 linkage, ∆G0≠ values further decrease to 13.9 and 17.5 kcal/mol, respectively.
These calculation results indicate that the activity of 1P was further enhanced.

Figure 2. Reaction profile for the transfer hydrogenation reaction by 1P−Me, diB−1P, and Acr−1P.
Third, we explored the electronic processed to explain the substituent and framework effects. In thedehydrogenation step, the population of each part of the ligand increases and the ligand population
reaches to maximum in the intermediate 4OP; see Figure 3. This is why the EWD substituent as well as
the larger conjugated framework facilitate the dehydrogenation step and stabilizes 4OP.

Figure 3. NBO analysis along the transfer hydrogenation reaction by 1P.
3－ 137 －

Ⅳ 研究業績 (2014)

Finally, we clarified the oxidation state of the phosphorus central atom. In 1P, there is a hybrid sp
lone pair orbital, a P−N σ−bonding orbital, a P−N π-bonding orbital and a P−N π* anti-bonding orbitalaround the phosphorus center; see the upper half of Scheme 3. In 4OP, the P−N σ−bonding orbital, thehybrid sp lone pair orbital of the phosphorus element, and the nitrogen p lone pair orbital are retained;
see the lower half of Scheme 3. However, the phosphorus p lone pair orbital disappears.

Instead, one

Comparing the orbitals of 1P and 4OP,

PH σ-bonding orbital and one PO σ-bonding orbital appear.

we come to the following conclusion: the phosphorus p lone pair was consumed to form the P−H andP−O σ-bonds when going from 1P to 4OP (the dehydrogenation step).
oxidation state should increase by 2 in this reaction step.

As a result, the phosphorus

Note that the phosphorus center bears atypical tetrahedral geometry in 4OP, indicating that the oxidation state of the phosphorus center is +III
as well known.

This interpretation is consistent with the presence of tree σ-bonding orbitals (P−N, P−O,

and P−H) around the phosphorus center in 4OP.

Reversely, the phosphorus oxidation state would

decrease by 2 when going from 4OP to 1P in the transfer hydrogenation step, indicating that theoxidation state of the phosphorus center in 1P is +I. This understanding is also consistent with previous
interpretation of the phosphorus oxidation state in 1P.

Scheme 3. Important Kohn-Sham orbitals of 1P and 4OP.
In brief, transfer hydrogenation of azobenzene with NH3BH3 mediated by a trivalent phosphorus
compound 1P occurs through a phosphorus-ligand cooperation catalytic cycle. In this cooperation catalytic
cycle, the phosphorus oxidation state changes between +I and +III.

This is completely different from thetransition metal-ligand cooperation catalytic cycle, where the metal oxidation state does not change.

The

reactivity of the phosphorus compound can be improved by a) electron withdrawing substituent; b) extending
the C=C double bonds on the framework to large conjugated benzene rings (diBen−1P); c) Connecting thetwo benzene rings in diBen−1P with a CH2 linkage (Acr−1P); d) Constructing a pyrrole ring around theapical atom.

Larger conjugated framework promoted phosphorus compound is much more efficient thanthe electron withdrawing substituent promoted one.
4
－ 138 －

Ⅳ 研究業績 (2014)

Original papers[1] Guixiang ZENG, Satoshi MAEDA, Tetsuya TAKETSUGU, and Shigeyoshi SAKSKI“Catalytic Transfer Hydrogenation by Trivalent Phosphorus Compound: Electronic Process, Ligand
Influence, and Prediction” In preparation.
2. Presentation at academic conferences
Guixiang ZENG, Satoshi MAEDA, Tetsuya TAKETSUGU, and Shigeyoshi SAKSKI “Catalytic Transfer
Hydrogenation by Trivalent Phosphorus Compound:

Combination of Phosphorus-Ligand Cooperation and

PI/PIII Redox” The 15th International Congress of Quantum Chemistry, Beijing June 8~13, 2015
3. Others
Guixiang ZENG, Satoshi MAEDA, Tetsuya TAKETSUGU, and Shigeyoshi SAKSKI “Mechanistic Study on
C-H Alkylation of Alkenes with Alcohols Catalyzed by a Cationic Ru(II) Hydride Complex: Direct C-O
Bond Activation” The 12th symposium of Fukui Institute for Fundamental Chemistry, Kyoto, January. 23,
2015.

5－ 139 －

Ⅳ 研究業績 (2014)

中垣 雅之
中垣雅之
FIFC フェロー

FIFC フェロー
1. 今年度の研究の要約（A4 3-5 ページ、図・表なども適宜挿入する）【 緒 言 】 Co(II) と 2 つ の ピ ラ ジ ン 環 を も つ イ ミ ド 配 位 子 と の 錯 体[Co(dpzca)2] (スキーム 1)は、高温領域で 4 重項、低温領域で 2 重項をとり、スピンクロスオーバー現象を示す 1。一方、ピラジン環の１つをピリジン環に置き換えた類似体[Co(pypzca)2]は、低温においても高スピン状態のみをとる 2。このような僅かな配位子の差によるスピンクロスオーバー現象の違いは興味深く、その起源の解明には金属錯体の電子状態と分子間相互作用の双方を正しく評価する詳細な理論研究が不可欠である。本研究では、結晶中でのスピン状態のエネルギー変化に着目し、スピンクロスオーバーに関する振る舞いの異なる２つの金属錯体について比較を行った。
【計算方法】[Co(dpzca)2]及び[Co(pypzca)2]錯体について、孤立分子及び結晶中での各スピン状態の構造と相対エネルギーを求めた。構造最適化には密度汎関数法を用い、QM/MM 法 3 を用いて周囲の分子の影響を考慮した。相対エネルギーは複数の計算法により評価した後、B3LYP-D 法及びGMC-QDPT 法で求めた。GMC-QDPT 法の参照関数には、
Co に配位した N 原子の lone pair 軌道、
Co 原子の 3d 及び 4d 軌道を活性軌道とした RASSCF(11e,12o)波動関数を用いた。遷移金属の内殻電子は Stuttgart-Dresden-Born の ECP で置き換え、原子価軌道には triple-zeta 基底関数を用いた。Co 原子に隣接した 6 つの N 原子には aug-cc-pVDZ を、その他の原子には cc-pVDZ を用いた。
【結果及び考察】2 重項及び 4 重項状態の最適化構造は、それぞれ 90K 及び 298K における結晶構
造とよい一致を示した(表 1)。Co 原子と配位する N 原子との結合長は、孤立系での計算においても実験値に近い値が得られたが、結晶内では平均誤差 0.01Åで実験値によく一致した。また、カルボニル基の二面角で示される配位子の歪みは結晶中の分子間相互作用由来であり、QM/MM 法でのみ実験値に近い値が得られた。
表１.

最適化構造及び X 線結晶構造の構造パラメータ
X 線結晶構造

最適化構造
2 重項 a)

4 重項

90Ka)

298K

孤立系

QM/MM

孤立系

QM/MM

r(Co-Nca) / Å

1.921 / 1.953

1.917 / 1.945

1.999

2.075

1.913 / 1.945

2.050

r(Co-Npz) / Å

2.001 / 2.170

1.970 / 2.197

2.157

2.150

1.971 / 2.188

2.146

r(Co-Npz) / Å

2.001 / 2.170

1.982 / 2.216

2.157

2.150

1.991 / 2.198

2.146

a(Npz-Co-Npz) / deg.

165.7 / 161.4

165.2 / 158.8

157.0

154.8

165.1 / 159.4

155.0

d(O-C-C-O) / deg.

0.0 / 0.0

3.7 / 18.6

4.5

21.2

2.4 / 18.6

18.4a) 2 つの配位子が異なる値をもつ－ 140 －

Ⅳ 研究業績 (2014)

表２に示すように、スピン状態間のエネルギー差は、密度汎関数法では用いる汎関数に大きく依存する。また、MP4(SDQ)法では 17.1 kcal/mol とかなり大きくなり、MP4 法はこの種の錯体には使用できない。GMC-QDPT 法では 4.3 kcal/mol であり、スピン転移が起こる実験事実を考慮すると妥
当な値であると考えられる。また、M06L を除くすべての計算で 4 重項の方が 2 重項よりも安定であることから、低温結晶中の 2 重項状態の安定化は主に結晶中の分子間相互作用に起因していると考えられる。
表 2. [Co(dpzca)2]のスピン状態間のエネルギー差⊿E(2et-4et) (kcal/mol)
method⊿Emethod

⊿E

PBE0

7.1

HF

49.1

B3LYP

2.4

MP2

16.6

B3LYP-D

0.7

MP3

26.7

M06

7.1

MP4(SDQ)

17.1

M06L

−1.8

RASSCF

23.8

GMC-QDPT

4.3分子間相互作用エネルギーの評価のため、結晶構造を用いたピラジン二量体のモデル計算を行い、CCSD(T)法の値と比較したところ、B3LYP-D 法が CCSD(T)と近い値を与えることから、QM/MM 法の計算には B3LYP-D 汎関数を用いた。
図１に示すように、[Co(dpzca)2]の結晶中のスピン状態のエネルギー差は B3LYP-D 法を用いた計
算では、低温結晶中の 2 重項状態が最も安定であり、高温結晶では 4 重項状態が 2 重項状態よりも安定である。QM 部分を GMC-QDPT 法で計算した場合はスピン状態の逆転は見られなかったが、高温結晶構造では低スピン状態が高スピン状態より 7.0 kcal/mol 不安定であるのに対して、低温結晶構造では 2.8 kcal/mol しか不安定とならず、低温構造における低スピン状態の安定性の増大という傾向は実験と一致している。

図 1 [Co(dpzca)2]の結晶中のスピン状態のエネルギー差 (kcal/mol)[Co(pypzca)2]は、孤立分子の計算では構造,スピン状態のエネルギー差共に[Co(dpzca)2]との違いは見いだせなかった。一方、結晶条件下の計算では、低温結晶構造における 2 重項状態の安定化
が[Co(dpzca)2]よりも小さく、B3LYP-D 法の結果ではどちらの結晶構造においても 4 重項が基底状－ 141 －

Ⅳ 研究業績 (2014)

態として得られた(図 2)。この結果は[Co(pypzca)2]ではスピンクロスオーバーが観測されないという実験結果に矛盾しない。

図 2 [Co(pypzca)2]の結晶中のスピン状態のエネルギー差 (kcal/mol)
２つの錯体のスピン状態のエネルギー差の違いが結晶中でのみ見られることから、両者の結晶構造に関して比較を行った。[Co(dpzca)2]では実験・計算結果の双方において、低温結晶構造の格子ベクトルが高温結晶構造よりも短い。一方、QM/MM 法で求められた[Co(pypzca)2]の低温結晶構造の格子ベクトルは、高温結晶構造よりも長い。
[Co(dpzca)2] 結 晶 で は 低 温 結 晶 構 造 で ピ ラ ジ ン 環 が 垂 直 方 向 の ピ ラ ジ ン 環 に 近 づ き 密 な π-staking 構造を形成する。一方、[Co(pypzca)2] 結晶ではピリジン環の水素原子の立体反発が、隣接分子に近づくことを阻害している(図 3)。また、c 軸方向の隣接分子との間の分子間相互作用は主にカルボニル基によるπ-π及び CH-π相互作用である。[Co(dpzca)2]の低温結晶構造ではカルボニル基が１つの隣接分子と相互作用に有利な様に近接する(図 3)。一方、[Co(pypzca)2] 結晶では制限された構造変化によって、カルボニル基と隣接分子との距離が増加し分子間相互作用が減少する。

図 3. QM/MM 結晶構造中の隣接分子との原子間距離－ 142 －

Ⅳ 研究業績 (2014)

以上の結果から、[Co(dpzca)2]と[Co(pypzca)2]錯体の違いは電子状態ではなく分子間相互作用に由来し【文献】[1] M. G. Cowan, J. Olguín, S. Narayanaswamy, J. L. Tallon, and S. Brooker, J. Am. Chem. Soc. 2012, 134, 2892
[2] M. G. Cowan and S. Brooker, Dalton Trans., 2012, 41, 1465
[3] S. Aono and S. Sakaki, Chem. Phys. Lett. 2012, 544, 77

2. 論文(1) Masayuki Nakagaki, Shigeyoshi Sakaki“CASPT2 study of inverse sandwich-type dinuclear 3d transition metal
complexes of ethylene and dinitrogen molecules: similarities and differencesin geometry, electronic structure, and spin multiplicity”
Phys. Chem. Chem. Phys. 17, 16294-16305(2015).

3. 学会発表(1) 中垣 雅之，青野信治，榊 茂好「Co(II)錯体の電子状態と分子間相互作用: スピンクロスオーバーの制御因子」
第 17 回理論化学討論会 2014 名古屋 2014/5/22-24 2P25 ポスター
(2) 中垣 雅之，青野信治，榊 茂好「スピンクロスオーバーを示す Co(II)錯体の電子状態と結晶内分子間相互作用」
第 8 回分子科学討論会 2014 東広島 広島 2013/9/21-24 4P103 ポスター
4. その他(1) 中垣 雅之，青野信治，榊 茂好
スピンクロスオーバーを示すCo(II)錯体の電子状態と結晶内分子間相互作用」
第12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 2015/1/23－ 143 －

Ⅳ 研究業績 (2014)

