Annual Report

2015

年
報
年 報

2010
2015

京都大学
福井謙一記念研究センター

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はじめに2015 年度（平成 27 年度）の京都大学福井謙一記念研究センターの活動をまとめた
年報をお届けします。本センターは、京都大学本部構内の北、約 1 キロの高野川沿いの静かな住宅街に独立して位置しております。専任教員は理論研究部門と総合研究部
門に准教授各 1 名を持っているに過ぎませんが、センター長のほか副センター長とスーパーバイザーとして工学研究科、理学研究科、化学研究所所属の 12 名の教員にご協力頂いており、このメンバーが運営委員会を構成しています。そして優れた博士
研究員に研究活動の機会を与える制度を持っており、若手研究者が国際的な雰囲気の中で日夜研究にいそしんでいます。福井センターフェローと呼ばれる博士研究員はセンターの雇用で、自分自身のアイデアで一定期間、自由闊達に研究できる身分を保証しています。
2006 年（平成 18 年）9 月に福井謙一記念研究部第一のリサーチリーダーとして世界的な理論化学者の諸熊奎治先生（分子科学研究所名誉教授）を米国エモリー大学から招聘し、研究面でのリーダーシップを発揮して頂いております。諸熊先生は、科学技術振興機構の戦略的創造研究推進事業の予算で博士研究員を採用され、全員がセンターで研究に励んでおられます。さらに 2009 年度（平成 21 年度）には福井謙一記念
研究部第二も設置し、名古屋大学名誉教授（前副学長）の大峯巖先生をリサーチリー
ダーとして招聘し、研究体制を拡大しました。なお、大峯先生は 2010 年（平成 22 年）
4 月に分子科学研究所長に転出されました。その後任として、2011 年（平成 23 年）4月に京都大学物質―細胞統合システム拠点（iCeMS）特任教授の榊茂好先生を研究部第二のリサーチリーダーとして招聘しました。榊先生は、遷移金属化合物や類縁化合物に関する研究で顕著な業績を挙げておられ、現在は科学研究費補助金「d －電子
複合系の理論化学：新しい高精度大規模計算法による微視的理解と予測」を推進しておられます。榊先生は、この予算で博士研究員を採用され、そのメンバーはセンター
で研究に励んでいます。私達は、センターが若手研究者の登竜門となることを期待しています。実際に、センターの博士研究員であった多くの方々が、現在、国内外の大学、研究機関で活躍しておられます。
当センターの歴史を簡単にご紹介します。ご承知のように故福井謙一京都大学名誉教授はフロンティア軌道理論を提案したご功績により、1981 年（昭和 56
年）にわが国で最初のノーベル化学賞を受賞されました。福井先生が京都大学
ご退官後に研究を続けられるため、京都市と産業界などのご支援で 1985 年（昭和 60 年）に財団法人「基礎化学研究所」が設立されました。専任研究員数名の規模でしたが、研究のレベルは高く、当時の研究員は現在、東京大学、名古屋大
学、分子科学研究所の教授になり、理論化学分野でトップクラスの研究者として活躍しています。この基礎化学研究所は 1998 年（平成 10 年）の福井先生のご逝
去の後、2002 年（平成 14 年）に本学に寄贈され、福井謙一記念研究センターと－i－

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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
榊

茂好、田中

績、中辻

博、

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。

本センターは、国際活動も活発で、2005 年（平成 17 年）よりチェコおよびスロバ
キアと理論化学・計算化学シンポジウムを定期的に開催しております。2011 年（平成 23 年）には国内外（主にドイツ、東欧、中国、韓国）から第一線の研究者を招き、第 1 回福井センター理論化学・計算化学国際シンポジウムを開催しました。こうした国際連携活動をさらに活性化するという観点から、2016 年（平成 28 年）2 月に国際連携研究室を設置し、その運営上必要となるコーディネーター役として、特定助教 1名を配置しました。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研究拠点の役割を果たし、国際連携活動を展開して行きたいと考えております。
例年晩秋から初冬に福井センターシンポジウムを開催しており、国内外のトップクラスの研究者による特別講演、運営委員の講演、並びに京都大学内外からのポスター発表を行っております。研究発表のレベルは高く、特別講演に来られた講師からも毎年高い評価を得ております。
さらに社会貢献活動の一環として、2011 年（平成 23 年）が福井先生のノーベル化学賞受賞 30 周年にあたるため、これを節目として本センター玄関ロビーに先生ゆかりの文物の展示コーナーを設置しました。コーナーでは先生が使用された机、椅子、
ノーベル賞メダル・賞状（複製）、研究ノート・メモ、写真などを展示し、常設展示として一般に公開しています。
また、現在本センターの 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、本センターの名を大い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、研究活動は極めて活発です。今後も、京都大学あるいは国内外との共同研究を積極的に進めて行きたいと考えております。とくに実験科学者との共同研究は重要であり、そのような連携研究をさらに活発化したいと考えております。
この年報により、本センターの活動に興味をお持ち頂ければ幸甚です。そして、それが共同研究の契機となり、時間をかけて大きな成果に結実していくことを念願しています。最後になりましたが、本センターの順調な活動はひとえに工学研究科、理学研究科、化学研究所のご協力、ご援助の賜物であり、ここに心から御礼申し上げる次第です。

平成 28 年 10 月
京都大学福井謙一記念研究センター長

赤木和夫－ ii －

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目

はじめに
Ⅰ

次

京都大学福井謙一記念研究センター長赤木和夫�������

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 ������������������������

3(3) スーパーバイザー ����������������������

6(4) 専任教員 ��������������������������

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

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

20(7) シニアリサーチフェロー �������������������

21

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

25

２．共同研究員組織 �������������������������

25

３．博士研究員プロフィール ���������������������

26

４．共同研究員プロフィール ���������������������

39

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 ��������������

42

２．福井センターセミナー ����������������������

43

３．国際交流 ����������������������������

43

４．社会へのアウトリーチ活動 ��������������������

44

５．その他（報告）��������������������������

44

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

45

２．FIFC リサーチフェロー����������������������

56

３．リサーチリーダー ������������������������

61

４．シニアリサーチフェロー ���������������������

70

５．博士研究員 ���������������������������

76

６．共同研究員 ��������������������������� 135－ iii －

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Ⅴ

資料
１．研究業績一覧 …………………………………………………………………… 147
２．共同研究者受入れ状況 ………………………………………………………… 154
３．海外渡航一覧 …………………………………………………………………… 155
４．福井謙一記念研究センターシンポジウム
５．福井センターセミナー

ポスター・プログラム ……… 156

ポスター・プログラム …………………………… 164

  （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/wp-content/themes/fifc/pdf/AnnualReport2015.pdf）－ iv －

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Ⅰ 専任教員 ･ スーパーバイザー (2015)Ⅰ

専任教員・スーパーバイザー

１．教員組織平成２７年度
職

協

議

名

氏

センター長

赤 木

和 夫

副センター長八 尾誠

副センター長田 中勝 久

工学研究科材料化学専攻

副センター長

池 田

昌 司

専

員

名

備

考

工学研究科高分子化学専攻
理学研究科物理学・宇宙物理学専攻

任

工学研究科長伊 藤 紳三郎

工学研究科高分子化学専攻

理学研究科長森 脇

淳

理学研究科数学・数理解析専攻

化学研究所長時 任

宣 博

化学研究所物質創製化学研究系
物質－細胞統合システム拠点

教

授

北 川

進

教

授

佐 藤

啓 文

工学研究科分子工学専攻

教

授

佐 々

真 一

理学研究科物理学・宇宙物理学専攻

教

授

渡 辺

宏

化学研究所分子レオロジー

教

授

田 中

功

工学研究科材料工学専攻

教

授

田 中

庸 裕

工学研究科分子工学専攻

教

授

谷 村

吉 隆

理学研究科化学専攻

教

授

山 本

量 一

工学研究科化学工学専攻

教

授

高 田

彰 二

理学研究科生物科学専攻

准 教 授

林

重 彦

理学研究科化学専攻

総合研究部門

准 教 授

池 田

昌 司

専

任

理論研究部門

准 教 授

（欠員中）

国際学術連携研究室

特定助教

水 野

英 如

専

任

永瀬グループFIFC リサーチ
フェロー

永 瀬

茂

研究員

諸熊グループFIFC リサーチ
フェロー

諸 熊

奎 治

研究員

榊グループ

リサーチ
リーダー

榊

茂 好

研究員

田中グループ

シニアリサーチ
フェロー

田 中

一 義

研究員

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（工学研究科合成・生物化学専攻）－1－

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Ⅰ 専任教員 ･ スーパーバイザー (2015)

２. 教員プロフィール
⑴

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）－2－

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Ⅰ 専任教員 ･ スーパーバイザー (2015)⑵

副センター長【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).
－3－

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Ⅰ 専任教員 ･ スーパーバイザー (2015)【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、磁気的性質、誘電的性質、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、 日 本 金 属 学 会、Materials Research Society、
Optical Society of America【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. X. Meng, U. Guler, A. V. Kildishev, K. Fujita, K. Tanaka, and V. M. Shalaev,“Breaking symmetry of plasmonic nanostructures: an efficient route towards（過去 5 年以内）
unidirectional spaser”, Scientific Reports 3 (2013) 1241-1-5.
2. T. Kawamoto, K. Fujita, H. Akamatsu, T. Nakamura, T. Kinoshita, M. Mizumaki, N.
Kawamura, M. Suzuki, Y. Kususe, S. Murai, and K. Tanaka, “Eu M4,5- and L2,3edge x-ray magnetic circular dichroism of ferromagnetic amorphous oxides in EuOTiO2 system”, Physical Review B 88 (2013) 024405-1-9.
3. X. Meng, A. V. Kildishev, K. Fujita, K. Tanaka, and V. M. Shalaev, “Wavelengthtunable spasing in the visible”, Nano Letters 13 (2013) 4106−4112.
4. 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.
5. 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.
6. 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.
7. T. Yajima, F. Takeiri, K. Aidzu, H. Akamatsu, K. Fujita, M. Ohkura, W. Yoshimune,
S. Lei, V. Gopalan, K. Tanaka, C. M. Brown, M. A. Green, T. Yamamoto, Y.i
Kobayashi, and H. Kageyama, “A labile hydride strategy to synthesize heavily
nitridized BaTiO3”, Nature Chemistry 7 (2015) 1017-1023.
【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）－4－fukui2015.indb 4

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Ⅰ 専任教員 ･ スーパーバイザー (2015)【氏名（ふりがな）】 池田