Yue Chen
Yue Chen
SPR Fellow
SPR Fellow
1. Summary of the research of the year
The Interaction between f Orbital and Radical N2-bridge Ligand in Single-Molecule
MagnetSince the discovery of the magnetic relaxation properties of the Mn12-acetate cluster, pursuing the efficient
single-molecule magnet (SMM) that functions at higher temperature is still a grand challenge. A substantial
spin reversal barrier U of the total spin S is essential for the magnetic property of SMM. Because thebehavior of SMM is related to the total spin and the axial anisotropy D and U can be simply estimated by
U=|D|S2, two strategies are expected to useful for designing the SMM with high U value. One is to maximize
the total spin S by synthesis of high-nuclearity clusters. However, the clusters with many exchange-coupledtransition metals can achieve large S value but is accompanied by low D value that induces finally low U
value. This is likely due to the complicated interrelationship between S and D. Therefore, in recent years,
considerable attention has focused on the other strategy: designing SMM with large anisotropy barriers.
Lanthanide ions are commonly employed in the SMM because its unquenched f orbital moments and strong
spin-orbit coupling can produce high anisotropy. In 2003, Ishikawa et al. developed first mono-lanthanide
SMM [LnPc2]n (Ln = Tb3+ and Dy3+; H2Pc = phthalocyanine;

n = -1, 0, +1) which present considerably-1

greater U value (260 cm ) than the reported 3d-SMM; see Scheme 1. Furthermore, the some polymetallic
lanthanide complexes have been reported to possess clear SMM property and large U value. The
understanding of magnetic interaction between lanthanide ions and between lanthanide and ligand is usefulfor improving the polymetallic lanthanide SMM. Recently, Long et al. found the radical bridge ligand canaffect the SMM property significantly in dinuclear lanthanide complexes. For example, the N23- radical
bridged lanthanide complex {[(Me3Si)2N]2Ln(THF)(μ-η2:η2-N2)(THF)Ln[(Me3Si)2N]2}1- (abbreviated as[Ln(N2)Ln]1-, Ln = Gd, Tb, Dy, Ho, Er) have remarkable electronic structure. In Gd complex, a strong
intramolecular exchange coupling (J = -27 cm-1) was observed. The Tb complex is marked as the mostsuccessful SMM to date due a record blocking temperature TB of 14 K for M(H) hysteresis, and the Dy
complex also shows TB of 8.4 K. However, the Ho and Er complexes do not show any M(H) hysteresis.
Because these complexes has quite similar geometries in which the N-N bond length is between 1.394 and1.408Å, the difference of Ln properties influence the SMM properties significantly. In this work, wetheoretically analyzed the electronic structure of [Ln(N2)Ln]1- (Ln = Gd, Tb, Dy, Ho, Er) and revealed theinteraction between N2-birdged and lanthanide.
Because the Gd3+ has f7 electronic configuration, the electronic structure of [L3Gd(N2)GdL3]n (n = 0, -1) ismore simple than other lanthanide analogues. We firstly analyzed the electronic structure of Gd complexes,
and then revealed the similarity and difference with other lanthanide complexes. In the neutral[L3Gd(N2)GdL3], the N2-bridge ligand is expected to be N22- in which theis empty andis doubly

occupied. The two Gd center can couple via two manner high-spin state (State A) and low-spin state (State－ 144 －

Ⅳ 研究業績 (2014)B); see Scheme 1. Since the one additional electron in [L3Gd(N2)GdL3]1- is supposed inof N23-bridge-ligand, the three spin centers (two Gd3+ and N23-) can couple into three spin states; see high-spin stateC, low-spin state D, and low-spin state E in Scheme 1. The difference in geometry is tiny between state A
and B. The N1-N2 bond length of bridged N2 ligand is 1.234 Å that agrees well with experimental value of
1.278 Å. In state A, the spin density on Gd1, N2, and Gd3 are 7.07, -0.05, and 7.07, respectively, while they
are 7.08, 0.00, and -7.08 in state B. In both state A and B, theis empty andis doubly occupied,

indicating that the electronic structure of N2-bridge ligand is N22-; see Figure S1. The energies of state A and
B are nearly the same; see Table 1. The same geometry and energy indicates that the two Gd atoms in state A
and B have little exchange correlation to each other. For anionic complex [L3Gd(N2)GdL3]1-, the low-spinstate D and E is lower than the high-spin state C but their geometries have little difference; see Figure 1. The
geometries of state A-D are Ci symmetrical but state E is C1 symmetrical. For Tb, Dy, Ho, and Er systems,
the similar case in the geometry was found. The state A and B are nearly degenerate, but the energies of state
D is not always the lowest one.
L3Ln

0

N

L3Ln

LnL3

N

x*

z*

z*

fn

fn

High-spin State A

Low-spin State B

LnL3

N

L3Ln

LnL3

N

L3Ln

f

n

x*

High-spin State C

z*
n

f

LnL3

N

z*
n

1-

N

x*

z*

f

1-

N

x*

n

z
fn

1-

N

y

LnL3

N

x*

fn

L3Ln

0

N

f

f

n

Low-spin State D

fn
Low-spin State E

Scheme 1. Different spin-coupling states.
Table 1. The energies of different spin states calculated by DFT.
Gd

Tb

Dy

Ho

Er

State A

22.5

22.2

21.0

23.0

27.8

State B

22.5

22.2

21.0

23.0

26.2

State C

0.0

0.0

0.0

0.0

0.0

State D

-1.6

0.4

0.0

-0.4

-1.9

State E

-0.8

-1.0

-3.0

0.0

-1.0

Unit: kcal/mol.

－ 145 －

Ⅳ 研究業績 (2014)

N1
Gd1

Gd2

N2

Gd1-N1

Gd2-N1

State A
State B
State CState D
State E

2.335
2.335
2.210
2.209
2.209

2.348
2.348
2.217
2.215
2.218

N1-N2

Gd1-N2Gd2-N2

1.234
1.234
1.385
1.388
1.386

2.348
2.348
2.217
2.215
2.214

2.335
2.335
2.210
2.209
2.211

Figure 1. The geometries of different states optimized by DFT.
Since the little influence of ligand field on the splitting f orbitals, these systems have strong
multi-configuration character. The electronic structures of state C and D are analyzed by CASPT2/CASSCF
method. The 14 f orbitals of two lanthanide atoms and thecalculation; see Figure 2. The

of N2 moiety were included in the CASSCF

of N2 moiety was not involved in the calculation of Tb-Er because it isalways doubly occupied. For Gd complexes, because CASSCF calculation of state C (16-tet) requires 16
of N2 moiety was involved.

orbitals at least,
7

Since Gd has f configuration, the state C and D are 16-tet and 14-tet, respectively. Four 16-tet states andfour 14-tet states were calculated by CASPT2/CASSCF(17e,16o). Among these states, there are three
low-lying energy state (X14Au, a16Au, and A14Ag) and five high energy states. The ground state is X14Au,
and a16Au and A14Ag are only 0.6 and 0.7 kcal/mol above X14Au, but the high energy states are above theground state by 49 kcal/mol at least. Because only these low-lying states are crucial to the magnetic
properties of Gd complex, the detailed electronic structure of these states were present here but the highenergy states were presented in supporting information.

Figure 2. The active orbitals involved in the casscf calculation.
In X14Au, four configurations

,

,

, and

with respective

weight of 30%, 24%, 18%, and 18% contribute most.30 The φ3ag is the bonding orbital between
moiety andof Ln2of N2 moiety, and the φ8ag is the anti-bonding orbital; see Figure 3. There results indicate aweak bonding interaction betweenof Gd andof N2 moiety. The Mulliken spin population on Gd1,

N2 moiety, and Gd2 are 6.91, -0.81, and 6.91, respectively. It seems like there is one β-spin electron localizedon N2 moiety which couples with seven α-spin electron of each Gd atoms formally. Actually, the negative－ 146 －

Ⅳ 研究業績 (2014)

spin population on N2 moiety arises from the spin polarization of φ8ag induced by the α-spin electrons of Gd
atoms; see Figure 3. Therefore, the formally anti-spin coupling state low-spin state D is the outcome ofspin-polarization.
Table 2. The Mulliken spin population of the Ln and N2 moiety in the ground state
Ground state

Gd

N2

Gd(N2)Gd

14

X Au

6.91

-0.81

Tb(N2)Tb

12

X Ag

5.90

-0.79

Dy(N2)Dy

10

X Au

4.88

-0.76

Ho(N2)Ho

8

X Ag

3.81

-0.62

Er(N2)Er

6

2.79

-0.58

X Au

In a14Ag, there is no dominant configuration but 16 important configurations contributes nearly 100%,and they are

,

,

, and

(i = 1-7) where the φiau and φiag

correspond to the Ag and Au symmetrical molecular orbital composed mainly of the same atomic f orbital of
Gd.30 The Mulliken spin population on Gd1, N2 moiety, and Gd2 are 6.03, 0.93, and 6.03, respectively, which
is different from that in X14Au. The lower spin population on Gd is induced by the exchange coupling
between two Gd atoms and coupling between N2 moiety and Gd.
As expected, A16Au has one main configuration with weight of nearly 100%, in which the
double occupied and(φag8) are(φag9) is singly occupied and the rest f orbitals are singly occupied. The Mulliken

spin population on Gd1, N2 moiety, and Gd2 are 7.03, 0.92, and 7.03, respectively. This state is thewell-known high-spin coupled state. In A16Au, theof Gd andof N2 moiety do not have bonding

14

overlap unlike that in the ground state X Au.
It is apparent that the low-spin state X14Au is more stable than the high-spin state A16Au, which isconsistent with the experimental observation. The -type bonding overlap betweenof Gd andof14

N2 moiety is crucial to the stability of X Au and expected to be responsible for the single magnet manner.
Though Tb(III) has only one more electron than Gd(III), the electronic structure of Tb complex becomes
more complicated. The energy differences among of the ten states (five 14-tet states and five12-tet state) areless than 3.0 kcal/mol. Similar to Gd complex, the ground state of Tb complex is low-spin state X12Ag
instead of high-spin 14-tet state. The lowest two excited 12-tet states (A12Au and B12Ag) are 0.3 and 1.1
kcal/mol above the ground state, and the lowest two excited 14-tet states (a14Au and b14Ag) are both about
1.3 kcal/mol higher. Similar to the ground state X14Au of Gd complex, there no dominant configuration in
X12Ag

of

Tb

complex,

but

four

configurations

,

,
, and

contribute significantly with total weight of 55%, indicating important role of the bonding interaction (φ3auand φ8ag) between

of Tb andof N2 moiety. The Mulliken spin population on Tb and N2 moiety are

5.90 and -0.79, respectively. The negative spin population on N2 moiety should also arise from the spinpolarization; see Figure 3. The first excited 12-tet state A12Au has nearly the same occupation numbers andspin population but different irreducible representation to the ground state. The a14Au contains two
configurations
contains two configurations

with weight of 50% and 50%, and b14Ag

and
and

－ 147 －

with weight of both 50%.

Ⅳ 研究業績 (2014)

The a14Au and b14Ag both have similar occupation numbers to the ground state but the positive spin
population (0.93) on N2 moiety. However, the bonding overlap between

of Tb andof N2 moiety

was not found, like the case in the high-spin state A16Au of Gd complex.

(A)

(B)

(C)

(D)

(E)
Figure 3. Spin polarization in the ground state of Gd complex (A), Tb complex (B), Dy complex (C), Ho
complex (D), and Er complex (E).
The ground state of Dy complex is how-spin 10-tet and nearly triply degenerate (X10Au, X’10Au, and
X”10Au). There are six low-lying excited 10-tet states that are 0.3-0.5 kcal/mol above the ground state. Theenergies of all the calculated excited state are among 0.3 and 1.3 kcal/mol relative to ground state. Different
from the ground states of Gd and Dy complex, there is no bonding overlap between
N2 moiety but the overlap betweenof Dy andof Dy andofof N2; see Figure 3. The spin distribution on Dy

and N2 are 4.88 and -0.76, respectively, where the negative spin population on N2 moiety is also attributed tothe spin polarization.
The Ho has a low-spin ground state X8Ag and the Er complex has a low-spin ground state X6Au. In bothstates, there is no bonding overlap between
of Ln andof Dy andof N2 moiety but weaker overlap betweenof N2 moiety; see Figure 3. The Mulliken spin population on the N2 moiety in Ho and Er

complexes are -0.62 and -0.58, respectively; see Table 2. Meanwhile, there are a lot of low-lying excitedstate, including both high-spin and low-spin states.

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Ⅳ 研究業績 (2014)

From Gd to Er complex, there are some similarities. (1) All the ground states are the low-spin coupledstate, where the N2 has negative spin population. (2) The multi-reference character is significant since many
configurations contribute comparably to the ground state; (3) There are a lot of low-lying excited states. (4)The high-spin state and low-spin state have little difference in geometry. Meanwhile, the differences areimportant. (1) In Gd and Tb complexes, theof Ln andof N2 can form a -type bonding andanti-bonding orbitals. However, only the overlap between

of Ln andof N2 instead of -type

bonding overlap above was observed in Dy, Ho, and Er complexes; see Figure 3. In addition, the overlap
betweenof Ln andof N2 becomes weak from Dy to Er. (2) From Gd to Er, the number of

low-lying excited states increases because of the increasing of f-electrons. (3) The spin population of N2 on
the ground state becomes less negative from Gd to Er.
Based on the results above, the interaction between Ln and N2 moiety among these five complexes canbe categorized into two types. The first is the -bonding type that includes Gd and Tb complexes, and thesecond is general orbital overlap type that includes Dy, Ho, and Er complexes. These two different types are
related to two factors: f-orbital splitting and f-orbital energy. Even though f-orbital is inner-shell and notaffected by the ligand field significantly, the small splitting of f-orbital has crucial role to the magnetic
properties at very low temperature. The splitting of f-orbital can be reflected by the change of f-orbital
occupation number on the ground state from Gd to Er. In Gd complex, the

(

),

(

) are allsingly occupied,31 where the term in parenthesis is the major component of corresponding. With the

(

),

(

),

(

),

,

increase of one electron from Gd to Tb, the occupation numbers of(), andandincrease to about 1.5,

whereas the other orbitals are still singly occupied. From Tb to Dy, the occupation number ofincrease to about 1.5 too, buttotoare still singly occupied. From Dy to Ho to Er, only theis still singly occupied. We can deduce that the f-orbital energy order in these complexes is~<~Among 7 f-orbital, only

<

<

<

can form -bonding overlap withdisappearance of -bonding overlap is likely due to the decrease ofchanges little. Because (1) theand (3) orbital lobes ofEr, the, but the orbital splitting is small.
of N2. From Tb to Dy, theof Dy since theis the highest f-orbital, (2) the occupation number ofextends towards

energyincreases,, the overlap between

andoccurs. From Dy toenergy decreases continuously, the overlap degree between

anddecreases.

2. Original papers(1) 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. 43, 11478-11492(2014)(2) Shubin Yang, Changlun Chen, Yue Chen, Jiaxing Li, Dongqi Wang, Xiangke Wang
"Competitive Adsorption of PbII, NiII, and SrII Ions on Graphene Oxides: A CombinedExperimental and Theoretical Study”
ChemPlusChem 80(3),480–484 (2015)

3. Presentation at academic conferences(1) Yue Chen, Shigeyoshi Sakaki－ 149 －

Ⅳ 研究業績 (2014)

ChemPlusChem 80(3),480–484 (2015)

3. Presentation at academic conferences(1) Yue Chen, Shigeyoshi Sakaki“Catalysis of Mo-Mo Quintuple Bond in Synthesis of Benzene from Alkyne. A Theoretical
Study”The XXVI International Conference on Organometallic Chemistry (ICOMC 2014), July 13
to 18, 2014, Sapporo, Japan
4. Others(1) Yue Chen, Shigeyoshi Sakaki“Theoretical Study on the H2 and X-H bond Activation by Mo-Mo quintuple bond”
第12回京都大学福井謙一記念研究センターシンポジウム -諸熊奎治先生傘寿記念-,
Kyoto. Jan. 23, 2015

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Ⅳ 研究業績 (2014)

Sayyed Fareed Bhasha
Advanced
Scientist
Advanced Scientist
1.