昌司 （いけだ

あつし）【職名】 准教授【所属】 東京大学 総合文化研究科 広域科学専攻 相関基礎科学系【研究室】 駒場キャンパス 16 号館 727A 号室【直通電話】 03-5454-6755【電子メールアドレス】 atsushi.ikeda@phys.c.u-tokyo.ac.jp【ホームページ】 http://park.itc.u-tokyo.ac.jp/ikeda-group/【研究分野】 統計力学、化学物理【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、2016 年 3 月 東京大学総合文化研究科准教授【所属学会】 日本物理学会、分子科学会【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－5－fukui2015.indb 5

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Ⅰ 専任教員 ･ スーパーバイザー (2015)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
10. 2016年 平成28年度日本学士院賞－6－fukui2015.indb 6

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Ⅰ 専任教員 ･ スーパーバイザー (2015)【氏名（ふりがな）】 佐藤

啓文 （さとうひろふみ）【職名】 教授【所属】 工学研究科分子工学専攻【研究室】 A4 棟 026【直通電話】 075-383-2548【FAX】 075-383-2799【電子メールアドレス】 hirofumi@moleng.kyoto-u.ac.jp【ホームページ】 http://www.riron.moleng.kyoto-u.ac.jp/【研究分野】 理論化学・量子化学・統計力学【現在の研究課題】 理論化学・物理化学【研究内容キーワード】 化学反応・自己集合・溶媒和【最終学歴】 1996 年 5 月 京都大学理学研究科化学専攻博士後期課程修了【学位】 1996 年 5 月京 都大学博士（理学）【略歴】 1996 年 8 月 岡崎国立共同研究機構分子科学研究所助手、2002 年 5 月 京都大学工学研究科講師、2004 年 5 月 京都大学工学研究科助教授、2010 年 7 月 京
都大学工学研究科教授【在外研究歴】 2004 年 6 月 -2004 年 12 月 連 合 王 国 Oxford 大 学 PTCL 訪 問 研 究 員（Paul A.
Madden 教授）【所属学会】 日本化学会、分子科学会、理論化学研究会、溶液化学研究会、イオン液体研
究会【学会活動】 日本化学会 理論化学・情報化学・計算化学ディビジョン幹事（2011 年度 -）、副主査（2015 年度 -）理論化学研究会 第三期世話人（2009 年 -）分子科学会 幹事（2012 年度 -2013 年度）、運営委員（2012 年度 -）溶液化学研究会 運営委員（2015 年度 -）【主な著書、学術論文】 1. Maxim Shishkin and Hirofumi Sato,“Self-consistent parametrization of DFT+U（過去 5 年以内）
framework using linear response approach: Application to evaluation of redox
potentials of battery cathodes”Phys. Rev. B 93(8), 085135 (2016).
2. Yoshihiro Matsumura and Hirofumi Sato,“An integral equation theory forsolvation effects on the molecular structural fluctuation”J. Chem. Phys. 143(1),014104 (2015).
3. Kento Kasahara and Hirofumi Sato,“Development of three-dimensional site-site
Smoluchowski-Vlasov equation and application to electrolyte solutions”J. Chem.
Phys. 140(24), 244110 (2014).
4. Seigo Hayaki, Yoshifumi Kimura, and Hirofumi Sato,“Ab Initio Study on an
Excited-State Intramolecular Proton-Transfer Reaction in Ionic Liquid”J. Phys.
Chem. B 117(22), 6759- 6767 (2013).
5. Hirofumi Sato,“A modern solvation theory: quantum chemistry and statisticalchemistry”Phys. Chem. Chem. Phys. 15(20), 7450-7465 (2013).
【学術関係の受賞】 日本化学会・進歩賞（2002年）
分子構造総合討論会奨励賞（2006年）
公益信託分子科学研究奨励森野基金（2008年）
溶液化学研究会学術賞（2009年）－7－

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Ⅰ 専任教員 ･ スーパーバイザー (2015)【氏名（ふりがな）】 佐々

真一 （ささしんいち）【職名】 教授【所属】 京都大学

大学院理学研究科【研究室】 理学部 5 号館

物理学宇宙物理学専攻

424 号室【直通電話】 075-753-3743【FAX】 075-753-3819【電子メールアドレス】 sasa@scphys.kyoto-u.ac.jp【ホームページ】 http://www.ton.scphys.kyoto-u.ac.jp/nonlinear/sasa/member_j.html【研究分野】 統計物理学【現在の研究課題】 マクロダイナミクスの創発【研究内容キーワード】 エントロピー、ダイナミクス、統計力学【最終学歴】 1991 年 3 月 京都大学大学院理学研究科博士後期課程物理学第一専攻修了【学位】 1991 年 3 月 理学博士 （京都大学）【略歴】 1991 年 4 月 京都大学理学部助手、1994 年 8 月 東京大学大学院総合文化研究科
助教授、2007 年 4 月 東京大学大学院総合文化研究科准教授、2009 年 4 月 東京
大学大学院総合研究科教授、2012 年 11 月 京都大学大学院理学研究科教授【在外研究歴】 1995.9- 1996.8 米国イリノイ大学

客員研究准教授【所属学会】 日本物理学会【学会活動】 2016.4-2017.3 日本物理学会領域 11 副代表【主な著書、学術論文】 1. Thermodynamic entropy as a Noether invariant, S.-I. Sasa, Yuki Yokokura, Phys.
Rev. Lett 116 140601/1-140601/6（2016）（過去 5 年以内）
2. Replica symmetry breaking in trajectories of a driven Brownian particle, Masahiko
Ueda, S.-I. Sasa, Phys. Rev. Lett 115 080605/1-080605/5（2015）
3. Derivation of Hydrodynamics from the Hamiltonian Description of Particle
Systems, S.-I. Sasa, Phys. Rev. Lett 112 100602/1-100602/5（2014）
4. Computation of large deviation statistics via iterative measurement-and-feedback
procedure, T. Nemoto, S.-I. Sasa, Phys. Rev. Lett 112 090602/1-090602/5（2014）

5. Pure glass in finite dimensions, S.-I. Sasa, Phys. Rev. Lett 109 165702/1-165702/4（2012）－8－

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Ⅰ 専任教員 ･ スーパーバイザー (2015)【氏名（ふりがな）】 渡辺

宏 （わたなべひろし）【職名】 教授【所属】 京都大学化学研究所【研究室】 化学研究所本館 N542-C【直通電話】 0774-38-3135【FAX】 0774-38-3139【電子メールアドレス】 hiroshi@scl.kyoto-u.ac.jp【ホームページ】 http://rheology.minority.jp/jp/【研究分野】 分子レオロジー【現在の研究課題】 高分子ダイナミクス【研究内容キーワード】 絡み合い，動的不均一性，粗視化【最終学歴】 1985. 3 月 大阪大学

理学博士

【学位】 阪大理博【略歴】 1983.4-1994.7: 大阪大学理学研究科 助手
1994.8-2002.12: 京都大学化学研究所 助教授
2003.1: 京都大学化学研究所 教授【在外研究歴】 1987.4-1989.3: 米国 Minnesota 大学化学工学科

博士研究員【所属学会】 日 本 レ オ ロ ジ ー 学 会 ; The Society of Rheology (USA); The Korean Society ofRheology; The American Chemical Society; The American Physical Society【学会活動】 2015.5-2017.5: 日本レオロジー学会 会長
2016.8-2020.8: President, The International Committee on Rheology
2011.3- 現在 : Associate Editor of Macromolecules (ACS)【主な著書、学術論文】 1. Y. Matsumiya and H. Watanabe , "Nonlinear Stress Relaxation of Miscible（過去 5 年以内）
Polyisoprene/Poly(p-tert-butyl Styrene) Blends in Pseudo-monodisperse State",
Macromolecules, 49, 4544-4556 (2016).
2. Youngdon Kwon, Yumi Matsumiya, and Hiroshi Wtanabe, Viscoelastic andOrientational Relaxation of Linear and Ring Rouse Chains undergoing Reversible
End-Association and Dissociation", Macromolecules, 49, 3593-3607 (2016).
3. Y. Matsumiya, N. Rakkapao, and H. Watanabe, "Entanglement Length in Miscible
Blends of cis-Polyisoprene and Poly(p-tert-butylstyrene)", Macromolecules, 48,
7889-7908 (2015).
4. K. Timachova, H. Watanabe, and N. P. Balsara, "Effect of molecular weightand salt concentration on ion transport and the transference number in polymer
electrolytes", Macromolecules, 48, 7882-7888 (2015).
5. H. Watanabe, Y. Matsumiya , Y. Masubuchi ,O. Urakawa, and T. Inoue,"Viscoelastic Relaxation of Rouse Chains undergoing Head-to-Head Association
and Dissociation: Motional Coupling through Chemical Equilibrium",
Macromolecules, 48, 3014–3030 (2015).
6. Y. Masubuchi and H. Watanabe, "Origin of Stress Overshoot under Start-up Shearin Primitive Chain Network Simulation", ACS MACRO Letters, 3, 1183-1186(2014). 3, 1183-1186
7. E. van Ruymbeke, V. Shchetnikava, Y. Matsumiya, and H. Watanabe, "Dynamic
dilution effect in binary blends of linear polymers with well-separated molecularweights", Macromolecules, 47, 7653-7665 (2014).
8. Y. Matsumiya, Y. Masubuchi, T. Inoue, O. Urakawa, C.-Y. Liu, E. van Ruymbeke,and H. Watanabe, "Dielectric and Viscoelastic Behavior of Star-branched
Polyisoprene: Two Coarse-Grained Length Scales in Dynamic Tube Dilation",－9－

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Macromolecules, 47, 7637-7652 (2014).
9. Y. Masubuchi, Y. Matsumiya, and H. Watanabe,"Test of orientation/stretch-induced
reduction of friction via primitive chain network simulations for polystyrene,
polyisoprene and poly-n-buthylacrylate ", Macromolecules, 47, 6768-6775 (2014).
10. Y. Masubuchi, Y. Matsumiya, H. Watanabe, G. Marrucci, and G. Ianniruberto,"Primitive Chain Network Simulations for Pom-pom Polymers in Uniaxial
Elongational Flows", Macromolecules, 47, 3511-3519 (2014).
11. K. Horio, T.Uneyama, Y. Matsumiya, Y.Masubuchi, and H.Watanabe, "RheoDielectric Responses of Entangled cis-Polyisoprene under Uniform Steady Shearand LAOS", Macromolecules, 47, 246-255 (2014).
12. H. Watanabe, Y. Matsumiya, and E. van Ruymbeke, "Component relaxation times
in entangled binary blends of linear chains: Reptation/CLF along partially or fully
dilated tube", Macromolecules, 46, 9296-9312 (2013).
13. Q. Huang, N. J. Alvarez, Y. Matsumiya, H. K. Rasmussen, H. Watanabe, and O.
Hassager, "Extensional Rheology of Entangled Polystyrene Solutions Suggests
Importance of Nematic Interactions", ACS Macro Letters, 2, 741-744 (2013).
14. Y. Matsumiya, K. Kumazawa, M. Nagao, O. Urakawa, and H. Watanabe,"Dielectric Relaxation of Monodisperse Linear Polyisoprene: Contribution ofConstraint Release", Macromolecules, 46, 6067-6080 (2013).
15. S. Suzuki, T. Uneyama, and H. Watanabe, "Concentration Dependence ofNonlinear Rheological Properties of Hydrophobically Modified Ethoxylated
Urethane (HEUR) Aqueous Solutions ", Macromolecules, 46, 3497-3504 (2013).
16. Y. Matsumiya, H. Watanabe, A. Takano, and Y. Takahashi, "Uniaxial Extensional
Behavior of (SIS)p-type Multiblock Copolymer Systems: Structural Origin ofHigh Extensibility", Macromolecules, 46, 2681–2695 (2013).
17. T. Uneyama, S. Suzuki, and H. Watanabe, "Concentration Dependence of
Rheological Properties of Telechelic Associative Polymer Solutions", Phys. Rev. E,
86, 031802 (2012).
18. Y. Matsumiya, Q. Chen, A. Uno, H. Watanabe, A. Takano, K. Matsuoka, and Y.
Matsushita, "Dielectric behavior of Styrene-Isoprene (SI) diblock and SIIS triblock
copolymers: Global dynamics of I blocks in spherical and cylindrical domains
embedded in glassy S matrix", Macromolecules, 45, 7050-7060, (2012).
19. E. Tamura, Y. Kawai, T. Inoue, and H. Watanabe, "Rheo-Optical Study of
Viscoelastic Relaxation Modes in Block Copolymer Micellar Lattice System",
Macromolecules, 45, 6580-6586 (2012).
20. Q. Chen, Y. Matsumiya, T. Iwamoto, K. Nishida, T. Kanaya, H. Watanabe, A.
Takano, K. Matsuoka, and Y. Matsushita, "Dielectric Behavior of Guest cisPolyisoprene Confined in Spherical Microdomain of Triblock Copolymer",
Macromolecules, 45, 2809–2819 (2012).
21. T. Yaoita, T. Isaki, Y. Masubuchi, H. Watanabe, G. Ianniruberto, and G. Marrucci,"Primitive Chain Network Simulation of Elongational Flows of Entangled
Linear Chains: Stretch/Orientation-induced Reduction of Monomeric Friction",
Macromolecules, 45, 2773–2782 (2012).
22. E. van Ruymbeke, Y. Masubuchi, and H. Watanabe, "Effective Value of the
Dynamic Dilution Exponent in Bidisperse Linear Polymers: from 1 to 4/3",
Macromolecules, 45, 2085-2098 (2012).
23. S. Suzuki, T. Uneyama, T. Inoue, and H. Watanabe, "Nonlinear Rheology of
Telechelic Associative Polymer Networks: Shear Thickening and Thinning
Behavior of Hydrophobically Modified Ethoxylated Urethane (HEUR) in Aqueous
Solution", Macromolecules, 45, 888-898 (2012).
24. Q. Chen, Y. Matsumiya, and H. Watanabe, "Dynamics in Miscible Blends of
Polyisoprene and Poly(p-tert-butyl styrene): Thermo-Rheological Behavior ofComponents ", Polymer J., 44, 102-114 (2012).
【学術関係の受賞】 2008.5: 高分子学会賞
2012.5: 日本レオロジー学会賞
2015.10: Bingham Award, The Society of Rheology (USA).
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Ⅰ 専任教員 ･ スーパーバイザー (2015)【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. G. Kobayashi, Y. Hinuma, S. Matsuoka, A. Watanabe, M. Iqbal, M. Hirayama,
M. Yonemura, T. Kamiyama, I. Tanaka & R. Kanno. Pure H- conduction in（過去 5 年以内）
oxyhydrides. Science 351, 1314-1317, (2016).
2. Y. Ikeda & I. Tanaka. Stability of the omega structure of transition elements.
Physical Review B 93, 094108 (2016).
3. A. Togo & I. Tanaka. First principles phonon calculations in materials science.
Scripta Mater 108, 1-5, (2015).
4. A. Togo, L. Chaput & I. Tanaka. Distributions of phonon lifetimes in Brillouinzones. Physical Review B 91, 094306 (2015).
5. A. Seko, A. Togo, H. Hayashi, K. Tsuda, L. Chaput & I. Tanaka. Prediction of
Low-Thermal-Conductivity Compounds with First-Principles Anharmonic LatticeDynamics Calculations and Bayesian Optimization. Physical Review Letters 115,
205901 (2015).
6. A. Seko & I. Tanaka. Special quasirandom structure in heterovalent ionic systems.
Physical Review B 91, 024106 (2015).
7. A. Seko, A. Takahashi & I. Tanaka. First-principles interatomic potentials for ten
elemental metals via compressed sensing. Physical Review B 92, 054113 (2015).
8. M. Nishijima, T. Ootani, Y. Kamimura, T. Sueki, S. Esaki, S. Murai, K. Fujita,
K. Tanaka, K. Ohira, Y. Koyama & I. Tanaka. Accelerated discovery of cathodematerials with prolonged cycle life for lithium-ion battery. Nature Communications
5, 4553 (2014).
【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 －

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Ⅰ 専任教員 ･ スーパーバイザー (2015)【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，英国王立科学会【主な著書、学術論文】 1. Effect of Ti 3+ Ions and Conduction Band Electrons on Photocatalytic and
Photoelectrochemical Activity of Rutile Titania for Water Oxidation, Fumiaki（過去 5 年以内）
Amano, Masashi Nakata, Akira Yamamoto, and Tsunehiro Tanaka, J. Phys. Chem. C,
2016, 120(12), 6467-6474.
2. Tuning the Selectivity toward CO Evolution in the Photocatalytic Conversion of
CO2 by H2O through the Modification of Ag-loaded Ga2O3 with a ZnGa2O4 Layer(Back Cover), Zheng Wang, Kentaro Teramura, Zeai Huang, Saburo Hosokawa,
Yoshihisa Sakata, Tsunehiro Tanaka, Catalysis Science & Technology, 2016, 6,1025-11032.
3. 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, Advanced Materials, 2015, 27, 4688-4694.
4. 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.
5. 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
6. 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)
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 Au 25
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.
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Ⅰ 専任教員 ･ スーパーバイザー (2015)【氏名】 谷村

吉隆 （たにむら

よしたか）【職名】 教授【所属】 京都大学大学院理学研究科化学専攻【研究室】 京都大学理学部 6 号館北棟 256 号室【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】 化学物理
【現在の研究課題】 非線形光学応答【研究内容キーワード】 統計物理学【最終学歴】 1989 年 3 月

慶應義塾大学物理学専攻博士課程修了【学位】 1989 年 3 月

博士号取得 （慶応義塾大学）【略歴】 1994 年 4 月

分子科学研究所理論研究系 助教授
総合研究大学院数物化学研究科 助教授（併任）京都大学大学院理学研究科 助教授（併任）京都大学大学院理学研究科 教授

1998 年 4 月
2003 年 6 月【在外研究歴】 1989 年 6 月
1991 年 9 月

イリノイ大学・シャンペン校 ベックマン研究所・研究員
ロチェスター大学化学科 博士研究員【所属学会】 日本物理学会、 日本化学会、 アメリカ化学会【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 年 分子科学研究奨励森野基金
2012 年 フンボルト賞 （ドイツ）
2014 年 J. Chem. Phys. Editors’choice in Theoretical Methods and Algorithms
2015 年 アメリカ物理学会フェロー－ 13 －

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Ⅰ 専任教員 ･ スーパーバイザー (2015)【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. N. Oyama, J. J. Molina, R. Yamamoto, Purely hydrodynamic origin for swarming（過去 5 年以内）
of swimming particles, Phys. Rev. E 93, 043114 (2016).
2. J. J. Molina, K. Otomura, H. Shiba, H. Kobayashi, M. Sano, and R. Yamamoto,
Rheological evaluation of colloidal dispersions using the smooth profile method:
formulation and applications, J. Fluid Mech. 792, 590-619 (2016).
3. A. J. Dunleavy, K. Wiesner, R. Yamamoto, and C. P. Royall, Mutual information
reveals multiple structural relaxation mechanisms in a model glassformer, Nature
Communications 6, 6089 (2015).
4. 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).
5. 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).
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 －

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Ⅰ 専任教員 ･ スーパーバイザー (2015)【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.

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Ⅰ 専任教員 ･ スーパーバイザー (2015)【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、蛋白質科学会、日本化学会【主な著書、学術論文】 1. Molecular mechanism of wide photoabsorption spectral shifts of color variants of（過去 5 年以内）
human cellular retinol binding protein II. Cheng Cheng, Motoshi Kamiya, Yoshihiro
Uchida, Shigehiko Hayashi*, J. Am. Chem. Soc., 137, 13362-13370 (2015)
2. Linear response path following: a molecular dynamics method to simulate global
conformational changes of protein upon ligand binding. Koichi Tamura andShigehiko Hayashi*, J. Chem. Theory Comput., 11, 2900-2917 (2015)
3. Atomistic design of microbial opsin-based blue-shifted optogenetics tools. Hideaki
E. Kato, Motoshi Kamiya, Seiya Sugo, Jumpei Ito, Reiya Taniguchi, Ayaka Orito,
Kunio Hirata, Ayumu Inutsuka, Akihiro Yamanaka, Andres D. Maturana, Ryuichiro
Ishitani, Yuki Sudo, Shigehiko Hayashi*, and Osamu Nureki*, Nat. Commun., 6,7177 (2015)
4. Quantum Biology of Retinal. Klaus Schulten and Shigehiko Hayashi, Quantum
Effects in Biology, Cambridge University Press, Chapt. 11, 237-263 (2014).
5. Molecular mechanism of ATP hydrolysis in F1-ATPase revealed by molecularsimulations and single molecule observations. Shigehiko Hayashi*, et al., J. Am.
Chem. Soc., 134, 8447-8454 (2012)
6. Crucial role of protein flexibility in formation of a stable reaction transition statein an α-amylase catalysis. Kosugi Takahiro and Shigehiko Hayashi*. J. Am. Chem.
Soc., 134, 7045-7055 (2012)－ 16 －

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⑷

専任教員

【氏名（ふりがな）】 水野

英如（みずのひでゆき）【職名】 助教【所属】 東京大学大学院総合文化研究科広域科学専攻相関基礎科学系【直通電話】 03-5454-4376【電子メールアドレス】 hideyuki.mizuno@phys.c.u-tokyo.ac.jp【研究分野】 ソフトマター物理学【現在の研究課題】 ガラス・粉体系の振動・熱物性【研究内容キーワード】 ガラス、粉体、振動モード、熱容量、熱伝導率【学歴】 2012 年 3 月 京都大学大学院工学研究科化学工学専攻博士後期課程修了【学位】 2012 年 3 月 京都大学博士（工学）【略歴】 2012 年 4 月 LIPhy, Universite Grenoble 1 and CNRS, France, Postdoctoral fellow、
2014 年 4 月 Institut fuer Materialphysik im Weltraum, DLR, Germany, Postdoctoral
fellow、2016 年 2 月 京都大学福井謙一記念研究センター 研究員、特定助教、2016 年 6 月東京大学大学院総合文化研究科 助教【所属学会】 日本物理学会【主な著書、学術論文】 1. H. Mizuno and R. Yamamoto, “General Constitutive Model for Supercooled
Liquids: Anomalous Transverse Wave Propagation”, Physical Review Letters,（過去 5 年以内）
Vol.110, p.095901 (5pages), 2013.
2. H. Mizuno, S. Mossa, and J.-L. Barrat, “Elastic heterogeneity, vibrational states,
and thermal conductivity across an amorphisation transition”, Europhysics Letters(EPL), Vol.104, p.56001 (6pages), 2013.
3. H. Mizuno, S. Mossa, and J.-L. Barrat, “Acoustic excitations and elastic
heterogeneities in disordered solids”, Proceedings of the National Academy of
Sciences of the United States of America, Vol.111, p.11949-11954 (6pages), 2014.
4. H. Mizuno, S. Mossa, and J.-L. Barrat, “Beating the amorphous limit in thermal
conductivity by superlattices design”, Scientific Reports, Vol.5, p.14116 (15pages),2015.