Summary of the research of the year

The increase of carbon dioxide (CO2) content in the atmosphere is a serious threat to the environment.
The development of the transformation of CO2 into useful chemicals has been one of the important
topics in the last decade. In this regard, various attempts have been made using transition-metal
complexes. Among various CO2 transformations, direct carboxylation of organic halide with CO2
has been elusive until recently, though such direct carboxylation is attractive because of theimportance of carboxylic acids for valuable applications. Martin and co-workers introduced thetransformation of benzyl halide to phenylacetic acid with CO2 using a Ni catalyst (Scheme 1). This
Ni-catalytic system contains Zn powder and MgCl2. If Zn powder is absent, no catalytic conversion
occurs. If MgCl2is not added, the yield is very low. The experimentally proposed reaction
mechanism suggests that a NiI intermediate might be crucial in the catalytic cycle, as shown in
Scheme 2. However, mysterious is the role of MgCl2; it is not clear why MgCl2 plays a crucial role inproviding good yield of the product. We theoretically investigated this Ni-catalyzed carboxylation of
benzyl chloride to phenylacetic acid to elucidate the role of MgCl2. All the calculations were carriedout with the B3LYP-D functional using Gaussian 09 package.

Scheme 1. Ni-catalyzed carboxylation of PhCH2Cl with CO2.

Scheme 2. Plausible mechanism for the Ni-catalyzed carboxylation reaction of PhCH2Cl with CO2.
In this reaction, it is likely that the catalytic cycle begins with the oxidative addition of benzyl
chloride 1 to Ni(PCp3)2 2 (Cp = cyclopentyl); see scheme 2. Starting from 3, the oxidative addition of
the PhCH2-Cl bond occurs to afford a four-coordinated NiII-intermediate cis-NiII(Cl)(CH2Ph)(PCp3)24 via a transition state TS3-4. The ΔG°‡ is 9.3 kcal/mol, indicating that the oxidative addition easily
occurs (Fig 1). The complex 4 isomerizes to a more stable trans-form NiII(Cl)(CH2Ph)(PCp3)2 5.
1－ 151 －

Ⅳ 研究業績 (2014)

TS3-4

1+2

6.2

3

0.0

-3.1
Ni(PCp3)2

PhCH2Cl

2

1

Cp = cyclopentyl
1.

4
-33.4

5
-41.5

2.

Fig. 1 Changes in the Gibbs energy and geometry by the oxidative addition of 1 to 2. Cp represent
cyclopentyl group. Bond lengths are in Å and angles in degree.
MgCl2 interacts with the CO2 moiety of Ni(I) species formed after the one-electron reduction of 5 toform an adduct Ni(CH2Ph)(PCp3)2(1-CO2)(MgCl2). The Mg-O distance (1.951 Å) and the O-C-O
angle (133.6°) which is smaller than in Ni(I)-CO2 adduct. These geometrical features indicate that the
Mg-O and Ni-CO2 interactions are considerably stronger in Ni(CH2Ph)(PCp3)2(1-CO2)(MgCl2) than.
The ΔΔG0‡ (ΔG0‡( TS8-9)-ΔG0‡(TS12-13)) value (12.0 kcal/mol) strongly suggests that MgCl2
accelerates the CO2 insertion into the Ni-CH2Ph bond as a non-innocent additive.
The final step is the one-electron reduction of 13 with Zn. The calculated ΔG0 value for this step is-12.4 kcal/mol. The anion exchange between Zn(O2CCH2Ph)2 and MgCl2 occurs with a considerably
negative ΔG0 of -15.4 kcal/mol, indicating that the formation of Mg(O2CCH2Ph)2 isthermodynamically more favourable. These results suggest that MgCl2 also assists the one-electron
reduction. Because MgCl2 is consumed in the reaction, two-equivalent of MgCl2 to benzyl chloride isnecessary (Scheme 1).7 The Gibbs free energy profile for the total catalytic cycle clearly indicates that
MgCl2 promotes the carboxylation of benzyl chloride with CO2.
In conclusion, we proposed that MgCl2 plays crucial roles in the CO2 insertion as a non-innocent
additive and one-electron reduction process. To the best of our knowledge, this is the first report thatrecognizes these roles of MgCl2 and provides correct understanding of the roles in the CO2 conversion
reaction.
3.

List of original papers
1. Sayyed, F. B.; Sakaki, S. “The Crucial Roles of MgCl2 as a Non-innocent Additive in the
Ni-Catalyzed Carboxylation of Benzyl Halide with CO2”. Chem.Commun. 2014, 50,
13026-13029.

4.

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:2－ 152 －

Ⅳ 研究業績 (2014)

Theoretical Understanding of Electronic Processes“
Inorg. Chem. DOI: 10.1021/ic5003429 (2014).
5.

List of presentations at meetings(1) The Crucial role of Ni(I) species in Ni-catalyzed Carboxylation of Aryl Halides with CO2:
Theoretical Study. F. B. Sayyed, Y. Tsuji and S. Sakaki, ICOMC2014, July13-17, Sapporo

3－ 153 －

Ⅳ 研究業績 (2014)

山田 健太
山田	
  健太
	
 

特推研究フェロー

特推研究フェロー	 	
 1. 今年度の研究の要約	 	
 今年度は、昨年度に引き続き、長時間に亘って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。
	
 【はじめに】
われわれが目指してゆく低炭素社会に向けた、次世代エネルギーの 1 つである水素ガスは、入手可能な天然資源として大量には存在しない。そこで、近年、遷移金属錯体の存在下において、電気化
学的な酸化還元反応による水素ガスの生成が注目されている[1]。
	  水 1 分子の分解(式 1)は吸熱反応であり、必要なエネルギーは 2.46 eV である。この反応を進行さ
H2O → H2 + (1/2)O2(1)

せるために必要なエネルギーとして、化石燃料の代わりに、太陽光や風力などを用いる。つまり、この反応を用いることによって、自然エネルギーを、化学エネルギーに変換し、水素ガスとして蓄えることができる。式 1 の逆反応である水素ガスの酸化(燃焼)では、二酸化炭素(CO2)は発生せず、
2.46 eV のエネルギーが得られることが分かる。
	  可能な限り少ないエネルギーによる水素ガスの生成を目的とした、プロトン還元活性をもつ遷移金属触媒の報告が、多くの実験研究によって行われている。特に、コスト面から Pt といった貴金属ではなく、Co や Ni、Mo など卑金属を用いた触媒の提案が盛んである。本研究では、これまで提案されてきた触媒のなかで、長時間に亘って高い水素発生活性を示す Ni(II)錯体[2]を取り上げた。
その錯体における 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に取り組んできた。
【計 算 方 法 】
DFT (B3PW91 汎関数) 法を使用し、溶媒分子を連続誘電体として扱う CPCM 法で溶媒効果を考慮
して構造最適化を行った。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N

子価電子には(311111/22111/411/11)基底を用いた。

S

生成する水素ガスに関与する H には

S
Ni
N

N

N

S

S

S
Ni
N

S
N

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、

meridional,1m

図 1：注目した Ni(II)錯体の６配位構造がとる、２
つの異性体
%%

%
%

288 K における EtOH:H2O=1:1 の混合溶媒を用い

facial,1f%%%%－ 154 －

Ⅳ 研究業績 (2014)

験値を使った内挿から決定した。

N

H2

kcal/mol だけ、わずかに 1f が安定である結果が得られた。また、両異性体とも三重項状態が安定となった。

	  スキーム１に 1 %から、実験から提案されている

N

NiII

H+

S

$%&

1m のみであるが、計算によると溶液中では 0.8

S

N

2

1

に示すような facial 型(1f)と meridional 型(1m)の異性体が存在する。X 線結晶解析で観測できるのは

NiII

S N

7

取り上げた Ni(II)錯体の６配位構造(1)には、図１

–

S

! "#

%

【結果と考察】

!"#
$%(

%

た実験条件を再現するために、複数の温度での実

e–

–

N

S H!" S
+
NH!

6

N

5

S

4
e–

H+

!"#$%'

始まる水素発生サイクルを示す。このサイクルは、

S
NiI
NH

–

N
S

3
	
 

	
 

プロトン付加→１電子還元→プロトン付加→１

スキーム１	
 電子還元の順序で進行する（CECE 機構）。
	  Step 1 では、プロトンはピリジン環の N に付加する場合、1m から３つの異性体が生じるので、2には合計４つの異性体が存在する。続いて生じる１電子還元に掛かる還元電位の計算結果は、実験を概ね再現した。一方、1 で１電子還元が起こる場合を考えると、その還元電位の計算値は実験値と大きく異なっている。これらの結果は、Step 1 はプロトン付加→１電子還元の順序で進むことを支持している。
	  Step 2 において、3 に対するプロトン付加は、Ni(I)に付加するのではなく、ピリジン環の N への付加(4)が約 20 kcal/mol が安定であった。１電子還元は、ピリジン環の π 性反結合性軌道で起こり(5)、それに連続してピリジン環の N から Ni(I)へのプロトン移動による異性化反応が生じる(6、図２)。
ただし、この順序とは逆に、プロトン付加に先んじて１電子還元が起こる可能性を、現在の計算結果からだけでは否定できない。

20.6
0.0

5A f

TS5_6f

1.4

5Bf

–13.2

6A f

図２：Step 2 における、１電子還元体(5)からプロトンが移動する異性化反応のエネルギープロファイルと、そのときの SOMO の変化。図中の数字の単位は、kcal/mol である。

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Ⅳ 研究業績 (2014)

	  Step 3 は、Ni(II)–H とピリジル環の N–H 間のカップリングを経由して、水素ガスが発生する反応である（図３）。この反応の障壁は 0.6 kcal/mol と非常に低く、7 からの H2 の解離には障壁を見つけられなかった。これらは、本研究で取り上げた Ni(II)触媒が高い水素発生活性をもつ理由であると考えられる。また、この低い反応障壁は、H2 になる２つの H 以外の幾何構造が大きく変化せず、
Hδ–···Hδ+–N が直線状構造になることで、遷移状態が安定化することに起因する。

0.0

2.047

S2

–1.9

6A f

H36

C14
N15

S24

6Bf

H35

N4

Ni–H35=2.440

TS6_7f

2.056

C3

7f

H35

2.197 C25
S13 2.534
Ni 2.393
S24

2.562

N4

–6.3

22
1.3 N26

1.754

C14
N15

0

2.045

C3 S2

–1.3

8
.99

2.020 C25
2.504
2.356 S24

S13

2.052 Ni

H36!"#$%&'()*+,'

76N26

2.0

73

0.7

2.492

C3

2.558
2.434

C25

2.652

N4

N26

H35

52

2.062

S13

Ni

1.062

1.9

C14
N15

45

1.4

1.666

H36

2.046

S2

H2
–27.8

1f

図３：Step 3 における、6 から水素ガスが発生する反応のエネルギープロファイルと、そのときの幾何構
造の変化。図中の数値の単位は、kcal/mol と Å である。

【文 献 】 [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.

2. 論文	
 1. Yamada, K.; Kawashima, Y.; Tachikawa, M. “Accurate Prediction of Hyperfine Coupling
Constants in Muoniated and Hydrogenated Ethyl Radicals: Ab Initio Path Integral Simulation
Study with Density Functional Theory Method” J. Chem. Theory. Comput. 2014, 10, 2005–2015.

2. Mashiko, T.; Yamada, K.; Hiraoka, S.; Nagashima, U.; Tachikawa, M. “Molecular dynamics
simulation of self-assembled nanocubes in methanol” Mol. Simul. 2014, 41, 845–849.

3. Yamada, K.; Kawashima, Y.; Tachikawa, M. “Quantum simulation for muoniated and deuterated
methyl radicals in implicit water solvent: combined ab initio path integral molecular dynamics andthe polarizable continuum model simulation study” Mol. Simul. 2014, 41, 832–839.
	 － 156 －

Ⅳ 研究業績 (2014)

3. 学会発表	 1. ○Hiyama, M.; Yamada, K.; Mochizuki, T.; Akiyama, H.; Koga, N. “Theoretical study of pH
dependence on photoluminescence of firefly luciferin”, 18th International Symposium on
Bioluminescence and Chemiluminescence, P0027, Uppsala Universitet, Uppsala, Sweden (Jun.
2014)

2. ○山田健太、榊茂好 “ニッケル(II)錯体のプロトン還元触媒作用に関する理論的研究”、錯体化学会第 64 回討論会、2PB-029、中央大学後楽園キャンパス、東京 (9, 2014)

3. ○山田健太、榊茂好 “Ni(II)錯体の構造、電子状態とプロトン還元活性に関する理論的研究”、
第 8 回分子科学討論会 2014 東広島、4P126、広島大学東広島キャンパス、東広島 (9, 2014)

4. ○山田健太 “Ni(II)錯体の分子構造とプロトン還元活性に関する理論研究”、第 2 回 CUTE
シンポジウム「コンピュータ化学」、三重大学極限ナノエレクトロニクスセンター、津 (10,2014)

5. ○樋山みやび、野口良史、望月敏光、山田健太、秋山英文、古賀伸明 “ホタル生物発光関連分子における分光的性質についての理論研究”、 機能物性融合科学研究会シリーズ(1)「光機能」、P14、東京大学柏キャンパス（物性研究所）、柏 (12, 2014)	 4. その他	
 1. ○山田健太、榊茂好	 「プロトン還元活性を示すNi(II)錯体による触媒反応機構に関する理論的研究」第12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	
  2015/01/23	
  P51	 	
 － 157 －

Ⅳ 研究業績 (2014)

Shuwei Tang
ShuweiTang
SPR Fellow
SPR Fellow
1. Summary of the research of the year
Reaction Mechanism and Regioselectivity of [Ni(NHC)/AlMe3]-Catalyzed Olefin
Hydroarylation through C−H Activation

The hydroarylation of unsaturated olefins through direct functionalization ofaromatic C-H bond is a typical delegate in the class of C-C bond formation reaction.
However, current metal catalyzed hydroarylation that generating linear products still faces
many deficiencies, such as requiring directing groups, occurring with specific heteroarenes,or occurring with modest preference for linear over the branched product. An efficient
cooperation of transition metals (TMs) with Lewis acids (LAs) is expected to be a powerfulimplement for such aromatic C-H bond activation. Recently, Nakao and co-workers
reported a combination of nickel, Lewis acid, and N-heterocyclic carbene (NHC) ligand
directly catalyzed the aromatic C-H bond of N, N-dimethylbenzamide with good to
excellent yields and broad substrate applicability. However, the mechanistic details and theorigins of regioselectivity about this reaction are not elucidated at present. Also, the role of
LA in the Ni-catalyzed aromatic C-H activation is not clear at all.
Here, we theoretically investigated the Ni0(NHC)/LA catalyzed hydroarylation of
linear olefins using DFT method with M06 functional (Scheme 1).
Scheme 1(1) The most favorable catalysis cycle of this reaction consists four key elementary
steps：coordination of N, N-dimethylbenzamide to the nickel (0) center, C-H bondactivation of aryl group, isomerization of alkylation production, and C-C bond reductive
elimination, as presented in Scheme 2. In the C-H activation process, the H transfer occurs
from aryl group to alkene without forming a Ni-hydride intermediate, which is understood
to be the oxidative addition to the metal-ligand moiety. In the C-C reductive elimination
step, the TS without propene coordination is more favorable.