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FIFC 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】 FIFC 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 同教授、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、2015 年 4 月 同リ
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. M. Yamada, T. Akasaka, and S. Nagase, Endohedral Metal Atoms in Pristine and（過去 5 年以内）
Functionalized Fullerene Cages, Acc. Chem. Res., 43, 92-102 (2010).
2. X. Lu, L. Feng, T. Akasaka, and S. Nagase, Current Statues and Future
Developments of Endohedral Metallofullerenes, Chem. Soc. Rev., 41, 7723-7760(2012).
3. S. Nagase, Multiple Bonds between Lead Atoms and Short Bonds between
Transition Metals, Pure Appl. Chem., 85, 649-659 (2013).
4. X. Lu, T. Akasaka, and S. Nagase, Carbide Cluster Metallofullerenes: Structure,
Properties, and Possible Origin, Acc. Chem. Res., 46, 1627-1635 (2013).
5. M. Yamada, T. Akasaka, and S. Nagase, Carbene Additions to Fullerenes, Chem.
Rev., 113, 7209-7264 (2013).
6. 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).
7. J. –D. Guo, D. J. Liptrot, S. Nagase, and P. P. Power, The Multiple Bonding in
Heavier Group 14 Element Alkene Analogues is Stabilized Mainly by Dispersion
Force Effects, Chem. Sci. 6, 6235-6244 (2015).
【学術関係の受賞】 2012 年 文部科学大臣表彰科学技術賞（研究部門）、2012 年 福井メダル (AsiaPacific Association of Theoretical & Computational Chemists) 、2013 年 日本化学会賞

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Ⅰ 専任教員 ･ スーパーバイザー (2015)【氏名（ふりがな）】 諸熊

奎治 （もろくまけいじ）【職名】 FIFC 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 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. 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 －

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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、錯体化学会【主な著書、学術論文】 1. Absorption of CO2 and CS2 into the Hofmann-Type Porous Coordination Polymer:（過去 5 年以内）
Electrostatic versus Dispersion Interactions, M. M. Deshmukh, M. Ohba, S.
Kitagawa, and S. Sakaki, J. Am. Chem. Soc., 135, 4840-4849 (2013).
2. Theoretical Study of Reactivity of Ge(II)-hydride Compound: Comparison withRh(I)-Hydride Complex and Prediction of Full Catalytic Cycle by Ge(II)-hydride,N. Takagi, S. Sakaki, J. Am. Chem. Soc., 135, 8955-8965 (2013).
3. 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).
4. 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).
5. 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).
6. 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).
7. How Can We Understand Au8 Cores and Entangled Ligands of Selenolate- andThiolate-Protected Gold Nanoclusters Au24(ER)20 and Au20(ER)16 (E = Se, S; R =Ph, Me)? A Theoretical Study, N. Takagi, K. Ishimura, M. Matsui, R. Fukuda, T.
Matsui, T. Nakajima, M. Ehara, and S. Sakaki, J. Am. Chem. Soc., 137, 8593-8602(2015).
8. 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, M. Nakagaki and S. Sakaki, Phys. Chem.
Chem. Phys., 17, 16294-16305 (2015).
9. Theoretical and Computational Study of a Complex System Consisting ofTransition Metal Element(s): How to Understand and Predict Its Geometry,
Bonding Nature, Molecular Property, and Reaction Behavior, S. Sakaki, Bull.
Chem. Soc. Jpn., 88, 889-938 (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 －

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シニアリサーチフェロー【氏名（ふりがな）】 田中

一義 （たなかかずよし）【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】 福井記念研究センター 206【直通電話】 075-711-7867【FAX】 075-781-4757【電子メールアドレス】 ktanaka@moleng.kyoto-u.ac.jp【ホームページ】 http://www.fukui.kyoto-u.ac.jp/members_ja【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）
4. 元素ブロック材料の基礎と実用化のための理論化学 ,「中條善樹監修 , 元素
ブロック高分子−有機・無機ハイブリッド材料の新概念−」( 共著 , シーエム
シー , 2015)
5. ボール物理化学 第 2 版（上）（監訳ならびに共訳，化学同人，2015）
6. ボール物理化学 第 2 版（下）（監訳ならびに共訳，化学同人，2016）（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).

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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).
8. スズ版グラフェン“スタネン”がつくられた！（単著） 化学 , 71, No. 1, 2126 (2016).

（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. 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 Effecton Vibronic Couplings (Y. Shigemitsu, M. Uejima, T. Sato, K. Tanaka, and Y.
Tominaga) J. Phys. Chem. A, 116, 9100-9109 (2012).
4. A Triphenylamine Double-Decker: From a Delocalized Radical Cation to a
Diradical Dication with an Excited Triplet State (Y. Yokoyama, D. Sakamaki, A.
Ito, K. Tanaka, and M. Shiro) Angew. Chem. Int. Ed., 51, 9403-9406 (2012).
5. Mechanisms of Localization in Isotope-Substitutes Dynamical Jahn-Teller Systems(N. Iwahara, T. Sato, K. Tanaka, and L. F. Chibotaru) Eur. Phys. Lett., 100, 43001
1-6 (2012).
6. Chemical Reactivity in Nucleophilic Cycloaddition to C70: Vibronic Coupling
Density and Vibronic Coupling Constants as Reactivity Indices (N. Haruta, T.
Sato, and K. Tanaka) J. Org. Chem., 77, 9702-9706 (2012).
7. A Polymacrocyclic Oligoarylamine with a Pseudobeltane Motif: Towards a
Cylindrical Multispin System (D. Sakamaki, A. Ito, K. Furukawa, T. Kato, M.
Shiro, and K. Tanaka) Angew. Chem. Int. Ed., 51, 12776-12781 (2012).
8. Meta-Para-Linked Octaaza[18]cyclophanes and Their Polycationic States (D.
Sakamaki, A. Ito, K. Furukawa, T. Kato, and K. Tanaka) J. Org. Chem., 78, 29472956 (2013).
9. Vibronic Couplings in Cycloadditions to Fullerenes (N. Haruta, T. Sato, N.
Iwahara, and K. Tanaka) J. Phys. C: Conf. Ser., 428, 012003 1-7 (2013).
10. Vibronic Coupling Density and Related Concepts (T. Sato, M. Uejima, N. Iwahara,
N. Haruta, K. Shizu, and K. Tanaka) J. Phys. C: Conf. Ser., 428, 012010 1-19
(2013).
11. Vibronically Induced Activation Mechanism in Photocatalysis of Highly Dispersed
Vanadium Oxide Supported on Silica, V2O5/SiO2: Evidence in Phosphorescence
Spectra (N. Iwahara, T. Sato, K. Tanaka, and T. Tanaka) Chem. Phys. Lett., 584,
63-66 (2013).
12. Reaction Mechanism in the Mechanochemical Synthesis of Dibenzophenazine:
Application of Vibronic Coupling Density Analysis (N. Haruta, T. Sato, K. Tanaka,
and M. Baron) Tetrahedron Lett., 54, 5920-5923 (2013).
13. Redox Modulation of para-Phenylenediamine by Substituted Nitronyl Nitroxide
Groups and Their Spin States (A. Ito, R. Kurata, D. Sakamaki, S. Yano, Y. Kono,
Y. Nakano, K. Furukawa, T. Kato, and K. Tanaka) J. Phys. Chem. A, 117, 1285812867 (2013).
14. Vibronic Couplings in C60 Derivatives for Organic Photovoltaics (N. Iwahara, T.
Sato, K. Tanaka, and H. Kaji) Chem. Phys. Lett., 590, 169-174 (2013).
15. Preparation of D-A Polymer with Disilanobithiophene as New Donor Component
and Application to High-voltage Bulk Heterojunction Polymer Solar Cell (J.
Ohshita, M. Nakashima, D. Tanaka, Y. Morihara, H. Fueno, and K. Tanaka) Polym.
Chem., 5, 346-349 (2014).

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Ⅰ 専任教員 ･ スーパーバイザー (2015)

16. Enhancement of Fluorescence in Anthracene by Chlorination: Vibronic Coupling
and Transition Dipole Moment Density Analysis (M. Uejima, T. Sato, K. Tanaka,and H. Kaji) Chem. Phys., 430, 47-55 (2014).
17. Pseudo Jahn-Teller Origin of Distortion in [6]Cycloparaphenylene (Y. Kameoka, T.
Sato, T. Koyama, K. Tanaka, and T. Kato) Chem. Phys. Lett., 598, 69-74 (2014).
18. Highly Coplanar (E)-1,2-Di(1-naphthyl)disilene Involving a Distinct CH-πInteraction with the Perpendicularly Oriented Protecting Eind Group (M.
Kobayashi, N. Hayakawa, K. Nakabayashi, T. Matsuo, D. Hashizume, H. Fueno, K.
Tanaka, and K. Tamao) Chem. Lett., 43, 432-434 (2014).
19. A Designed Fluorescent Anthracene Derivative: Theory, Calculation, Synthesis,
and Characterization (M. Uejima, T. Sato, M. Detani, A. Wakamiya, F. Suzuki, H.
Suzuki, 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, 1424414256 (2014).
21. Synthesis and Polymerization of a para-Disubstituted T8-caged HexaisobutylPOSS 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 OxidizedStates (D. Sakamaki, A. Ito, T. Matsumoto, and K. Tanaka) RSC Adv., 4, 3947639483 (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 La 2 @C 80 in Nucleophilic andElectrophilic 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
Design for 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).

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Ⅰ 専任教員 ･ スーパーバイザー (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).
34. A Triphenylamine with Two Phenoxy Radicals Having Unusual Bonding Pattersand a Closed-Shell Electronic State (D. Sakamaki, S. Yano, T. Kobashi S. Seki, T.
Kurahashi, S. Matsubara, A. Ito, and K. Tanaka) Angew. Chem. Int. Ed., 54, 82678270 (2015).
35. New Tris- and Pentakis-Fused Donors Containing Extended Tetrathiafulvalenes:
New Positive Electrode Materials for Reachargeable Batteries (S. Iwamoto, Y.
Inatomi, D. Ogi, S. Shibayama, Y. Murakami, M. Kato, K. Takahashi, K. Tanaka, N.
Hojo, and Y. Misaki) Beilstein J. Org. Chem., 11, 1136-1147 (2015).
36. Fluorescence Enhancement of Non-Fluorescent Triphenylamine: A Recipe to
Utilize Carborane Cluster Substituents (M. Uebe, A. Ito, Y. Kameoka, T. Sato, andK. Tanaka) Chem. Phys. Lett., 633, 190-194 (2015).
37. Highly Efficient Blue Electroluminescence Using Delayed-Fluorescence Emitterswith Large Overlap Density between Luminescent and Ground States (K. Shizu,
H. Noda, H. Tanaka, M. Taneda, M. Uejima, T. Sato, K. Tanaka, H. Kaji, and C.
Adachi) J. Phys. Chem. C, 119, 26283-26289 (2015).
38. para-Bisvinylhexaisobutyl-Substituted T 8 Caged Monomer: Synthesis andHydrosilylation Polymerization (T. Maegawa, Y. Irie, H. Imoto, H. Fueno, K.
Tanaka, and K. Naka) Polym. Chem., 6, 7500-7504 (2015).
39. Coplanar Oligo(p-phenylenedisilenylene)s as Si=Si Analogues of Oligo(pphenylenevinylene)s: Evidence for Extended π-Conjugation through the CarbonSilicon π-Frameworks (L. Li, T. Matsuo, D. Hashizume, H. Fueno, K. Tanaka, andK. Tamao) J. Am. Chem. Soc., 137, 15026-15035 (2015).
40. Isolation and Characterization of Persistent Radical Cation and Dication of
2,7-Bis(dianisylamino)pyrene (R. Kurata, K. Tanaka, and A. Ito) J. Org. Chem.,
81, 137-145 (2016).
41. (Z)-1,2-Di(1-pyrenyl)disilene: Synthesis, Structure, and Intramolecular ChargeTransfer Emission (M. Kobayashi, N. Hayakawa, T. Matsuo, B. Li, T. Fukunaga, D.
Hashizume, H. Fueno, K. Tanaka, and K. Tamao) J. Am. Chem. Soc., 138, 758-761(2016).
42. Synthesis and Characterization of 6,13-Diamino-Substituted Pentacenes (A. Ito,
M. Uebe, K. Takahashi, H. Ishikawa, D. Sakamaki, H. Sato, T. Matsumoto, and K.
Tanaka) Chem. Eur. J., 22, 2165-2170 (2016).
43. O2-Triggered Directional Switching of Photocurrent in Self-Assembled Monolayer
Composed of Porphyrin- and Fullerene-Terminated Helical Peptides on Gold (H.
Uji, K. Tanaka, and S. Kimura) J. Phys. Chem. C, 120, 3684-3689 (2016).
（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－ 24 －

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Ⅱ 博士研究員 (2015)

Ⅱ

博士研究員

１．博士研究員組織
平成２７年度
職

名

氏

名

嶺澤

範行

齋藤

拓也

福井センターフェロー
多羅間 充 輔西本
福井センターフェロー

伊勢川 美 穂鈴木

諸熊グループ研究フェロー

佳央

聡

Akhilesh Kumar Sharma
Pedro J. Castro Pelaez

福井センターフェロー

榊グループ
研究フェロー

青野

信治

中垣

雅之

Shuwei Tang
Hong Zheng
Nishamol Kuriakose

２．共同研究員組織
職

名

氏

名

W.M.C. Sameera
諸熊グループ共同研究員

Yanying Zhao
Ming-Chung Yang

－ 25 －

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Ⅱ 博士研究員 (2015)

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】 研究員【所属】 理化学研究所 計算科学研究機構 量子系分子科学研究チーム【研究室】 〒 650-0047 神戸市中央区港島南町 7-1-26【直通電話】 078-940-5812【FAX】 078-304-4962【電子メールアドレス】 noriyuki.minezawa@riken.jp【研究分野】 理論化学・計算化学【現在の研究課題】 大規模分子系の非断熱分子動力学シミュレーション【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
2016 年 1 月 理化学研究所 計算科学研究機構【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).

－ 26 －

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Ⅱ 博士研究員 (2015)【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, and Takahiro Sakaue, “Driven anomalous diffusion: An example
from polymer stretching”, Phys. Rev. E, 92, 012601 (13 pages total) (2015).
（過去 5 年以内）
2. Takuya Saito, “Rate in template-directed polymer synthesis”, Phys. Rev. E, 89,
062716 (8 pages total) (2014).
3. Takuya Saito, Takahiro Sakaue, “Cis-trans dynamical asymmetry in driven polymertranslocation”, Phys. Rev. E, 88, 042606 (5 pages total) (2013).
4. Takuya Saito, Takahiro Sakaue, “Process time distribution of driven polymertransport”, Phys. Rev. E, 85, 061803 (7 pages total) (2012).
5. 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).
6. 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－ 27 －

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Ⅱ 博士研究員 (2015)【氏名（ふりがな）】 多羅間

充輔 （たらまみつすけ）【職名】 特定研究員【所属】 福井謙一記念研究センター【研究室】 208
【直通電話】 711-7863【電子メールアドレス】 tarama@fukui.kyoto-u.ac.jp【ホームページ】 http://www.fukui.kyoto-u.ac.jp/users/tarama/index.html【研究分野】 非線形ダイナミクス、アクティブマター、ソフトマター【現在の研究課題】 アクティブソフトマターのダイナミクス【研究内容キーワード】 アクティブマター、ダイナミクス、変形、非線形ダイナミクス、細胞運動【学歴】 修士（理学）2012/3/26
博士（理学）2015/3/23

京都大学理学研究科
京都大学理学研究科【学位】 博士（理学）【略歴】 福井センターフェロー（2015/4/1 より）【所属学会】 日本物理学会【学会活動】 アクティブマター研究会 2016（2016 年 1 月 22-23 日）の世話人をしました。
【主な著書、学術論文】 1. M. Tarama, Y. Itino, A.M. Menzel, and T. Ohta, “Individual and collective dynamics
of self-propelled soft particles”, Eur. Phys. J. Special Topics 223, 121–139 (2014).
（過去 5 年以内）
2. M. Tarama, A.M. Menzel, and H. Löwen, “Deformable microswimmer in a swirl:Capturing and scattering dynamics”, Phys. Rev. E 90, 032907 (2014).
3. M. Tarama, P. Cremer, D.Y. Borin, S. Odenbach H. Löwen, and A.M. Menzel,“Tunable dynamic response of magnetic gels: Impact of structural properties andmagnetic fields”, Phys. Rev. E 90, 042311 (2014).
4. T. Ohta, M. Tarama and M. Sano, “Simple model of cell crawling”, Physica D 318319, 3-11 (2016).
5. M. Tarama and T. Ohta, “Reciprocating motion of active deformable particles”,
Europhys. Lett. 114, 30002 (2016).
【学術関係の受賞など】 Research Fellow of Japan Society for the Promotion of Science (DC1) (Apr. 2012 Mar. 2015)
ポスター発表 優秀賞（平成24年度未踏科学サマー道場、Aug. 2014）
the Richard M. Noyes Fund Fellowship (Jul. 2014)－ 28 －

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Ⅱ 博士研究員 (2015)【氏名（ふりがな）】 西本

佳央 （にしもと

よしお）【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】 福井謙一記念研究センター 208【直通電話】 075-711-7894【電子メールアドレス】 nishimoto.yoshio@fukui.kyoto-u.ac.jp【研究分野】 理論化学・計算化学【現在の研究課題】 大規模量子化学計算・エネルギー高次微分【研究内容キーワード】 密度汎関数強束縛法・フラグメント分子軌道法・エネルギー微分【学歴】 2015 年 3 月
攻修了

名古屋大学大学院理学研究科博士課程（後期課程）物質理学専【学位】 2015 年 3 月

博士（理学）（名古屋大学）【略歴】 2015 年 4 月

京都大学福井謙一記念研究センター・福井センターフェロー【所属学会】 日本化学会【主な著書、学術論文】 1. Nishimoto, Y. “DFTB/PCM Applied to Ground and Excited State Potential Energy
Surfaces”, J. Phys. Chem. A 2016, 120, 771-784.
（過去 5 年以内）

2. Nishimoto, Y.; Nakata, H.; Fedorov, D. G.; Irle, S. “Large-Scale QuantumMechanical Molecular Dynamics Simulations Using Density-Functional TightBinding Combined with the Fragment Molecular Orbital Method”, J. Phys. Chem.
Lett. 2015, 6, 5034-5039.
3. Nishimoto, Y. “Time-dependent density-functional tight-binding method with thethird-order expansion of electron density”, J. Chem. Phys. 2015, 143, 094108.
4. Nishimoto, Y.; Fedorov, D. G.; Irle, S. “Third-order density-functional tight-binding
combined with the fragment molecular orbital method”, Chem. Phys. Lett. 2015,
636, 90-96.
5. Nishimoto, Y.; Fedorov, D. G.; Irle, S. “Density-Functional Tight-Binding
Combined with the Fragment Molecular Orbital Method”, J. Chem. Theory
Comput. 2014, 10, 4801-4812.

【学術関係の受賞など】 日本学術振興会特別研究員（DC1） 2012.4-2015.3－ 29 －

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Ⅱ 博士研究員 (2015)【氏名（ふりがな）】 伊勢川

美穂 （いせがわみほ）【職名】 センターフェロー【所属】 福井謙一記念研究センター【研究室】 諸熊グループ【電子メールアドレス】 isegawa.miho.5s@kyoto-u.ac.jp【研究分野】 計算化学
【現在の研究課題】（1）銅触媒による炭素 - ホウ素の生成機構の解明（2）ヒドロゲナーゼ模倣錯体による小分子活性化の反応機構の解明【研究内容キーワード】 小分子活性化、有機金属触媒、反応経路、DFT、反応性、選択性【学歴】 京都大学理学部【学位】 理学（京都大学）【略歴】 2009- 博士号取得 ( 理学、京都大学 )2010- 米国ミネソタ大学博士研究員
2013- 福井謙一記念研究センター研究員
2014- 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
2016- 福井謙一記念研究センターセンターフェロー【学会活動】 京都大学福井謙一記念センターシンポジウム 2016
【主な著書、学術論文】 1. Predicting pathways for terpene from first principles-routes to known and new（過去 5 年以内）
sesquiterpenes, M. Isegawa, S. Maeda, D. J. Tantillo, and K. Morokuma Chemical
Science, 5, 1555 (2014).
2. 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).
3. 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).
4. Photochemical Ring Opening and Closing of Three Isomers of Diarylethene: SpinFlip Time Dependent Density Functional Study, M. Isegawa and K. Morokuma, J.
Phys. Chem. A. 119, 4191 (2015).
5. Ionization Energies and Aqueous Redox Potentials of Small Organic Molecules:
Capabilities and Limitations of Modern Methods, M. Isegawa, D. A. Pantazis, F.
Neese, J. Chem. Theory Comput. 12, 2272 (2016).