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Ⅳ 研究業績 (2014)

Scheme 2(2) In the comparison of various ligands [small (IMes) vs. bulky ligand (IPr*)], thereaction mechanisms are same to each other, and the C-C reductive elimination is the rate
determining step. Compared to the IMes ligand case, the activation barriers in bulky ligand
system decrease 1~2kcal/mol, see Figure 1. In the part of ratio calculation of para- andmeta-products, our result is p/m=60:40, which is in good agreement with the experimental
value (p/m=58:42).

Figure 1. Energy profiles (ΔG°373.15K) of the hydroarylation of olefin without LA.

－ 159 －

Ⅳ 研究業績 (2014)(3) In order to understand the role of LA in the reaction mechanism, we investigated
the reaction in bulky NHC ligand (IPr*) that catalyzed by nickel and AlMe3. In our
calculation, the LA prefers to coordinate with amide part of N, N-dimethylbenzamide.
Figure 2 presents the Gibbs energy profile of hydroarylation of olefin with LA case. Due tothe charge transfer from aryl group to LA, the activation barriers considerably decrease incomparison with the situation without LA. Moreover, the presence of LA changes the rate
determining step, namely, from reductive elimination of C-C bond to C-H activation step.
For the ratio calculation for para- and meta-products, we have got a data of p/m=72:28,
significantly high than the situation with LA participation, and also in a good agreementwith experimental data of p/m=81:19 in qualitative. Therefore, the presence of Lewis acidincreases the regioselectivity of reaction.

Figure 2. Energy profiles (ΔG°373.15K) of the hydroarylation of olefin with LA.

(4) In order to get insight into the dependence of different M (M=Ni, Pd, Pt) on thereaction mechanism, we take the reaction promoted by Pd without LA case as an example.
Figure 3 describes the Gibbs energy profile of hydroarylation of olefin promoted by Pd.
Apparently, the mechanism is significant different from the Ni case, because a Pd-hydrideintermediate is located with high energy. Moreover, the rate determining step changes from
C-C bond elimination step to hydrolation process, and the activation barriers are－ 160 －

Ⅳ 研究業績 (2014)

considerably higher (~5 kcal/mol) than the Ni case. This may be one reason for the truththat Pd is not suitable for hydroarylation of linear olefins.

2. Original papers(1) Shuwei Tang, Shogo Okumura, Yoshiaki Nakao, and Shigeyoshi Sakaki, “Reaction
Mechanism and Regioselectivity of [Ni(NHC)/AlMe3]-Catalyzed Olefin Hydroarylation
through C-H Activation: A computational study”, in preparation.
(2) Shuwei Tang, Shogo Okumura, Yoshiaki Nakao, and Shigeyoshi Sakaki, “Alkylation
Reaction of Aromatics via C-H Activation Process: Theoretical Study of Metal and Ligand
Effects”, in preparation.
3. Presentation at academic conferences
Shuwei Tang, Shogo Okumura, Yoshiaki Nakao, and Shigeyoshi Sakaki, “Reaction
Mechanism and Regioselectivity of [Ni(NHC)/AlMe3]-Catalyzed Olefin Hydroarylation
through C-H Activation: A computational study”, 第 2 回 中尾 T CREST 合同研究会について, Tokyo, March 29, 2015.

－ 161 －

Ⅳ 研究業績 (2014)

4. Others
Shuwei Tang, Shogo Okumura, Yoshiaki Nakao, and Shigeyoshi Sakaki, Mechanism andRegioselectivity of [Ni(NHC)/AlMe3]-Catalyzed Olefin Hydroarylation through C-H
Activation: A computational study”, The 11th symposium of Fukui Institute for
Fundamental Chemistry, Kyoto, January 23, 2015.

－ 162 －

Ⅳ 研究業績 (2014)

Hong Zheng
Hong ZHENGSPR Fellow
SPR Fellow
1. Summary of the research of the year
Addition of Dinuclear Ruthenium Complex to Fullerene: Theoretical Study of Reaction
mechanism and Prediction
In the light of unique properties of transition-metal complex and fullerene, a large number oftransition-metal complexes of fullerene have been synthesized and are expected to be new materials for theirnovel properties. However, most of transition-metal complexes of fullerene are of η2-coordination orη5-coordination, while very few cases involve η1-coordination and deeper interpretation on them is still
destitute. Recently, a new kind of transition-metal complexes of fullerene C60{η1-Ru(CO)2(η5‑C5H5)}2,
which is recognized as the first kind of pure η1-coordination between transition metal and fullerene, wasdiscovered.

Scheme 1. Reaction between {(η5‑C5H5)Ru(CO)2}2 and C60-Ih.
In this work, extensive theoretical study on the formation mechanism and electronic structure of1

C60{η -Ru(CO)2(η5‑C5H5)}2 were performed. The reaction mechanism between {(η5‑C5H5)Ru(CO)2}2 andC60 was comprehensively investigated considering all possible pathways. As the product was obtained with asmall yield after a long period (4~6 months), implying a large energy barrier and maybe a small reactionenergy, one Li+ cation was introduced into the C60 cage for the purpose of refining the reaction mechanism.
Specially, the mechanism of excited state, corresponding to the photo irradiation in experiment, was probedand compared to the experimental proposal.
Reaction mechanism of singlet surface. When the Ru complex approaches the fullerene cage, three
types of reaction pathways arise, in which the C60 cage exhibits different orientations. Among all the reaction
patterns, pathA has the smallest activation barrier (ΔG‡= 45.80 kcal/mol) and hence becomes the mostprobable mechanism (Fig 1). The Ru-Ru distance has been dramatically enlarged (from 2.77 Å to 3.85 Å)
after the first peak and no direct orbital overlap between the Ru atoms exists in the intermediate state (INTA),
in which the Ru centers are linked barely by a bridging carbonyl and the Ru-C60 bonding feature is of
η2-fasion. Then, along with the cleavage of another Ru-CO bond, the two Ru centers in INTA will move tothe para sites of one six-member ring of the carbon cage and finally reach the product (PRO) geometry
through the second transition state (TSA2). TSA2, in which the Ru-Ru distance is furtherly elongated to 4.20

－ 163 －

Ⅳ 研究業績 (2014)Å and one Ru center is attached to the cage in the form of η1-coordination while the other one is 3.32 Å awayfrom the addition site, lies 9.68 kcal/mol above TSA1 in Gibbs energy and evidently is of the mostimportance in the whole reaction process.

Fig 1. Gibbs energy profiles of the optimum reaction pathway (pathA). The relative potential energies arealso presented in red color.
Reaction between {(η5‑C5H5)Ru(CO)2}2 and Li+@C60. Two types of reaction mechanisms between
the Ru complex and Li+@C60 were investigated and the better pathway is displayed in Fig 2. The Ru
complex can interact with Li+@C60 easier than C60 thanks to a negative reaction energy and a lower
activation barrier. The situation is rather ambiguous when the first Ru center reacts with the cage, whereas
the reaction of the second Ru center brings in a sharp barrier. The fact that the geometry structure of
Li+-TSA2 is alike to TSA2 implies the lowered activation energies would essentially originate from thechange of electronic feature.

Fig 2. Energy profiles of Li+-pathA.

－ 164 －

Ⅳ 研究業績 (2014)

Further analyses of electron populations of pathA and Li+-pathA recover significant differences ofelectron transfer between the two reactions: In pathA, the carbonyls donating about 0.3 e to the fullerene
cage plays the most important role during the electron transfer process, while the Cp rings show rather aninert performance; In Li+-pathA, not only the carbonyls but also the Cp rings donate electron to C60.
Evidently the Li+ cation can draw more charge from the Cp rings to promote electron transfer and thus thereaction will be efficiently smoothed.

Fig 3. Energy profiles of t-pathA.
Reaction mechanisms including photo irradiation. The multi-step reaction pathways in the presenceof photo irradiation were simulated and t-pathA with the same orientation of fullerene cage as pathA isdetermined to be the optimum mechanism (Fig 3). As depicted in Fig 3, the energy changes of triplet surfaces
are rather flat and intensive tendency of forward reaction can be expected since the triplet product t-PRO ismuch more stable than the triplet reagents t-ADA. As comparison, the excited Ru complexes of all
tautomeric forms and the further decomposition product (two (η5 ‑C5H5)Ru(CO)2 radicals) have been
calculated. It is found that the decomposition of the most stable triplet Ru complex is endothermic and hencesuch cleavage of Ru-Ru bond assumed in previous report is actually unreasonable.

Fig 4. Gibbs and potential energy differences among singlet and triplet dinuclear Ru complexes and double
Ru-centered radicals.
－ 165 －

Ⅳ 研究業績 (2014)

In this work, systematical theoretical study on the reaction between dinuclear Ru complex and C60
under various conditions were performed. The multi-step reaction between {(η5‑C5H5)Ru(CO)2}2 and C60 isslightly endothermic and needs a very large activation energy, which is consistent with the very low yield
experimentally reported. Also, being different from the rough reaction on the C60 cage, Li+-encapsulated C60
can easily react with the dinuclear Ru complex to afford Li+@C60{η1-Ru(CO)2(η5‑C5H5)}2 through a smaller
activation energy of 38 kcal/mol. It is revealed that not only carbonyls but also Cp rings donate electron to
the Li+@C60 species and therefore more electron transfer occurs within this Li+-included reaction. In
particular, the reaction at the triplet excited state happens with nearly no-barrier and negative reaction energy,
which is also consistent with the experimental result. The previous assumption of producing Ru-centeredradicals by means of cleaving Ru-Ru bond in the presence of photo irradiation has been excluded due to an
unreasonably endothermic cleavage process of the dinuclear Ru complex.

2. Original papers(1) Hong Zheng, Xiang Zhao, Shigeyoshi Sakaki,“Addition of Dinuclear Ruthenium Complex to Fullerene: Theoretical Study of Reaction
mechanism and Prediction” In preperation.
3. Others(1) Hong Zheng, Shigeyoshi Sakaki,“Theoretical Study on Crowded Organometallic Fullerene C60{ η 1-Ru(CO)2(η5-C5H5)}2”
The 11th symposium of Fukui Institute for Fundamental Chemistry, Kyoto, January 23,2015－ 166 －

Ⅳ 研究業績 (2014)

５．共同研究員

Maneeporn Puripat
Maneeporn Puripat
Visiting
Visiting Researcher
Researcher

1. Summary of the research of the year
Theoretical Study of Biginelli Reaction
The Biginelli reaction is a three-component reaction which was firstly published by the
Italian chemist Pietro Biginelli in 1893. Typically, it is the condensation of a benzaldehyde, an
acetoacetate and an (thio) urea and leads to dihydropyrimidines as product. It involves numerous
researches in the drug development programs for many pharmacological advantages such as
antihypertensive agents, potassium channel antagonists, anti-HIV agents, antitumor activity,
anti-epileptics, anti-malarials, anti-microbials, anti-inflammatories, anti-tubercular activity,
anti-bacterial activity and so forth. To enhance the efficiency of processes, several reports dealt withcatalyst variations which are Brϕnsted acids, Lewis acids, ionic liquids, biocatalysts andorganocatalysts.
In theoretical study of Biginelli reaction, finding transition state structures is essential
missions to analyze and predict its mechanisms. This knowledge is advantages for the design of amore effective process. Presently, there are numerous methods which were developed for searching
minimum energy reaction path automatically. One of them is the artificial force induced reaction(AFIR) method which was developed in 2010. It was applied to various organic reactions. Its ability
is to be able automatically and systematically explore all probable reaction pathways including
unexpected reaction paths.
Nevertheless, the mechanism of the Biginelli reaction is still not concluded. Thus, theBiginelli reaction mechanisms should be studied so that it can provide more understanding about
roles of catalysts. In this research, the plausible pathways of the Biginelli reaction using AFIR
method have been purposed.
For scope of the study, a benzaldehyde, an ethyl acetoacetate and a urea will be used as themodel for Biginelli Reaction. The transition structures will be located by means of AFIR using thedensity functional theory (DFT) at M06-2X with 3-21G basic set for the initial search and theirenergies will be recomputed with higher accurate methods 6-31+G(d) for final results. The
polarized continuum model (PCM) was employed in all calculations with the dielectric constant of
24.9 and 2.4 for ethanol and toluene, respectively. Moreover, the explicit solvent molecule(s) inethanol have been considered in the proton transfer steps to determine the effect of solvent proticity.
The intrinsic reaction coordinate (IRC) was employed to confirm the reaction pathway. In
all calculations, the first, and the second energy derivatives were calculated by the Gaussian09
program. The Global Reaction Route Mapping (GRRM) program was utilized to optimizations and
IRC calculations.
In this research, the entire reaction mechanism of the Biginelli reaction starting frombenzaldehyde, urea, and ethyl acetoacetate as reactants by using the recently-developed artificial
1－ 167 －

Ⅳ 研究業績 (2014)

force induced reaction (AFIR) method combined with DFT calculations have been investigated. The
most favorable pathway starts with the condensation of the urea and benzaldehyde, followed by theaddition of ethyl acetoacetate. Contrary to common believe, the rate-determining step of thisreaction is the cyclization step (C-N bond formation) with 21.5 kcal mol-1 activation energy.
Surprisingly, an extra urea can catalyze nearly all steps of all the routes. The role of the extra urea is
to stabilize the molecules and reserve a proton as proton donors and proton acceptors during theprocess. Thus, we can say that the Biginelli reaction is urea-catalyzed multicomponent reaction.
Also, the reaction mechanism was found to be identical in ethanol and toluene.
2. Original papers
─ Puripat, M.; Ramozzi , R.; Hatanaka, M.; Parasuk, W.; Parasuk, V.; Morokuma, K, J.
Org. Chem. 2015, Just Accepted.
3. Presentation at academic conferences─ The 12th FIFC Symposium, Kyoto, Japan, January 23rd, 2015.
─ The 16th International Conference on Density Functional Theory and its Applications in
Debrecen, Hungary, August 31st- September 4th, 2015.
4. Others-2－ 168 －

Ⅴ 資料 (2014)

Ⅴ資料

１．研究業績一覧（平成 26 年度）№

Volume (Number),first page tolast page

year

EPL

107, 28009

2014

Correlation of Local Order with Particle
Mobility in Supercooled Liquids is Highly
System Dependent

Phys. Rev. Lett.