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Ⅱ 博士研究員 (2015)【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, S. Maeda, K. Morokuma, Exploration of Quenching Pathways ofMultiluminescent Acenes Using the GRRM Method with the SF-TDDFT Method, J.
Phys. Chem. A, 119 pp 11479–11487 (2015)
3. S.Sasaki, S.Suzuki, W.M.C. Sameera, K. Igawa, K. Morokuma, G. Konishi,
Highly twisted N, N-dialkylamines as a design strategy to tune simple aromatichydrocarbons as steric environment-sensitive fluorophores, J. Am. Chem. Phys., inpress【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－ 31 －

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Ⅱ 博士研究員 (2015)【氏名】 Akhilesh Kumar Sharma【職名】 Postdoctoral Fellow【所属】 Morokuma Group, Fukui Institute for Fundamental Chemistry【研究室】 Room No. 203【直通電話】 075-711-7831【FAX】 075-781-4757【電子メールアドレス】 sharma@fukui.kyoto-u.ac.jp【研究分野】 Computational Chemistry【現在の研究課題】 Mechanistic study of organic and organometallic reactions【研究内容キーワード】 DFT, AFIR Methods, Reaction Mechanism, Stereoselectivity【学歴】 Master of Science, Himachal Pradesh University, Shimla, India (2006)【学位】 Ph.D., Indian Institute of Technology Bombay, Mumbai, India (2014)【略歴】 Research Associate, Indian Institute of Technology Bombay, Mumbai, India (20142015)【主な著書、学術論文】 1. A. K. Sharma, R. B. Sunoj, “Stereocontrol in proline-catalyzed asymmetricamination: a comparative assessment of the role of enamine carboxylic acid and（過去 5 年以内）
enamine carboxylate” Chem. Commun. 2011, 47, 5759.
2. A. K. Sharma, R. B. Sunoj, “Refined Transition-State Models for Proline-Catalyzed
Asymmetric Michael Reactions under Basic and Base-Free Conditions” J. Org.
Chem. 2012, 77, 10516.
3. D. Katayev, Y.-X. Jia, A. K. Sharma, D. Banerjee, C. Besnard, R. B. Sunoj, E.
P. Kündig, “Synthesis of 3,3-Disubstituted Oxindoles by Palladium-Catalyzed
Asymmetric Intramolecular α-Arylation of Amides: Reaction Development andMechanistic Studies” Chem. Eur. J. 2013, 19, 11916.
4. A. K. Sharma, D. Roy, R. B. Sunoj, “Mechanism of Catalytic Methylation of
2-Phenylpyridine Using di-tert-Butyl Peroxide” Dalton Trans. 2014, 43, 10183.
5. W. M. C. Sameera, A. K. Sharma, Satoshi Maeda, Keiji Morokuma, “Artificial
Force Induced Reaction Method for Systematic Determination of Complex
Reaction Mechanisms” Chem. Rec. 2016, (Accepted).
【学術関係の受賞など】 “2014 Eli Lilly and Company Asia Outstanding Thesis Award” for Best Thesis
Fellowship form Council for Scientific and Industrial Research (CSIR), India to
Pursue PhD (2007-2012)－ 32 －

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Ⅱ 博士研究員 (2015)【氏名】 Pedro J. Castro Pelaez【職名】 Research Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Office 212【直通電話】 075-711-7647【電子メールアドレス】 pedrojc7@gmail.com【研究分野】 Computational Chemistry【現在の研究課題】 Photochemistry, non-adiabatic processes【研究内容キーワード】 Photofunctional molecules, Potential energy surfaces, non-adiatbatic dynamics【学歴】 M.Sc of the Universitat Rovira I Virgili (Spain)
Ph.D of the Universitat Rovira I Virgili (Spain)【学位】 M.Sc in Theoretical and Computational Chemistry (2011)
Ph.D in Chemical Science and technology (2015)【略歴】 Ph.D fellow in Universitat Rovira I Virgili (Spain), 2011-2015【主な著書、学術論文】 1. Aurelie Perveaux, Pedro J. Castro, Mar Reguero, Hans-Dieter Meyer, Fabien Gatti,
Benjamin Lasorne, David Lauvergnat. Springer Proceedings In Physics 162, 2015,（過去 5 年以内）
p.386–390.
2. Aurelie Perveaux, Pedro J. Castro, David Lauvergnat, Mar Reguero, and Benjamin
Lasorne. J. Phys. Chem. Lett. 2015, 6, 1316−1320
3. Isabel Gómez, Pedro J. Castro and Mar Reguero. J. Phys. Chem. A 2015, 119,1983−1995.
4. V. José Cotuá, Sandra Cotes, Fernando Castro and Pedro J. Castro. Journal of Basic& Applied Sciences, 2013, 9, 16-20.
5. Pedro J. Castro, Isabel Gomez, Maurizio Cossi and Mar Reguero. The Journal of
Physical Chemistry A, 116(31), p.8148–8158, 2012.

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Ⅱ 博士研究員 (2015)【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., Mori T., and Sakaki S., “3D-RISM-MP2 Approach to Hydration Structureof Pt(II) and Pd(II) Complexes: Unusual H‑Ahead Mode vs Usual O‑Ahead One” J.
（過去 5 年以内）
Chem. Theory Comput. 12 1189-1206 (2016). [Cover]
2. 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
Delocalized Ground and Excited States in Solution” J. Chem. Theory Comput. 101062 (2014).
3. 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)
4. 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)
5. 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).
6. 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).

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Ⅱ 博士研究員 (2015)【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 “Inverse Sandwich-Type Dinitrogen
Complexes of Hetero-Dinuclear 3d Metals: Theoretical Prediction of Characteristic（過去 5 年以内）
Features of Geometry and Spin Multiplicity” Submitting to Phys. Chem. Chem.
Phys.
2. Masayuki Nakagaki and Shigeyoshi Sakaki “CASPT2 study of inverse sandwichtype dinuclear 3d transition metal complexes of ethylene and dinitrogen molecules:
similarities and differences in geometry, electronic structure, and spin multiplicity”
Phys. Chem. Chem. Phys. 17, 16294-16305(2015)
3. 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)
4. 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)－ 35 －

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Ⅱ 博士研究員 (2015)【氏名】 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.

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Ⅱ 博士研究員 (2015)【氏名】 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)
7. H. Zheng, X. Zhao, S. Sakaki, Reaction of Fullerene with Dinuclear Ruthenium
Complex: Theoretical Understanding and Prediction, in submission.

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Ⅱ 博士研究員 (2015)【氏名】 Nishamol Kuriakose【職名】 Postdoctoral Fellow【所属】 Sakaki Group, Fukui Institute for Fundamental Chemistry【研究室】 Room No. 203【電子メールアドレス】 nishamol@fukui.kyoto-u.ac.jp【研究分野】 Computational Chemistry【現在の研究課題】 Computational investigation on the bonding and reactivity of transition metal
complexes【研究内容キーワード】 DFT, transition metal complexes, σ -bond activation【学歴】 Master of Science, University of Kerala, Trivandrum, India (2008)【学位】 Ph.D., Academy of Scientific and Innovative research, India (2015)【主な著書、学術論文】 1. Nishamol Kuriakose, Shantanu Kadam, and Kumar Vanka,* (2012), A theoretical
study of metal−metal cooperativity in the homogeneous water gas shift reaction,（過去 5 年以内）
Inorg. Chem., 51, 1, 377−385.
2. Nishamol Kuriakose and Kumar Vanka,* (2013), Can molecular cages be effectiveat small molecule activation? A computational investigation, Inorg. Chem., 52, 8,
4238–4243.
3. Nishamol Kuriakose and Kumar Vanka,* (2014), New insights into small molecule
activation byacyclic silylenes: a computational investigation, Dalton Trans., 43,2194-2201.
4. Vaishali S. Shende,a Savita K. Shingote,a Sudhindra H. Deshpande,a Nishamol
Kuriakose,b Kumar Vanka,b* Ashutosh A. Kelkara* (2014), Asymmetric transferhydrogenation of imines in water/methanol co-solvent system and mechanistic
investigation by DFT study, RSC Adv., 4, 46351–46356.
5. Nishamol Kuriakose and Kumar Vanka,* (2015), Can substituted allenes be highly
efficient leaving groups in catalytic processes? A computational investigation, J.
Comput. Chem., 36, 795–804.
6. Nishamol Kuriakose and Kumar Vanka,* (2016), Can main group systems act as
superior catalysts for dehydrogenation reactions in comparison to transition metal
based systems? A computational investigation, Dalton Trans., Advance Article,
DOI: 10.1039/C5DT01058F.
7. Teruhiko Saito, Nishamol Kuriakose, Shigeyoshi Sakaki,* Yoshiaki Nakaoa*
Synthesis of neutral and anionic Aluminum containing Rhodium complexes andtheir reactivity toward cleavage of srong σ–bonds. (communicated).
【学術関係の受賞など】 Shell India Computational Talent Prize - India – 2013: Honorable Mention Awardfor the paper “Can Molecular Cages Be Effective at Small Molecule Activation? A
Computational Investigation.