113, 157801

2014

Diverging viscosity and soft granularrheology in non-Brownian suspensions

Phys. Rev. E

91, 012203

2015

Bull. Chem. Soc.
Jpn. (Award
Accounts)

87, 167-195

2014

Authors

Title

1

Takeshi Kawasaki, Atsushi
Ikeda, Ludovic BerthierThinning or thickening? Multiple
rheological regimes in dense suspensionsof soft particles

2

Glen M. Hocky, Daniele
Coslovich, Atsushi Ikeda,
and David R. Reichman

3

Takeshi Kawasaki, Daniele
Coslovich, Atsushi Ikeda,
and Ludovic Berthier池田

永瀬

Journal

昌司

茂

4

S. Nagase

Theory and Calculations of Molecules
Containing Heavier Main Group Elements
and Fullerenes Encaging Transition
Metals: Interplay with Experiment

5

Y. –J. Guo, T. Yang, S.
Nagase, and X. Zhao

Carbide Clusterfullerene Gd 2C2@C92 vs
Dimetallofullerene Gd 2@C94: A Quantum
Chemistry Survey

Inorg. Chem.

53, 2012-2021

2014

6

M. Yamada, H. Kurihara,
M. Suzuki, J. –D. Guo, M.
Waelchli, M. M. Olmstead,
A. L. Balch, S. Nagase, Y.
Maeda, T. Hasegawa, X. Lu,
and T. Akasaka

Sc2@C66 Revised: An Endohedral
Fullerene with Scandium Ions Nestledwithin Two Unsaturated Linear
Triquinanes

J. Am. Chem.
Soc.

136, 7611-7614

2014

7

T. Kuwabara, J. –D. Guo, S.
Nagase, M. Minoura, R. H.
Herber, and M. Saito

Enhancement of Stannylene Characterin Stannole Dianion Equivalents
Evidenced by NMR and Mössbauer
Spectroscopy and Theoretical Studies
of Newly Synthesized Silyl-Substituted
Dilithiostannoles

Organometallics

33, 2910-2913

2014

8

Y. Maeda, Y. Hasuike, K.
Ohkubo, A. Tashiro, S.
Kaneko, M. Kikuta, M.
Yamada, T. Hasegawa, T.
Akasaka, J. Zhou, J. Lu, S.
Nagase, and S. Fukuzumi

Photochemical Behavior of Single-Walled
Carbon Nanotubes in the Presence of
Propylamine

ChemPhysChem

15, 1821-1826

2014

9

Y. -J. Guo, B. – C. Gao, T.
Yang, S. Nagase, and X. Zhao

Sc2S@C68: An Obtuse Di-Scandium
Sulfide Cluster Trapped in a C2v Fullerene
CagePhys. Chem.
Chem. Phys.

16,
15994-16002

2014

10

P. Zhao, T. Yang, Y. –J. Guo,
J. –S. Dang, X. Zhao, and S.
NagaseDimetallic Sulfide Endohedral
Metallofullerene Sc2S@C76: Density
Functional Theory Characterization

J. Comput.
Chem.

35,
1657-1663

2014

11

H. Fang, H. Cong, M. Suzuki,
L. Bao, B. Yu, Y. Xie, N.
Mizorogi, M. M. Olmstead,
A. L. Balch, S. Nagase, T.
Akasaka, and X. Lu

Regioselective Benzyl Radical
Addition to an Open-Shell Cluster
Metallofullerene. Crystallographic
Studies of Cocrystallized Sc3C2@Ih-C80
and Its Singly Bonded Derivative

J. Am. Chem.
Soc.

136,
10534-10540

2014

12

Q. Zhou, H. Li, Y. Lian, M.
Suzuki, L. Bao, W. Cai, W. –W. Wang, S. Nagase, X. Lu,
and T. Akasaka

Regioselective Synthesis and Molecular
Structure of the First Derivativeof Praseodymium-Containing
Metallofullerenes

Chem. Commun.

50, 9876-9878

2014－ 169 －

Ⅴ 資料 (2014)

Volume (Number),first page tolast pageyear

Chem. Asian J.

9, 2604-2611

2014

Syntheses, Structures, and Reactivities of
Two Chalcogen-Stabilized Carbones

Angew. Chem.
Int. Ed.

53, 9569-9571

2014

T. Kuwabara, J. -D. Guo,
S. Nagase, T. Sasamiri N.
Tokito, and M. Saito

Isolation and Characterization of[5,6]-Pyrrolidino-Sc3N@Ih-C80
Diastereomers

Chem. Commun.

50,
12552-12555

2014

16

Y. Maeda, M. Kimura,
C. Ueda, M. Yamada, T.
Kikuchi, M. Suzuki, W. –W. Wang, N. Mizorogi, N.
Karousis, N. Tagmatarchis, T.
Hasegawa, M. M. Olmstead,
A. L. Balch, S. Nagase, and T.
AkasakaSynthesis, Structures, and Electronic
Properties of Triple- and Double-Decker
Ruthenocenes Incorporated by a Group
14 Metallole Dianion Ligand

J. Am. Chem.
Soc.

136,
13059-13064

2014

17

M. O. Ishitsuka, H. Nikawa,N. Mizorogi, F. Kimura, T.
Kimura, T. Kato, S. Nagase,and T. Akasaka

Magnetic Alignments of Endohedral
Metallofullerene Nanorods under
Magnetic Fields

Fullerenes,
Nanotubes,
CarbonNanostruct.

23, 35-39

2014

18

T. Iwamoto, Z. Slanina,
N. Mizorogi, J. –D. Guo,
T. Akasaka, S. Nagase, H.
Takaya, N. Yasuda, T. Kato,and S. Yamagao

Partial Charge Transfer in the Shortest
Possible Metallofullerene Peapod, La@
C82Ì[11]Cycloparaphenylene

Chem. Eur. J.

20,14403-14409

2014

19

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

Recent Progress in the Chemistry ofEndohedral Metallofullerenes

Chem. Commun.
(Feature Article)

50,14701-14715

2014

20

Y. Takano, Z. Slanina, J.
Mateos, T. Tsuchiya, H.
Kurihara, F. Uhlik, M. A.
Herranz, N. Martín, S.
Nagase, and T. Akasaka

Unprecedented Chemical Reactivityof a Paramagnetic Endohedral
Metallofullerene La@Cs-C82 that Leads
Hydrogen Addition in the 1,3-Dipolar
Cycloaddition Reaction

J. Am. Chem.
Soc.

136,
17537-17546

2014

21

H. Zheng, X. Zhao, L. He, W.
–W. Wang, and S. Nagase

Quantum Chemical Determinationof Novel C82 Monometallofullerenes
Involving a Heterogeneous Group

Inorg. Chem.

53, 12911-12917

2014

22

N. Kano, S. Tsukada, Y.
Shibata, T. Kawashima,
H. Sato, J. –D. Guo, and S.
NagaseInterconversion among Dianionic,
Anionic, and Neutral Compounds Bearing
a Bond between Two PentacoordinatedGermanium Atoms

Organometallics

34, 56-62

2015

23

M. Yamada, H. Kurihara, M.
Suzuki, M. Saito, Z. Slanina,
F. Uhlik, T. Aizawa, T. Kato,
M. M. Olmstead, A. L. Balch,
Y. Maeda, S. Nagase, X. Lu,
and T. Akasaka

Hiding and Recovering Electrons in a
Dimetallic Endohedral Fullerene: AirStable Products from Radical Additions

J. Am. Chem.
Soc.

137, 232-238

2015

24

M. Yamada, Y. Muto, H.
Kurihara, Z. Slanina, M.
Suzuki, Y. Maeda, Y. Rubin,
M. M. Olmstead, A. L. Balch,
S. Nagase, X. Lu, and T.
Akasaka

Regioselective Cage Opening of La2@
D2(10611)-C72 with 5,6-Diphenyl-3-(2pyridyl)-1,2,4-triazine

Angew. Chem.
Int. Ed.

54, 2232-2235

2015

25

F. Uhlík, Z. Slanina, S.-L.
Lee, B. Wang, L. Adamowicz,
and S. Nagase

Water-Dimer Stability and Its Fullerene
Encapsulations

J. Comput.
Theor. Nanosci.

12, 959-964

2015

№

Authors

Title

Journal13

T. Yang, X. Zhao, S. Nagase,and T. Akasaka

Diels-Alder Reaction on Free C68
Fullerene and Endohedral Sc3N@C68
Fullerene Violating the Isolated Pentagon
Rule: Importance of Pentagon Adjacency

14

T. Morosaki, T. Suzuki, W. –W. Wang, S. Nagase, and T.
Fujii

15

－ 170 －

Ⅴ 資料 (2014)№

諸熊

Authors

Title

JournalVolume (Number),first page tolast page

year

奎治

26

R. I. Kaiser, L. G.
Muzangwa, T. Yang, D. S.
N. Parker, A. M. Mebel, A.
Jamal, and K. Morokuma

A Crossed Molecular Beam and Ab
Initio Study on the Formation of 5and 6-Methyl-1,4-Dihydronaphthalene(C11H12) via the Reaction of Meta-Tolyl(C7H7) with 1,3-Butadiene (C4H6

Phys. Chem.
Chem. Phys.

17, 7699-7706

2015

27

A. S. Lisovenko, K.
Morokuma, A. Y. Timoshkin

Initial gas phase reactions between
Al(CH3)3/AlH3 and ammonia: atheoretical study

J. Phys. Chem. A

119, 744-51

2015

28

B. Liu, J. Liu, H.-B. Li, R.
Bhola, E. A. Jackson, L. T.
Scott, A. J. Page, S. Irle, K.
Morokuma and C. Zhou

Nearly Exclusive Growth of Small
Diameter Semiconducting SingleWall Carbon Nanotubes from Organic
Chemistry Synthetic End-Cap Molecules

Nano Lett.

15, 586-595

2015

29

D. S. N. Parker, B. B. Dangi,
R . I. Kaiser, A. Jamal,
M. Ryazantsev and K.
Morokuma

Formation of 6-Methyl-1,4Dihydronaphthalene in the Reaction of
the Para-Tolyl Radical with 1,3-Butadiene
under Single Collision Conditions

J. Phys. Chem. A

118,12111-12119

2014

30

A. J. Page, F. Ding, S. Irle
and K. Morokuma

Insights into Carbon Nanotube andGraphene Formation Mechanisms from
Molecular Simulations: A Review

Rep. Prog. Phys.

78, 036501/1-38

2015

31

M. Hatanaka and K.
Morokuma

Exploring the reaction coordinates for
f-f emission and quenching of lanthanide
complexes – thermo-sensitivity ofterbium(III) luminescence

J. Chem. Theo.
Comp.

10, 4184-4188

2014

32

M. Isegawa, F. Liu, S. Maeda
and K. Morokuma

Complete active space second order
perturbation theory (CASPT2) study ofN(2D) + H2O reaction paths on D1 andD0 potential energy surfaces: direct androaming pathways

J. Chem. Phys.

141, 154303/1-9

2014

33

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

Systematic Exploration of Minimum
Energy Conical Intersection Structuresnear the Franck-Condon Region

J. Phys. Chem. A

118,12050-12058

2014

34

S. Maeda, Y. Harabuchi, Y.
Ono, T. Taketsugu, and K.
Morokuma

Intrinsic Reaction Coordinate:Calculation, Bifurcation, and AutomatedSearchInt. J. Quant.
Chem.

115, 258-269

2015

35

S. Maeda, T. Taketsugu, K.
Morokuma, and K. Ohno

Anharmonic Downward Distortion
Following for Automated Explorationof Quantum Chemical Potential Energy
Surfaces

Bull. Chem. Soc.
Jpn.

87, 1315-1334

2014

36

X. Li, L. W. Chung, K.
Morokuma and G. Li,

A Theoretical Study on the UVR8Photoreceptor: Sensing Ultraviolet-B
by Tryptophan and Dissociation of
Homodimer

J. Chem. Theo.
Comp.

10, 3319-3330

2014

37

M. Isegawa, F. Liu, S. Maeda,
and K. Morokuma

Ab initio reaction pathways forphotodissociation and isomerization of
nitromethane on four singlet potential
energy surfaces with three roaming paths

J. Chem. Phys.

140,244310/1-11

2014

38

H-B. Li, A. J. Page, C.
Hettich, B. Aradi, C. Köhler,
T. Frauenheim, S. Irle and K.
MorokumaGraphene Nucleation on a SurfaceMolten Copper Catalyst: Quantum
Chemical Molecular Dynamics
Simulations

Chem. Sci.

5, 3493-3500

2014

39

G. P. Petrova, H.-B. Li, K.
Maruoka and K. Morokuma

Asymmetric phase-transfer catalysis
with homo- and heterochiral quaternaryammonium salts: a theoretical study

J. Phys. Chem. B

18, 5154-5167

2014－ 171 －

Ⅴ 資料 (2014)№

Authors

Title

JournalVolume (Number),first page tolast page

year

40

G. P. Petrova, Z. Ke, S.
Park, H. Sugiyama and K.
Morokuma

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

Chem. Phys.
Lett.

600, 87-95

2014

41

D. S. N. Parker, B. B. Dangi,
R. I. Kaiser, A. Jamal, M. N.
Ryzantsev, K. Morokuma, A.
Korte and W. Sande

An Experimental and Theoretical Studyon the Formation of 2-Methylnaphthalene(C11H10/C11H3D7) in the Reactions of
the Para-Tolyl (C7H7) and Para-Tolyl-d7(C7D7) with Vinylacetylene (C4H4),

J. Phys. Chem. A

118, 2709-2718

2014

42

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

Graphene Nucleation from Amorphous
Nickel Carbides: QM/MD Studies on theRole of Subsurface Carbon Density

J. Phys. Chem. C

118,11078-11084

2014

榊

茂好

43

Yuh Hijikata and Shigeyoshi
SakakiInteraction of Various Gas Moleculeswith Paddle-Wheel-Type Open Metal
Sites of Porous Coordination Polymers:
Theoretical Investigation

Inorg. Chem.

53, 2417-2426

2014

44

Masayuki Nakagaki and
Shigeyoshi Sakaki

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

J. Phys. Chem. A

118, 1247-1257

2014

45

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

46

Hiroshi Sato, Wataru Kosaka,
Ryotaro Matsuda, Akihiro
Hori, Yuh Hijikata,Rodion
V. Belosludov, Shigeyoshi
Sakaki, Masaki Takata,
Susumu Kitagawa

Self-Accelerating CO Sorption in a Soft
Nanoporous Crystal

Science343, 167-170

2014

47

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, 1010-1020

2014

48

Guixian Zeng, Satoshi
Maeda, Ttetsuya Taketsugu,
and Shigeyoshi Sakaki

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

Angew. Chem.
Int. Ed.

128, 4721-4725

2014

49

Yue Chen and Shigeyoshi
Sakaki

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

Dalton Trans.