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Ⅱ 博士研究員 (2015)

４. 共同研究員プロフィール【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 QM/MM methods, theoretical inorganic chemistry, florescent probs.
【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)
JSPS postdoctoral fellow, FIFC, Kyoto University. Japan (2014)【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, “Transition metal catalysis by density functional
theory and density functional theory molecular mechanics”, WIREs Comput. Mol.
（過去 5 年以内）
Sci., Wiley-VCH, 2012, 2, 375-380.
2. L. Maestre, W. M. C. Sameera, M. M. Díaz-Requejo, F. Maseras, P. J. Pérez. “AGeneral Mechanism for the Copper- and Silver-Catalyzed olefin aziridination
reactions: concomitant involvement of the singlet and triplet pathways”, J. Am.
Chem. Soc. 2013, 135, 1338-1348.
3. 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, K. Morokuma, “TheONIOM Method and its Applications”, Chem. Rev. 2015, 115, 5678-5796.
4. W. M. C. Sameera, M. Hatanaka, T. Kitanasono, S. Kobayashi, K. Morokuma,“The Mechanism of Iron(II)-catalyzed Asymmetric Mukaiyama Aldol Reaction in
Aqueous Media: Density Functional Theory and Artificial Force-Induced Reaction
Study”, J. Am. Chem. Soc. 2015, 137, 11085-11094.
5. W. M. C. Sameera, S. Maeda, K. Morokuma, “Computational catalysis using theartificial force induced reaction (AFIR) method”, Acc. Chem. Res. 2016, 49, 763773.
【学術関係の受賞など】 Assistant professor, Hokkaido University, Japan. (2016)
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)－ 39 －

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Ⅱ 博士研究員 (2015)【氏名】 Yanying Zhao
【職名】 Visiting Scholar【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 203【直通電話】 075-711-7834【FAX】 075-711-7834【電子メールアドレス】 zhaoyying2008@hotmail.com【研究分野】 Molecular Spectroscopy and Computational Chemistry【現在の研究課題】 Reaction of photo-functional molecules【研究内容キーワード】 Excited State Proton Transfer Theoretical Study by GRRM
【学歴】 Sept. 2000, Master of Sci., Department of Chemistry, Hebei Normal University, China
Sept. 2004, Doctor of Sci., Department of Chemistry, Fudan University, China【学位】 Doctor of Science from Fudan University, China【略歴】 October. 2007, Assistant Professor, Associate Professor, Zhejiang Sci-Tech University,
China【所属学会】 Chemical Society of China【主な著書、学術論文】 1. Chen Xiao, Zhao Yanying*, Zhang Haibo, Xue jiadan, Zheng Xuming* Excitedstate proton transfer dynamics of thioacetamide in S2(π-π*) state: resonance Raman（過去 5 年以内）
spectroscopic and quantum mechanical calculations study. J. Phys. Chem. A 119,
832-842(2015)
2. Zhao Yanying, Xu Qiang* Chapter 15, Metal-organic frameworks as platforms
for hydrogen generation from chemical hydrides in Organometallics and Related
Molecules for Energy Conversion, Green Chemistry and Sustainable Technology.
Springer-Verlag Berlin Heidelberg 421-467(2015). W.-Y. Wong (ed.), DOI
10.1007/978-3-662-46054-2_15.
3. Li Dan, Zhao Yanying*, Xue Jia-Dan, Zheng Xuming Structural dynamics of
4-formaldehyde imidazole and imidazole in light absorbing S2(π-π*) state Journalof Raman Sepctroscopy 46(3), 293-301(2015).
4. Zhao Yanying*, Zhang Yuchen, Liu Xin, Zheng Xuming Formation,
characterization, structure and bonding analysis of the metal-carbon bond OM(ŋ6-C6H6) (M = Sc, Ti) complexes in solid matrix: Infrared spectroscopic andtheoretical study. J. Orgmet. Chem. 777, 25-30(2015)
5. Zhao Yanying*, Fan Kexue, Huang Yongfei, Zheng Xuming Matrix isolation
infrared spectra, assignment and DFT investigation on reactions of iron andmanganese monoxides with CH3C1. Spectrochimica Acta Part A-Molecular andBiomolecular Spectroscopy 116, 96-101(2013)
6. Zhao Yanying* C-Cl Activation by Group IV Metal Oxides in Solid Argon
Matrixes: Matrix Isolation Infrared Spectroscopy and Theoretical Investigations of
the Reactions of MOx (M = Ti, Zr; x=1, 2) with CH3Cl. J. Phys. Chem. A 117(27),5664-5674(2013)【学術関係の受賞など】 Project Grants 521 521 Talents Cultivation, Zhejiang Sci-Tech University, Zhejiang,
Zhejiang, 2012~Present－ 40 －

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Ⅱ 博士研究員 (2015)【氏名】 Ming-Chung Yang
【職名】 Foreign joint researcher【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 203【直通電話】 075-711-7834【FAX】 075-711-7834【電子メールアドレス】 mingchungmc@gmail.com【研究分野】 Computational Chemistry【現在の研究課題】 Theoretical study of catalytic reaction【研究内容キーワード】 Fullerene-Transition metal complexes【学歴】 June 2006, Master’s degree., National Taiwan University
January 2012, Philosophy’s degree, National Tsing Hua University【学位】 Philosophy’s degree from National Tsing Hua University【略歴】 Postdoctoral Fellow, Applied Chemistry Department, Chiayi University【主な著書、学術論文】 1. Ming-Chung Yang, Ming-Der Su, The addition reactions between N‑heterocycliccarbenes and fullerenes (C60 and C70): a density functional study, Theoretical（過去 5 年以内）
Chemistry Accounts, 2015, 134, 38.
2. Ming-Chung Yang, Tsung-Wei Shih, Yu-Chi Li, Jia-Ying Ma, and Ming-Der Su, A
Model Study on Molecular Properties and Mechanistic Investigations of P=C=E14
Molecules, European Journal of Inorganic Chemistry, 2015, 1795-1803.
3. Tsung-Wei Shih, Ming-Chung Yang, and Ming-Der Su, Doubly Bonded E13=P and
B=E15 Molecules and Their Reactions with H2, Acetonitrile, Benzophenone, and
2,3-Dimethylbutadiene, Inorganic Chemistry, 2015, 54, 5154.
4. Ming-Chung Yang, Ming-Der Su, Theoretical Designs for Fullerene Carbenes, C60E-C60 and C70-E-C70 (E = Group 14 Elements): A Target for Experimental Studies, J.
Phys. Chem. C, 2015, 119, 12668.

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Ⅲ 研究広報活動 (2015)

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 13 回

京都大学福井謙一記念研究センターシンポジウム日時2016 年（平成 28 年）2 月 5 日

場

所

京都大学福井謙一記念研究センター（3F 大会議室）

講

演

田中

一義（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）「発光性分子材料の理論化学的設計」
10:15 − 11:15
西森秀稔（東京工業大学 大学院理工学研究科 教授）「量子アニーリング理論と D-Wave マシン」
11:30 − 12:30
永谷清信（京都大学 大学院理学研究科 助教）「Ｘ線自由電子レーザーとの付き合い方」（八尾誠先生の都合により、代講）
14:00 − 15:00
―

休

憩

―

ポスターセッション

15:30 − 17:20

懇親会（１F 多目的ルーム）

17:30 − 19:00－ 42 －

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Ⅲ 研究広報活動 (2015)

２．福井センターセミナー
第 13 回

福井センターセミナー

日時2015 年（平成 27 年）9 月 26 日

場所

京都大学福井謙一記念研究センター（1F 多目的室）

15:00 ～ 15:40

W.M.C.SAMEERA

15:00 − 17:20(FIFC)“Artificial force induced reaction method for mechanisms involving
Transition metal complexes and clusters”
15:40 ～ 16:20

Takuya SAITO(FIFC)“Driven Anomalous Diffusion in Polymer Stretching”
16:30 ～ 17:20

Masayuki OHZEKI (Kyoto Univ.)“Accelerated Langevin Dynamics and its application to machinelearning”

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）－ 43 －

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Ⅲ 研究広報活動 (2015)

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） 榊

茂好

リサーチリーダー

滋賀県立膳所高等学校（2） 諸熊奎治

2015 年（平成 27 年）5 月 9 日

FIFC リサーチフェロー 他

京都大学アカデミックディ

2015 年（平成 27 年）10 月 4 日（3） W.M.C. SAMEERA 他
私立市川高等学校（千葉県）

（4） 榊

茂好

リサーチリーダー

京都府立南陽高等学校

（5） 榊

茂好

一義

2015 年（平成 27 年）11 月 6 日

リサーチリーダー

私立星陵高等学校（静岡県）（6） 田中2015 年（平成 27 年）10 月 14 日

2015 年（平成 27 年）12 月 9 日

シニアリサーチフェロー

京都市成長産業創造センター

2015 年（平成 27 年）12 月 17 日

５．その他（報告）諸熊 奎治 FIFC リサーチフェローは、巨大分子の化学反応の計算方法を構築した功績により日本学士院会員に選出された（平成 27 年 12 月 14 日開催の第 1094 回総会）。
また、第 34 回京都府文化賞の特別功労賞を受賞。量子化学の第一人者として、電子計
算機を駆使した分子の構造と機能の予測、その反応設計の功績が認められた（平成 28 年
2 月 9 日）。

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Ⅳ 研究業績 (2015)

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)
Equilibrium phase diagram of a randomly pinned glass-former
Upon cooling, glass-forming liquids show a dramatic increase of their viscosities and relaxation times
before they eventually fall out of equilibrium at low temperatures. This laboratory glass transition is a purely
kinetic effect since it occurs at the temperature at which the relaxation time of the system crosses the timescale imposed by the experiment, e.g. via the cooling rate. Despite the intensive theoretical, numerical, andexperimental studies of the last five decades, the mechanism responsible for the slowing down and thus forthe (kinetic) glass transition is still under debate and hence a topic of intense research. From a fundamental
point of view the ultimate goal of these studies is to find an answer to the big question in the field: Does
there exist a finite temperature at which the dynamics truly freezes and, if it does, whether this ideal glasstransition is associated with a thermodynamic singularity or whether it is of kinetic origin.
Support for the existence of a kinetic transition comes from certain lattice gas models with a ``facilitateddynamics''.

In these models, the dynamics is due to the presence of ``defects'' and hence for such systems

the freezing is not related to any thermodynamic singularity.