43, 11478-11492

2014

50

Fareed Basha Sayyed,
Shigeyoshi Sakaki

The Crucial Roles of MgCl2 as a Noninnocent Additive in the Ni-Catalyzed
Carboxylation of Benzyl Halide with CO2

Chem. Commun.

50,
13026-13029

2014

51

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

Effects of PAr3 Ligands on Direct
Arylation of Heteroarenes with Isolated[Pd(2,6-Me2C6H3)(μ‑O2CMe)(PAr3)]4
Complexes

Organometallics

33, 6247-6252

2014

52

Keisuke Kishida, Yumiko
Watanabe, Horike Satoshi,
Yoshihiro Watanabe,
Yoshikuni Oku-mura, Yuh
Hijikata, Shigeyoshi Sakaki,
and Susumu Kitagawa

DRIFT and Theoretical Studies of
Ethylene/Ethane Separation on Flexible
Microporosity of [Cu 2(2,3-pyrazinedicarb
oxylate)2(pyrazine)]nEur. J. Inorg.
Chem.

2747-2752

2014－ 172 －

Ⅴ 資料 (2014)

Volume (Number),first page tolast pageyear

Org. Lett.

16, 4960-4963

2014

Generation of Dihydrogen Moleculeand Hydrosilylation of Carbon Dioxide
Catalyzed by Zinc Hydride Complex:
Theoretical Understanding and Prediction

Inorg. Chem.

53, 8485-8493

2014

55

Hajime Kameo, Tatsuya
Kawamoto, Shigeyoshi
Sakaki, and Hiroshi
Nakazawa

Can One σ*-Antibonding Orbital Interact
with Six Electrons of Lewis Bases?
Analysis of a Multiply Interacting σ*
OrbitalOrganometallics

33, 5960-5963

2014

56

Hajime Kameo, Tatsuya
Kawamoto, Shigeyoshi
Sakaki, Didier Bourissou,
and Hiroshi Nakazawa

Synthesis, Geometry, and Bonding
Nature of Heptacoordinate Compounds ofSilicon and Germanium Featuring Three
Phosphine Donors

Organometallics

33, 6557-6567

2014

57

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, 6444-6457

2014

N. Minezawa

Optimizing minimum free-energy
crossing points in solution: Linearresponse free energy/spin-flip density
functional theory approach

J. Chem. Phys.

141 (16), 164118(9 pages)

2014

59

N. Minezawa

State-specific solvation effect on theintramolecular charge transfer reaction insolution: A linear-response free energy
TDDFT method

Chem. Phys.
Lett.

608, 140-144

2014

60

N. Minezawa

Vertical excitation energies of linear
cyanine dyes by spin-flip time-dependent
density functional theory

Chem. Phys.
Lett.

622, 115-119

2014

齋藤

拓也

61

Takuya Saito

Rate in template-directed polymer
synthesis

Phys. Rev. E

89, 062716(8 pages)

2014№

Authors

Title

53

Tetsuaki Fujihara, Yuichiro
Horimoto, Taiga Mizoe,
Fareed Bhasha Sayyed,
Yosuke Tani, Jun Terao,
Shigeyoshi Sakaki, andYasushi Tsuji

Nickel-Catalyzed Double Carboxylationof Alkynes Employing Carbon Dioxide

54

Milind Madhusudan
Deshmukh and Shigeyoshi
Sakaki

嶺澤
58

Journal

範行

John Jairo Molina
62

Thanh-Nghi Nguyen, Magali
Duvail, Arnaud Villard, John
J. Molina, Philippe Guilbaud,
and Jean-François Dufrêche

Multi-scale modelling of uranyl chloride
solutionsJ. Chem. Phys

142 (2), 024501

2014

63

Adnan Hamid, John J.
Molina, and Ryoichi
Yamamoto

Direct Numerical simulations of
sedimenting spherical particles at nonzero Reynolds number

RSC Advances

4 (96),
53681-53693

2014

64

Adnan Hamid, John J.
Molina, and Ryoichi
Yamamoto

Simulation studies of microstructure ofcolloids in sedimentation

Mol. Sim10.1080/00268976.
2015.1059510

2015

65

Chunyu Shih, John J. Molina,
and Ryoichi Yamamoto

Dynamic polarisation of a charged colloid
in an oscillating electric field

Mol. Phys.

DOI:10.1080/00
268976.2015.10
59510

2015

－ 173 －

Ⅴ 資料 (2014)№

Authors

Title

JournalVolume (Number),first page tolast page

year

Jingdong Guo
66

Jing-Dong Guo, Shigeru
Nagase, and Philip P. Power

Dispersion Force Effects on the
Dissociation of “Jack-in-the-Box”
Diphosphanes and Diarsanes

Organometallics

34, 2028-2033

2015

67

Takahiro Sasamori, Tomohiro
Sugahara, Tomohiro Agou,
Jing-Dong Guo, Shigeru
Nagase, Rainer Streubel, andNorihiro Tokitoh

Synthesis and Characterization of a
1,2-Digermabenzene

Organometallics

34, 2106-2109

2015

68

Takuya Kuwabara, JingDong Guo, Shigeru Nagase,
Takahiro Sasamori, Norihiro
Tokitoh, and Masaichi Saito

Synthesis, Structures, and Electronic
Properties of Triple- and Double-Decker
Ruthenocenes Incorporated by a Group
14 Metallole Dianion Ligand

J. Am. Chem.
Soc.

136,
13059-13064

2014

Wei-Wei Wang
69

T. Morosaki, T. Suzuki, W.
-W. Wang, S. Nagase, and T.
Fujii

Syntheses, Structures, and Reactivities of
Two Chalcogen-Stabilized Carbones

Angew. Chem.
Int. Ed.

53, 9569-9571

2014

70

Q. Zhou, H. Li, Y. Lian, M.
Suzuki, L. Bao, W. Cai, W.
-W. Wang, S. Nagase, X. Lu
and T. Akasaka

Regioselective synthesis and molecular
structure of the first derivativeof praseodymium-containing
metallofullerenes

Chem. Commun.

50, 9876-9878

2014

71

Y. Maeda, M. Kimura,
C. Ueda, M. Yamada, T.
Kikuchi, M. Suzuki, W.
-W. Wang, N. Mizorogi, N.
Karousis, N. Tagmatarchis, T.
Hasegawa, M. M. Olmstead,
A. L. Balch, S. Nagase and T.
Akasaka

Isolation and characterization of[5,6]-pyrrolidino-Sc3N@Ih-C80
diastereomers

Chem. Commun.

50,
12552-12555

2014

72

H. Zheng, X. Zhao, L. He, W.
-W. Wang, and S. Nagase

Quantum Chemical Determinationof Novel C82 Monometallofullerenes
Involving a Heterogeneous Group

Inorg. Chem

53, 12911-12917

2014

畑中

美穂

73

Miho Hatanaka and Keiji
Morokuma

Exploring the reaction coordinates for
f-f emission and quenching of lanthanide
complexes – thermosensitivity ofterbium(III) luminescence

J. Chem. Theory
Comput.

10 (10),4184-4188

2014

74

Lung Wa Chung, W. M. C.
Sameera, Romain Ramozzi,
Alister J. Page, Miho
Hatanaka, Galina P. Petrova,
Travis V. Harris, Xin Li,
Zhuofeng Ke, Fengyi Liu,
Hai-Bei Li, Lina Ding, andKeiji Morokuma

The ONIOM Method and Its Applications

Chem. Rev.

ASAP

2015

75

Miho Hatanaka and Keiji
Morokuma

How Can Fluctional Chiral Lanthanide(III) Complexes Achieve a High
Stereoselectivity in Aqueous MukaiyamaAldol Reaction?

ACS Catal.

5 (6), 3731-3739

2015

76

Maneeporn Puripat, Romain
Ramozzi, Miho Hatanaka,
Waraporn Parasuk,
Vudhichai Parasuk, and Keiji
Morokuma

The Biginelli reaction is a urea-catalyzed
organocatalytic multicomponent reaction

J. Org. Chem

ASAP

2015

－ 174 －

Ⅴ 資料 (2014)№

Authors

Title

JournalVolume (Number),first page tolast pageyear

Romain Ramozzi
77

R. Ramozzi, N. Chéron, L.
El Kaïm, L. Grimaud, and P.
Fleurat-Lessard

Predicting new Ugi-Smiles couplings: a
combined experimental and theoretical
study

Chem. Eur. J.

20 (29),9094-9099.

2014

78

L. Wa Chung, W. M. C.
Sameera, R. Ramozzi, A.
J. Page, M. Hatanaka, G. P.
Petrova, T. V. Harris, X. Li, Z.
Ke, F. Liu, H.B. Li, L. Ding,
and K. Morokuma

The ONIOM Method and its Applications

Chem. Rev.

doi:10.1021/
cr5004419

2015

79

R. Ramozzi, K. Morokuma

R. Ramozzi, K. Morokuma, Revisiting
the Passerini reaction mechanism:
existence of the nitrilium, organocatalysis
of its formation and solvent effect

J. Org. Chem.

doi:10.1021/acs.
joc.5b00594

2015

80

J. Jiang, R. Ramozzi, K.
MorokumaRh(III)-Catalyzed C(sp3)-H Bond
Activation via an External Base
Metalation Deprotonation Mechanism

Chem. Eur. J.

accepted

2015

The ONIOM Method and its Applications

Chem. Rev.

[Online early
access].
DOI: 10.1021/
cr5004419.
Published
Online: Apr 8,
2015.

2015

Travis Harris

81

Lung Wa Chung, W. M. C.
Sameera, Romain Ramozzi,
Alister J. Page, Miho
Hatanaka, Galina P. Petrova,
Travis V. Harris, Xin Li,
Zhuofeng Ke, Fengyi Liu,
Hai-Bei Li, Lina Ding, andKeiji Morokuma

伊勢川

美穂

82

Miho Isegawa, Fengyi
Liu, Satoshi Maeda, Keiji
Morokuma

Ab initio reaction pathways forphotodissociation and isomerization of
nitromethane on four singlet potential
energy surfaces with three roaming paths

J. Chem. Phys.

140, 244310

2014

83

Miho Isegawa, Fengyi
Liu, Satoshi Maeda, Keiji
MorokumaComplete active space second order
perturbation theory (CASPT2) study ofN(2D) + H2O reaction paths on D1 andD0 potential energy surfaces: Direct androaming pathways

J. Chem. Phys.

141, 154303

2014

84

Miho Isegawa, Keiji
Morokuma

Photochemical Ring Opening and Closingof Three Isomers of Diarylethene: SpinFlip Time Dependent Density Functional
Study

J. Phys. Chem. A

199, 4191-4199

2015

85

L. W. Chung, W. M. C.
Sameera, R. Ramozzi, A.
J. Page, M. Hatanaka, G. P.
Petrova, T. V. Harris, X. Li, Z.
Ke, F. Liu, H-B. Li, L. Ding
and K. Morokuma

The ONIOM Method and its Applications

Chem. Rev.

In press

2015

86

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

A computational view on the reactionsof hydrocarbons with coinage metal
complexes

J. Organomet.
Chem.

784, 2-12.

2015

W. M. C. Sameera－ 175 －

Ⅴ 資料 (2014)

Volume (Number),first page tolast pageyear

J. Am. Chem.
Soc.

136, 14,5342-5350.

2014

Double exchange in a mixed-valentoctanuclear iron cluster, [Fe8(μ4-O)4(μ4-Cl-pz)12Cl4]–

Dalton Trans.

43,11269-11276.

2014

ACS Catal.

5, 3648-3661

2015

№

Authors

Title

87

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
reactions88

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.

JournalJulong Jiang

89

Julong Jiang, Jin-Quan Yu,
Keiji Morokuma

Mechanism and Stereoselectivityof Directed C(sp3)-H Activation
and Arylation Catalyzed by Pd(II)with Pyridine Ligand and TFA. A
Computational Study

90

Julong Jiang, Romain
Ramozzi, Keiji Morokuma

Rh(III)-Catalyzed C(sp3)-H Bond
Activation via an External Base
Metalation/Deprotonation Mechanism: A
Theoretical Study

Chem. Eur. J.

Accepted.

2015

91

Julong Jiang, Romain
Ramozzi, Shin Moteki,
Asuka Usui, Keiji Maruoka,
Keiji Morokuma

The Mechanism of Metal-Free C-H
Activation of Branched Aldehydes andAcylation of Alkenes Using Hypervalent
Iodine Compound: A Theoretical Study

J. Org. Chem.

Submitted

2015

10, 259-270

2014

山邊

信一

92

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

93

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,
134-148

2014

94

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 15,1140-1148

2014

95

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

Beilstein Journalof Organic
Chemistry

vol. 10,1765-1774

2014

96

Shinichi Yamabe, Guixiang
Zeng, Wei Guan, Shigeyoshi
SakakiA DFT Study on Proton Transfers inHydrolysis Reactions of Phosphate DiAnion and Sulfate Mono-Anion

Journal ofComputational
Chemistry,

Volume 35,
Issue 30,2195-2204.

2014

97

D. T. Usmanov, L. C. Chen,
Z. Yu, S. Yamabe*, S. Sakaki
and K.Hiraoka*

Atmospheric pressure chemical ionization(APCI) of using alternating current
corona discharge ion source

Journal of Mass
Spectrometry

vol. 50, No. 4,
651-7102015

98

Govinda P. Khanal, Rajendra
Parajuli, Elangannan
Arunan,Shinichi Yamabe,Kenzo Hiraoka and Eiko
Torikai,

Study of structures, energies andvibrational frequencies of (O2)n+(n=2-5)
clusters by GGA and meta-GGA density
functional methods

Computational
and Theoretical
Chemistry

vol. 1056,
24-36

2015

99

Shinichi Yamabe, Noriko
Tsuchida, Shoko Yamazaki
and Shigeyoshi Sakaki

Frontier orbitals and transition statesin the oxidation and degradation of
L-ascorbic acid: a DFT study

Org. Biomol.
Chemvol. 13,4002-4015

2015

100

aokazu Yoshikawa, Shinichi
Yamabe, Shigeyoshi Sakaki,

Transition States of the 3MLCT to 3MC
Conversion in Ru(bp)2(phen deriveativ)2+
complexes

Journal of
Molecular
Structure

vol. 1094,
98-1082015－ 176 －

Ⅴ 資料 (2014)

Volume (Number),first page tolast page

year

International
Journal of
Quantum
Chemistry

in press

2015

DRIFT and theoretical studies of
ethylene/ethane separation on flexible
microporosity of [Cu 2(2,3-pyrazinedicarbo
xylate)2(pyrazine)]nEur. J. Inorg.
Chem.

2747-2752

2014

103

Ryo Ohtani, Munehiro
Inukai, Yuh Hijikata, Tetsuya
Ogawa, Mikihito Takenaka,
Masaaki Ohba, and Susumu
Kitagawa

Sequential synthesis of coordination
polymersomes

Angew. Chem.
Int. Ed.

54, 1139-1143

2015

104

Shin-ichro Noro, Junya
Mizutani, Yuh Hijikata,
Ryotaro Matsuda, Hiroshi
Sato, Susumu Kitagawa,
Kunihisa Sugimoto, Yasutaka
Inubushi, Kazuya Kubo, andTakayoshi Nakamura

Porous coordination polymers withubiquitous and biocompatible metals anda neutral bridging ligand

Nat. Commun.

6, 5851

2015

Like-Charge Attraction of Molecular
Cations in Water: Subtle Balance between
Interionic Interactions and Ionic Solvation
EffectJ. Phys. Chem. B

118, 5499-5508

2014

№

Authors

Title

101

Nobuko Kanehisa,
Tsuyoshi Inoue,and Hiroshi
Takashima,

A DFT study of hydride transfers to thecarbonyl oxygen of DDQ

102

Keisuke Kishida, Yumiko
Watanabe, Satoshi Horike,
Yoshihiro Watanabe,
Yoshikuni Okumura, Yuh
Hijikata, Shigeyoshi Sakaki,
and Susumu Kitagawa

土方

青野
105

Journal優信治
Taichi Inagaki, Shiniji Aono,
Hiroshi Nakano, and Takeshi
Yamamoto

Guixiang Zeng（會

桂香）

106

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

107

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

108

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

109

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

110

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.

53 (13),6444-6457

2014

CASPT2 study of inverse sandwich-type
dinuclear 3d transition metal complexesof ethylene and dinitrogen molecules:
similarities and differences in geometry,electronic structure, and spin multiplicity

Phys. Chem.
Chem. Phys.

17,16294-16305

2015

中垣

111

雅之
Masayuki Nakagaki and
Shigeyoshi Sakaki－ 177 －

Ⅴ 資料 (2014)№

Authors

Title

JournalVolume (Number),first page tolast pageyear

Yue Chen112

Yue Chen, Shigeyoshi Sakaki

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

Dalton Trans.

43,11478-11492

2014

113

Shubin Yang, Changlun
Chen, Yue Chen, Jiaxing Li,
Dongqi Wang, Xiangke Wang

Competitive Adsorption of PbII, NiII,and SrII Ions on Graphene Oxides: A
Combined Experimental and Theoretical
Study

ChemPlusChem

80 (3),
480-484

2015

Sayyed Fareed Bhasha
114

Fareed Bhasha Sayyed andShigeyoshi Sakaki

The crucial roles of MgCl2 as a noninnocent additive in the Ni-catalyzed
carboxylation of benzyl halide with CO2

Chem. Commun.

50,
13026-13029

2014

115

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 (13),6444-6457

2014

116

Tetsuaki Fujihara, Yuichiro
Horimoto, Taiga Mizoe,
Fareed Bhasha Sayyed,
Yosuke Tani, Jun Terao,
Shigeyoshi Sakaki, Yasushi
Tsuji

Nickel-Catalyzed Double Carboxylationof Alkynes Employing Carbon DioxideOrg. Lett.

16 (18),4960-4963

2014

117

Kenta Yamada, Yukio
Kawashima, Masanori
Tachikawa

Accurate Prediction of Hyperfine
Coupling Constants in Muoniated andHydrogenated Ethyl Radicals: Ab Initio
Path Integral Simulation Study with
Density Functional Theory Method

J. Chem. Theory.
Comput.

10 (5),
2005-2015

2014

118

Takako Mashiko, Kenta
Yamada, Shuichi Hiraoka,
Umpei Nagashima, Masanori
Tachikawa

Molecular dynamics simulation of selfassembled nanocubes in methanol

Mol. Simul.

41 (10-12),845-849

2014

119

Kenta Yamada, Yukio
Kawashima, Masanori
Tachikawa

Quantum simulation for muoniated anddeuterated methyl radicals in implicit
water solvent: combined ab initio path
integral molecular dynamics and thepolarizable continuum model simulation
study

Mol. Simul.

41 (10-12),
832-839

2014

The Biginelli reaction is a urea-catalyzed
organocatalytic multicomponent reaction

The journalof organic
chemistry

Just Accepted

2015

山田

健太

Maneeporn Puripat

120

Maneeporn Puripat, Romain
Ramozzi, Miho Hatanaka,
Waraporn Parasuk,
Vudhichai Parasuk, Keiji
Morokuma＊以下に表示の研究業績（論文）は、共著である
No14&69. No15&71. No16&68. No21&72. No31&73. No32&83.
No37&82. No49&112. No50&114. No52&102. No53&116. No57&110.
No74,78,81&85. No76&120. No92&106.

－ 178 －

Ⅴ 資料 (2014)

２．共同研究者受入れ状況（平成 26 年度）

受入れ教員

共同研究者名

受入れ身分

受入れ期間

所属機関・職

研究内容

諸熊 奎治

PURIPAT,
Maneeporn

外国人
共同研究者

平成 26 年 2 月 27 日～
平成 27 年 2 月 26 日

Chulalongkorn
University（タイ）・
PhD 学生複雑分子系の理論
化学・計算化学

諸熊 奎治

FERNANDEZ
A Victor M

外国人
共同研究者

平成 26 年 4 月 1 日～
平成 26 年 7 月 3 日

Chemical Research of
Catalonia（スペイン）・
PhD 学生複雑分子系の理論
化学・計算化学諸熊 奎治

KAPUKOTUWE
WARAWWE,
Pulasthika
Bethmini

外国人
共同研究者

平成 26 年 5 月 14 日～
平成 27 年 5 月 13 日

ヨーテボリ大学（スウェーデン）・
PhD 学生複雑分子系の理論
化学・計算化学ZHENG, Jia-Jia

外国人
共同研究者

平成 26 年 8 月 1 日～
平成 27 年 1 月 31 日

Xi'an Jiaotong
University（中国）・
博士課程学生塩素化フラーレン
および金属内包フラーレンの理論的研究
EAPSI：AFIR法を用いたGRRM戦
略：テルペン形成
経路に対するメチル化の影響予測

永瀬

茂

諸熊 奎治

HUDSON,
Brandi M.

外国人
共同研究者

平成 26 年 6 月 17 日～
平成 26 年 8 月 19 日

カリフォルニア大学（アメリカ）・
大学院研究員榊

LEI, Ming

招へい
外国人学者

平成 26 年 6 月 28 日～
平成 26 年 8 月 31 日

Beijing University（中国）・教授

d電子複合系の理論
化学

諸熊 奎治

SAMEERA,
W.M. C.

外国人
共同研究者

平成 26 年 9 月 16 日～
平成 28 年 9 月 15 日

日本学術振興会・外国人特別研究員

合成キラル金属ポ
ルフィリンの反応
機構と選択性の計
算化学による研究

諸熊 奎治

POMOGAEVA
Anna
Vladimirovna

外国人
共同研究者

平成 26 年 11 月 15 日～
平成 26 年 12 月 23 日

Petersburg State
University（ロシア）・
博士研究員

アルキル金属アミ
ノボランの気相中および凝縮系における反応機構の理
論的研究

諸熊 奎治

NGUYEN,
Hoa My招へい
外国人学者

平成 27 年 1 月 6 日～
平成 27 年 2 月 16 日

ベトナム大学（ベトナム）・講師

計算化学法によるMRSAのβｰラクタ
ム抗生物質耐性に
関する研究

諸熊 奎治

JAMAL, Adeel
Ashraf

外国人
共同研究者

平成 27 年 2 月 1 日～
平成 28 年 1 月 31 日

Emory University（アメリカ）・
博士研究員

炭化水素の熱分解の第一原理に基づく反応速度論的モデルの構築

北海道大学（日本）・
博士研究員

反応経路自動探索法を基盤とする化学反応の理論設計
技術

University of South
Carolina（アメリカ）・
教授

複雑分子系の理論
化学

茂好

諸熊 奎治

鈴木 机倫

共同研究者

平成 27 年 3 月 1 日～
平成 28 年 2 月 29 日

諸熊 奎治

HEYDEN,
Andreas

招へい
外国人学者

平成 27 年 3 月 27 日～
平成 27 年 8 月 3 日－ 179 －

Ⅴ 資料 (2014)

３．海外渡航一覧（平成 26 年度）

職

名

氏

名

期間（自）

期間（至）

シニアリサーチフェロー

諸熊奎治

2014.4.24

2014.5.1

オーストラリア

シニアリサーチフェロー

諸熊奎治

2014.5.15

2014.5.27

スイス

シニアリサーチフェロー

諸熊奎治

2014.5.29

2014.6.6

アメリカ合衆国・カナダ

2014.6.27

2014.7.20

フランス

外国人共同研究者

RAMOZZI, Romain
Raoul, Marcel

目

的

地

池田

昌司

2014.7.19

2014.7.27

アメリカ合衆国榊茂好2014.7.20

2014.7.25

シンガポール

シニアリサーチフェロー

諸熊奎治

2014.9.13

2014.9.21

ロシア研究員（学術研究奨励）永瀬茂

2014.10.28

2014.11.3

スウェーデン

シニアリサーチフェロー

諸熊奎治

2014.10.29

2014.11.2

スウェーデン

研究員（学術研究奨励）榊茂好2015.2.21

2015.2.27

ドイツ

研究員（学術研究奨励）永瀬茂

2015.3.5

2015.3.11

インド

准

教

授

研究員（学術研究奨励）－ 180 －

Ⅴ 資料 (2014)

４．福井謙一記念研究センター

シンポジウム－ 181 －

ポスター・プログラム

Ⅴ 資料 (2014)

第 12 回京都大学福井謙一記念研究センターシンポジウム-諸熊奎治先生傘寿記念プログラム
日時

平成 27(2015)年 1 月 23 日（金）場所

京都大学福井謙一記念研究センター

講演会 (3 階大会議室 10:00～12:30)
 開会の辞 田中 一義（京都大学 福井謙一記念研究センター長） ・・・10:00-10:05
 ご挨拶  伊藤 紳三郎（京都大学 工学研究科長）       ・・・10:05-10:15
 北川 進 (京都大学 物質－細胞統合システム拠点) 司会：永瀬 茂（福井センター）「多孔性金属錯体の化学と応用」               ・・・10:15-11:15－ 休憩 － 田中 肇 (東京大学 生産技術研究所) 司会：山本 量一（京大院工）「水の局所構造化と熱力学異常・結晶化におけるその役割」   ・・・11:30-12:30－ 昼休み －傘寿記念講演 (3 階大会議室 14:00～15:00)
 諸熊 奎治 (京都大学 福井謙一記念研究センター) 司会：榊 茂好（福井センター）

Keiji Morokuma (Fukui Institute for Fundamental Chemistry, Kyoto University)「Chemical Theory of Complex Molecular Systems: Discovery and Insights from
Computational Studies of Chemical Reactions」

    ・・・14:00-15:00－ 休憩 －ポスターセッション (3 階大会議室 15:30～17:20)
お祝いの会・懇親会 (1 階多目的ルーム 17:30～19:00)－ 182 －

Ⅴ 資料 (2014)

ポスターリスト (3 階大会議室 15:30～17:20)


番号が奇数の方は前半(15:30-16:25)、番号が偶数の方は後半(16:25-17:20)には、ポスタ
ーボードの前で発表するようにしてください。

Authors with odd and even poster numbers should be present at the poster during thefirst half (15:30-16:25) and the second half (16:25-17:30) of the session, respectively.

1.

(H2O)n (n<26)クラスター中の水素結合ネットワークの解析○岩田 末廣 (慶応大理工)

2.

低障壁水素結合の量子化学 ―多成分系分子理論の応用―○立川 仁典 (横浜市大院生命ナノ)3.

分子を対象とした第一原理経路積分分子動力学法の実装と応用○河津 励[1,2]、立川 仁典[1] (横市大生命ナノ[1]、東大総文[2])

4.

基底関数に含まれる軌道指数を用いた解析接続法による光イオン化断面積の変分計算
森田 将人、松崎 黎、○藪下 聡 (慶大理工)5.

CS2 光解離反応の真空紫外サブ 20fs 光電子イメージング○堀尾 琢哉、Roman Spesyvtsev, 鈴木 俊法 (京大院理)6.

GRRM 法による未知化学の探索： H4C4
○大野 公一[1]、佐藤 寛子[2]、岩本 武明[1] (東北大院理[1]、国立情報学研究所[2])

7.

単成分人工力誘起反応（SC-AFIR）法とその応用○前田 理[1]，原渕 佑[1]，武次 徹也[1]，諸熊 奎治[2] (北大院理[1]、京大福井セ[2])8.

New Insights in Isocyanides Multicomponent Reactions○Romain Ramozzi and Keiji Morokuma (FIFC, Kyoto Univ.)

9.

Unveiling the Essence of Pd(II)-Catalyzed C(sp3)-H Activation: Is the CMD
Mechanism Still Applicable?
○Julong Jiang[1], Jin-Quan Yu[2] and Keiji Morokuma[1] (FIFC, Kyoto Univ.[1], Depart.
of Chem., The Scripps Research Institute[2])－ 183 －

Ⅴ 資料 (2014)

10. The Biginelli Reaction: An Organocatalyzed Multicomponent Reaction○ Maneeporn Puripat[1,2], Romain Ramozzi[1], Miho Hatanaka[1], Vudhichai
Parasuk[2,3] and Keiji Morokuma[1,4]  (FIFC[1], Nanosci. & Tech. Chulalongkorn
Univ.[2], Chem. Chulalongkorn Univ.[3], Chem & Emerson Center for Sci. Comp. Emory
Univ.[4])11. Glucose Transformation to 5-Hydroxymethylfurfural in Acidic Aqueous and Ionic
Liquid Solvents○ Arifin[1], Maneeporn Puripat [3], Daisuke Yokogawa[1,2], Vudhichai Parasuk[3],Stephan Irle[1,2] (Grad. School. of Sci. Nagoya Univ.[1], WPI-ITbM[2], Chula longkorn
Univ. [3])12. Exploring Full Catalytic Cycle of Rh(I)-BINAP Catalyzed Isomerization ofAllylamines○吉村 誠慶[1], 前田 理[2], 澤村 正也[2], 武次 徹也[2], 諸熊 奎治[3], 森 聖治[1]
(茨城大理[1], 北大院理[2], 京大福井セ[3])13. Spin-Flip Time-Dependent Density Functional Theory (SF-TDDFT) Study ofTokyoMagenta (TM) and TokyoGreen (TG)○W. M. C. Sameera, F. Lui, S. Maeda, K. Morokuma (FIFC)
14. Theoretical Study of Excitation Energy Transfer in Thermo-Sensitive Lanthanide
Luminescence Sensors○Miho Hatanaka, Keiji Morokuma (FIFC, Kyoto Univ.)
15. 緑色蛍光タンパク質の蛍光スペクトルに関する理論的研究○内田 芳裕[1]、東 雅大[2]、林 重彦[1] (京大院理[1]、琉球大理[2])16. hCRBPII 及びその変異体の構造とスペクトルに関する QM/MM 理論計算
○成 せい、神谷 基司、内田 芳裕、林 重彦 (京大院理)17. 両親媒性有機分子の自己組織化・包接のシミュレーション○田中 大地、林 重彦 (京都大学理学研究科)
18. 海ホタルルシフェリン類縁分子の化学発光における溶媒効果に関する理論的研究○福田 源大[1]、佐藤 啓文[2] (京大院工[1]、京大院工[2])－ 184 －

Ⅴ 資料 (2014)

19. 電荷移動錯体の分子間相互作用に関する理論的研究○坂本 純一[1]，佐藤 啓文[1,2] (京大院工[1]、京大 ESICB[2])20. 分子内電荷移動反応における状態固有の溶媒和効果○嶺澤 範行 (京大福井セ)
21. 引き伸ばされていく過渡的過程の高分子の揺らぎ○齋藤 拓也[1]、坂上 貴洋[2]  (京大福井セ[1]、九大理[2])22. ガラス転移における構造とフラジリティの関係：レプリカ理論によるアプローチ○枡井 基典[1]、佐藤 啓文[1,2]、池田 昌司[3] (京大院工[1]、京都大学電池元素戦略
ユニット[2]、京大福井センター[3])23. Theoretical Study on Effect of Si-bridging on Electronic Properties of
Cyclooligothienylenes○Eisuke Ohta[1,2], Takuya Ogaki[1], Toru Aoki[1], Yukiko Oda[1], Yasunori Matsui[1,2],
and Hiroshi Ikeda[1,2] (Grad. Sch. of Eng., Osaka Pref. Univ. [1], RIMED, Osaka Pref.
Univ.[2])24. FMO 法における酵素 NylB と基質の残基間相互作用エネルギー変化の統計的解析○安東 寛之[1]、馬場 剛史[1]、重田 育照[2]、渡邉 千鶴[3]、沖山 佳生[3]、福澤 薫[4]、望月 祐志[3,5]、中野 雅由[1] (阪大院・基礎工[1]、筑大院・数理[2]、東大・生産技術
研[3]、日大・歯[4]、立教大・理[5])25. BODIPY の光吸収スペクトルに関する理論的研究○浅岡 瑞稀、宮城 公磁、竹林 拓、北河 康隆、中野 雅由 (阪大院基礎工)
26. TbPc2 錯体における Pc 環の回転障壁に関する理論的研究○北河 康隆[1,4]、倉橋 裕幸[2]、加藤 恵一[3,4]、奥村 光隆[2,4]、山下 正廣[3,4]、中野 雅由[1]  (阪大院基礎工[1]・阪大院理[2]・東北大院理[3]・JST CREST[4])
27. 異核遷移金属鎖におけるジラジカル因子と三次非線形光学物性の相関：金属種配列効果○高椋 章太、北河 康隆、中野 雅由 (阪大院基礎工)－ 185 －

Ⅴ 資料 (2014)

28. イミノニトロキシド置換メタンイミノニトロキシド-Eu(Ⅲ)錯体の構造と光学物性に関する理論研究○中村 亮太[1]、重田 育照[2]、北河 康隆[1]、中野 雅由[1] (阪大院基礎工[1]、筑波大
院理工[2])
29. チアジルラジカル多量体における開殻一重項性と第二超分極率に関する理論研究○松井 啓史、福田 幸太郎、伊藤 聡一、南田 有加、中野 雅由 (阪大院基礎工)
30. ピラゾール架橋 2 核銅(II)錯体の電子状態と磁気的相互作用に関する理論的研究○宮城 公磁、浅岡 瑞稀、竹林 拓、北河 康隆、中野 雅由 (阪大院基礎工)
31. 1,4-ジラジカル化合物の電子構造と光応答特性についての理論研究○森田 啓介、岸 亮平、中野 雅由 (阪大院基礎工)
32. 1,3-ジラジカル化合物の電子励起および光応答特性についての理論研究○齋藤 真和、岸 亮平、森田 啓介、中野 雅由 (阪大院基礎工)
33. C60 部分骨格としての曲面縮環π共役系：開殻非線形光学物性の視点から○福田 幸太郎、南田 有加、中野 雅由 (阪大院基礎工)34. 単分子の伝導性に対するスピン分極の効果についての理論的研究○竹林 拓[1]、北河 康隆[1]、重田 育照[2]、奥村 光隆[3]、中野 雅由[1] (阪大院基礎工[1]、筑大院数理[2]、阪大院理[3])35. コラヌレン骨格を含む非局在開殻一重項曲面型π共役系の開殻性と非線形光学効果○南田 有加[1]、福田 幸太郎[2]、中野 雅由[2] (阪大基礎工[1]、阪大院基礎工[2])36. Multistep Reconstructions of Half-saturated Carbon Nanotubes○Wei-Wei Wang and Shigeru Nagase (FIFC, Kyoto Univ.)
37. Theoretical Study on Reaction of 1,2-Diarylgermyne with Acetylene○Jing-Dong Guo and Shigeru Nagase (FIFC, Kyoto Univ.)
38. キノイド構造と芳香族構造をそれぞれ有する分子ユニットからなる分子ワイヤにおける電子トンネリング効率に関する計算化学的研究○西澤 尚平[1]、 長谷川 淳也[2]、 松田 建児[1] (京大院工[1]、 北大触セ[2])

－ 186 －

Ⅴ 資料 (2014)

39. Theoretical Design of Fluorescent Triphenylamine Derivative Based on Reduced
Vibronic Coupling○ Yuichiro Kameoka[1], Masashi Uebe[1], Akihiro Ito[1], Tohru Sato[1,2],

andKazuyoshi Tanaka[1] (Grad. School of Eng. Kyoto Univ.[1], ESICB, Kyoto Univ.[2])40. Molecular Structures of Polyyne-Iodine Complexes○Dai Nagashima[1], Tohru Sato[1,2], Naoya Iwahara[1], Kazuyoshi Tanaka[1], Yoriko
Wada[3] and Tomonari Wakabayashi[3]  (Grad. School. of Eng. Kyoto Univ [1], ESICB,
Kyoto Univ. [2], Grad. School. of Sci. & Eng. Kinki Univ [3])41. Hellmann-Feynman Theorem and Vibronic Coupling Density in Degenerate
System○Naoki Haruta[1], Tohru Sato[1,2] and Kazuyoshi Tanaka[1]  (Kyoto Univ.[1], ESICB,
Kyoto Univ.[2])42. ポリイン分子の禁制遷移およびビスマス三量体の電子遷移に関する研究◯若林 知成[1]、和田 資子[2]、森澤 勇介[1]、佐藤 徹[3] (近大理工[1]、関学大理工[2]、
京大院工[3])
2

43. ヨウ素導入ドナー分子 EDO-TTF-I の陽イオンラジカル塩作製とその物性○中野 義明[1]、高橋 佑輔[1,2]、石川 学[1]、矢持 秀起[1]、売市 幹大[3] (京大低物
セ[1]、京大院理[2]、分子研[3])
44. 縮退軌道を有する分子系におけるヤーン・テラー歪み、および電子状態に関する理論的研究○大江 佳毅[1,2]、中野 義明[1]、高橋 佑輔[1,2]、大塚 晃弘[1]、矢持 秀起[1]、吉田 幸
大[3]、齋藤 軍治[3]、Dmitri V. Konarev[4]、Rimma N. Lyubovskaya[4] (京大低物セ[1]、京大院理[2]、名城大農[3]、ロシア科学アカデミー[4])
45. (EDO-TTF-Cl)2PF6 における gapped spin-liquid 状態発現の可能性○石川 学[1,5]、平松 孝章[1,5]、中野 義明[1]、前里 光彦[2]、大塚 晃弘[1]、売市 幹大[3]、薬師 久彌[4]、矢持 秀起[1]、齋藤 軍治[5] (京大低物セ[1]、京大院理[2]、分子研[3]、豊田理研[4]、名城大農[5])

－ 187 －

Ⅴ 資料 (2014)

46. ルドルスデン‐ポッパー型層状酸化物 NaRTiO4 における酸素八面体回転による反転対称性の破れ○松原 司[1]、藤田 晃司[1]、久家 俊洋[1]、田中 功[1]、田中 勝久[1]、東後 篤史[2]、赤松 寛文[3]、Arnab S. Gupta[3]、Venkatraman Gopalan[3] (京大院工[1]、京大学際融合研究推進セ[2]、ペンシルベニア大[3])47. 結晶中における Ru(II)-SO2 錯体の異性化反応：配位子および結晶分子効果○青野 信治、 榊 茂好 (京大福井セ)
48. スピンクロスオーバーを示す Co(II)錯体の電子状態と結晶内分子間相互作用○中垣 雅之, 青野 信治, 榊 茂好 (京大福井セ)
49. 分子軌道理論とバンド理論のハイブリッド計算手法による金属担持触媒の金属…表面間相互作用の研究○松井 正冬[1], 榊 茂好[1,2] (京大 ESICB[1], 京大福井セ[2])50. 計算化学によるＬ－アスコルビン酸の酸化の素過程の追跡○山邊 信一[1]、土田 敦子[2]、山崎 祥子[3]、榊 茂好[1] (京大福井セ[1]、埼玉医科大医[2]、奈良教育大教育[3])
51. プロトン還元活性を示す Ni(II)錯体による触媒反応機構に関する理論的研究○山田 健太、榊 茂好 (京大福井セ)
52. C-H Alkylation of Alkenes with Alcohols Catalyzed by a Cationic Ru(II) Hydride
Complex: A Theoretical Study○Guixiang Zeng[1], Satoshi Maeda[1],Tetsuya Taketsugu[1], and Shigeyoshi Sakaki [2](Depart. of Chem. Hokkaido Univ.[1], FIFC[2])53. Reaction Mechanism of [Ni(NHC)]-Catalyzed Olefin Hydroarylation through C−H
Activation: A Computational Study○Shuwei Tang and Shigeyoshi Sakaki (FIFC, Kyoto Univ.)
54. Theoretical Study on the H2 and X-H bond Activation by Mo-Mo quintuple bond○Yue Chen and Shigeyoshi Sakaki (FIFC, Kyoto Univ.)
55. Theoretical Study on Crowded Organometallic Fullerene C60 {(h5-C5H5)Ru(CO)2}2○Hong Zheng and Shigeyoshi Sakaki (FIFC, Kyoto Univ.)－ 188 －

Ⅴ 資料 (2014)

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－ 189 －

Ⅴ 資料 (2014)

６．その他（報告）日経産業新聞 2014.10.21-22 より抜粋
日本のイノベーター

京都大学：シニアリサーチフェロー

諸熊奎治

計算機化学（上）分子の反応予測を簡単に、（下）新薬や触媒、応用広がる
京都大学福井謙一記念研究センターのシニアリ浦和夫特命教授は「分子が多数集また物質を設

サーチフェローを務める諸熊奎治は、生命の営み計できるようになった」と説明する。みずほ情報にも関係する化学反応という現象を理論的に解明

総酬はエネルギー分割法を使って新薬の候補となしてきた。

る化学物質がたんぱく質と結びつきやすいかどう2013 年のノーベル化学賞では受賞はかなわなかったが、「重要な貢献をした 7人」に名を連ねた。

かを調べるソフトを東京大学と共同開発し昨年４月に販売を始めた。

京大ヘ進学した諸熊は後にノーベル化学賞を受さらに諸熊は 1995 年、たんぱく質のような巨大賞する教授の福井謙一の指導を受けた。1960 年

な分子の振る舞いを予測する「ONIOM（オニオム）法」

代初頭の日本には満足な性能のコンピューターがを開発した。80 年代以降、コンピューターの性なかった。

能は飛躍的に向上し、次第に大きな分子を扱える

昨年のノーベル化学賞を受けたマーティン・力ーようになったが、タンパク質のような巨大な分子をプラス氏の誘いで、64 年に米コロンビア大学ヘ留計算するのは難しかった。そこで諸熊は分子をい学したことで転機が訪れる。同大が使うコンピュー

くつかの部分にわけ、反応や機能に重要な役割を

ターは京大のものより1000 倍ほど速かった。
「米果たす中心部は量子力学を駆使して高い精度で計国で勝負したい」と考えたが、京大の関係者は強算し、周辺部は簡単な計算で処理して組み合わせ

く帰国を求めた。ただ一人、福井は「まあいいんじゃる方法を考えた。中心部から何重にも皮が重なるないか」と理解を示した。諸熊は退路を断つため

タマネギ（オニオン）を連想させたことから諸熊京大の助手を辞め、米国に残った。

が育った大阪府南部の名産品タマネギにちなんでまず手がけたのは水分子が 2 つ結合した構造の名づけた。オニオム法の登場で、化学合成を促す

解析だ。たった 2 っとはいえコロンビア大の新型

触媒や体内の酵素反応の解明が進んだ。宇部興計算機でも苦労した。毎週 48 時間計算し、答え

産は医薬品や合成繊維の原料を合成する触媒のを出すまでに 2 カ月かかった。利用者が少ない土

分子構造を解析する研究に生かす。

曜の朝から始め、月曜朝までコンピューターを動

いま諸熊が注目するのは、化学反応が始まる際かした。
「仮眠を取りつつ数時間ごとに紙で打ち出の分子の形が変わる様子の解明で、北海道大学

される結果を確認した」と振り返る。結果は当時と共同研究を進めている。解明できれば、効率の定説とは違った。構造は水素と酸素が水素結合的で狙った機能を持つ化学物質の合成が可能に

で直線状につながっていた。数年後に実験で同じなるかもしれない。

結果が出て注目を集めた。水の様々な性質の決め

京大の助手だった諸熊が最初に米国に渡ってか手になる基本構造は今では、高校の教科書にもら半世紀がたつ。
「マイナーだった計算機化学は載っている。

今や化学における大きな柱に成長した」と喜ぶ。

米ロチェスター大学の教授だった 76 年、「エネ

一方で分子の世界に残る謎はまだまだ多い。80

ルギー分割法」と呼ぶ手法を開発した。分子の歳になっても、研究への意欲は衰えない。師であ間には静電気や電子の動きなど様々な力やエネルる福井謙一（京大名誉教授）の名を冠した研究ギーが働く。

所で若手研究者を育てながら、今も研究の第一諸熊の下で共同開発に取り組んだ神戸大学の北線に残り、次のターゲットを見据えている。

－ 190 －

京都大学福井謙一記念研究センター

年報

2014

2015 年 10 月発行
発行人

赤 木 和 夫編

赤 木 和 夫者

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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