However, the first evidence that there does

indeed exist a thermodynamic singularity goes already back to Kauzmann who found that the residual
entropy (the difference of the entropy of the liquid state from that of the crystalline state) vanishes at a finite
temperature TK if it is extrapolated to temperatures below the laboratory glass transition. Subsequently many
theoretical scenarios that invoke the presence of a thermodynamic transition have been proposed. One ofthese is the so-called ``random first order transition'' (RFOT) theory which, inspired by the exact solution ofa mean-field spin glass, predicts that at TK the glass-former does indeed undergo a thermodynamic transition
at which the residual, or configurational entropy Sc (the logarithm of the number of the states which areavailable to the system) vanishes and concomitantly breaks the replica symmetry. A further appealing featureof RFOT is that it seems to reconcile in a natural way the (free) energy-landscape scenario andmode-coupling theory (MCT), a highly successful theory that describes the relaxation dynamics atintermediate temperatures.
Despite all these advances, the arguments put forward in the various papers must be considered as
phenomenological since compelling and undisputed experimental or numerical evidence to prove or disprove
any of these theories and scenarios is still lacking. The only exception are hard spheres in infinite dimensions,for which mean-field theory should become exact, but even in this case some unexpected problems arepresent. This lack of understanding is mainly due to the steep increase of the relaxation times whichhampeirs the access to the transition point of thermally equilibrated systems and hence most of the efforts to
identifying the transition point, if it exists, resort on unreliable extrapolation.
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Ⅳ 研究業績 (2015)

In the present work, we use computer simulation todetermine for a canonical glass-former with pinned
particles the ideal glass transition temperature TK as apoint at which Sc vanishes. For the first time this is done
without invoking any kind of extrapolation. Fig. 1(a)shows the entropy per (unpinned) particle as a functionofthefractionofpinnedparticlesatseveraltemperatures T and we recognize that with increasing c
the entropy decreases rapidly. For all temperatures thisdecrease is linear at small c but then the curves bend atintermediate c and follow a weaker c-dependence. For T< 0.5 this bent becomes sharp, strongly indicating that athermodynamic glass transition takes place. This
becomes more evident by evaluating the configurational
entropy obtained by subtracting from S the vibrational
entropy Svib. In order to estimate Svib, we havedetermined the inherent structures and calculated theeigenfrequencies. Using the harmonic approximation,
one can calculate Svib which is shown in Fig.1(a) as well(solid lines) and we see that it shows basically a linear
decrease with c, a trend which is due to the suppressionof the low frequency modes in the density of states. We
can now estimate the configurational entropy Sc as thedifference Sc = S - Svib and in Fig.1(b) we show thec-dependence of Sc for various temperatures. This figure
shows that, for T < 0.5, Sc quickly decreases withincreasing c and becomes basically zero at a finite valueof c, indicating that the system has entered the ideal
glass state in which the entropy is basically due toFig. 1 (a): Entropy of the system, s, as
evaluated

from

the

thermodynamic

integration, as a function of c (symbols).
The entropies of the disordered solid statesSvib,

obtained

using

the

harmonic

approximation, are drawn as solid lines.
Thedashed

lines

are

a

linearextrapolation from the low c sides. (b): The
configurational entropy Sc = S - Svib. The
error bars have been estimated from thesample to sample fluctuations..

harmonic vibrations. For T > 0.55, the approach of Sc tozero is milder and the bent is less sharp, indicating that the transition becomes a crossover.

Thermal fluctuations, mechanical response, and hyperuniformity in jammed solids
Jamming is a geometric phase transition occurring in dense particle systems in the absence oftemperature. We use computer simulations to analyze the effect of thermal fluctuations on several signaturesof the transition. We show that scaling laws for bulk and shear moduli only become relevant when thermal
fluctuations are extremely small, and propose their relative ratio as a quantitative signature of jamming
criticality. Despite the nonequilibrium nature of the transition, we find that thermally induced fluctuations－ 46 －

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Ⅳ 研究業績 (2015)

andmechanical responses obey equilibrium fluctuation-dissipation relations near jamming, provided theappropriate fluctuating component of the particle displacements is analyzed. This shows that mechanicalmoduli can be directly measured from particle positions in mechanically unperturbed packings, and suggeststhat the definition of a “nonequilibrium index” is unnecessary for amorphous materials.We find thatfluctuations of particle displacements are spatially correlated, and define a transverse and a longitudinalcorrelation length scale which both diverge as the jamming transition is approached. We analyze the frozen
component of density fluctuations and find that it displays signatures of nearly hyperuniform behavior atlarge length scales. This demonstrates that hyperuniformity in jammed packings is unrelated to a vanishingcompressibility and explains why it appears remarkably robust against temperature and density variations.
Differently from jamming criticality, obstacles preventing the observation of hyperuniformity in colloidal
systems do not originate from thermal fluctuations.

One-dimensional Kac model of dense amorphous hard spheres
We considered an one-dimensional chain of the d-dimensional boxes each of which contains N hard
spheres as a model system of liquids under confinement. By focusing on the large dimensional limit, weanalytically computed the phase diagram of the model.

From the chain length dependence of the transition

densities, we derived the critical behavior of the two relevant length scales of the glass transition.
We summarize the results in Fig 2. The upper panel is the phase diagram of the glass transition of theconfined liquid, where phi is the normalized density and L is the distance between the boundaries. There are
the two relevant length scales ξd and ξK, which diverge as ξd ~ (φd - φ)-1/4 and ξK ~ (φK - φ)-1, respectively.
When L > ξd, the system holds the ergodicity and is in the liquid phase. For ξK < L < ξd, the phase space splits
into the many sub-spaces and the ergodicity of the system is broken at least in the large dimensional limit.
In L < ξK region, the number of the sub-spaces becomes
sub-exponential and no longer contributes to the entropy.
Thus the equilibrium phase transition from the liquid
phase to the ideal glass phase occurs. These results are
consistent with the results for the p-spin mean-field spinglass model, where the critical behaviors ξd ~ (T - Td)-1/4
and ξK ~ (T - TK)-1 are observed. This confirms that the
proposed model is considered to be a hard sphere
extension of the p-spin mean-field spin glass model
under confinement. The result for ξd is also consistent
with

the

prediction

of

the

inhomogeneousmode-coupling theory for the dynamic correlation
length diverging at the mode-coupling transition point.
The lower panel of Fig. 2 is the phase diagram of thejamming transition. There are the two relevant lengthscales ξth and ξGCP which diverge as ξth ~ (φth - φ)-1/4 andFig. 2 Schematic phase diagram of ourmodel.

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Ⅳ 研究業績 (2015)

ξGCP ~ (φGCP - φ)-1, respectively. When L >ξth, there are no jammed states. For ξGCP < L < ξth, there exist
exponentially many jammed states. The number of the jammed states decreases with L, and becomes
sub-exponential when L < ξGCP.

The decoupling of the glass transitions in the two-component p-spin spherical model
Binary mixtures of large and small particles with disparate size ratio exhibit a rich phenomenology attheir glass transition points. In order to gain insights on such systems, we introduce and study a
two-component version of the p-spin spherical spin glass model. The model is composed of stronglyinteracting spins (strong spins) and weakly interacting spins (weak spins), which mimic the glass forming
binary mixtures of large and small particles with disparate size ratio.
We have found that when the strengths of the interactions of the weak and strong spins are not widely
separated, the model has only one glass phase. This glass phase is the frozen state of both the strong andweak spins and is described by the conventional 1RSB solution. On the other hand when the strengths of
the interactions are well separated, the model exhibits the decoupling of the glass transitions of the weak andstrong spins and, as a result, there appear the three distinct glass phases. We referred to them as the 1RSB(1),the 1RSB(2), and the 2RSB glass phases. The 1RSB(1) glass phase appears in the region where the number
fraction of the strong spins is very small. This glass phase is the frozen state of both the strong and weak
spins, although the transition into this phase is driven mainly by the freezing of the weak spins. The 1RSB(2)glass phase appears in the region where the number fraction of the strong spins is large. In this glass phase,
only the strong spins are frozen while the weak spins are left mobile. By cooling the 1RSB(2) glass further,the 2RSB glass phase is obtained, in which the weak spins are also frozen. The 2RSB glass phase ischaracterized by the two-step hierarchical structure of the free energy landscape. The 2RSB glass transition
becomes ether discontinuous or continuous depending on the number fraction of the strong spins. The
discontinuous 2RSB thermodynamic transition is accompanied with the jump of the second order derivativeof the free energy, namely the heat capacity. On the other hand, for the continuous 2RSB thermodynamic

Fig. 4 The phase diagram of the two-component p-spin spherical model.
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Ⅳ 研究業績 (2015)transition, the heat capacity changes continuously while the third order derivative of the free energy jumps
discontinuously. Based on the results, we have discussed the connection of the present model to therandomly pinned PSM. The phase diagram of the present model appears to be similar to that of the randomly
pinned PSM. We have analytically showed that the free energy of the two-component PSM becomes exactly
identical to that of the randomly pinned PSM in the small limit of the ratio between the strengths of theinteractions of the weak and strong spins. We have also discussed the implications of the present results for
the MCT for binary mixtures of large and small particles with disparate size ratio. We have found that the
1RSB solution can not correctly describe the 2RSB glass phase although it can capture a trace of the 2RSBtransitions for a certain range of parameters, which may leave questionable the applicability of the MCT todescribe the decoupling of the glass transitions in binary mixtures with disparate size ratio. for the glasstransitions of binary mixtures.

2. Original papers(1) “Equilibrium phase diagram of a randomly pinned glass-former”
Misaki Ozawa, Walter Kob, Atsushi Ikeda, Kunimasa Miyazaki
Proc. Natl. Acad. Sci. USA 112, 6914 (2015).
(2) “Reply to Chakrabarty et al.: Particles move even in ideal glasses”
Misaki Ozawa, Walter Kob, Atsushi Ikeda, Kunimasa Miyazaki
Proc. Natl. Acad. Sci. USA 112, E4821 (2015).
(3) “Thermal fluctuations, mechanical response, and hyperuniformity in jammed solids”
Atsushi Ikeda, Ludovic BerthierPhys. Rev. E 92, 012309 (2015).
(4)“One-dimensional Kac model of dense amorphous hard spheres”
Harukuni Ikeda, Atsushi Ikeda
EPL 111, 40007 (2015).

3. Presentation at academic conferences(1) Atsushi Ikeda
Replica theory analysis of the glass transitions of complicated systems: Network-formers
and ellipsoids
International Workshop on Dynamics in Viscous Liquids, 2015/5/4-5/7, Montpellier, France(2) 池田 昌司「少し複雑な系のガラス転移：レプリカ理論によるアプローチ」
東大物性研短期研究会「ガラス転移と周辺分野の科学」, 2015 年 7 月 30 日-8 月 1
日, 柏 （招待講演）－ 49 －

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Ⅳ 研究業績 (2015)(3) Atsushi Ikeda
Thermal fluctuations, mechanical response, and hyperuniformity in jammed solids
Japan-France Joint Seminar "New Frontiers in Non-equilibrium Physics of Glassy
Materials", 2015/8/11-14, Kyoto (Invited talk)(4) 池田 昌司「ガラス転移の統計力学：理想ガラスは存在するか？」
日本セラミックス協会 第 29 回秋季シンポジウム, 2015 年 9 月 16 日-9 月 18 日, 富山（招待講演）(5) Atsushi Ikeda
Thermodynamic glass transition of a randomly pinned glass-former
Third East Asia Joint Seminar on Statistical Physics, 2015/10/14-17, Seul, Korea (Invitedtalk)(6) 池田 昌司「過冷却液体のエネルギーランドスケープについて」
第３８回溶液化学シンポジウム・プレシンポジウム, 2015 年 10 月 20 日, 高知 （招待講演）
4. Others(1) 池田 昌司「ガラス転移のエネルギー曲面」
研究会「化学反応のポテンシャル曲面とダイナミックス」, 2016 年 3 月 28 日, 京都(invited)－ 50 －

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Ⅳ 研究業績 (2015)

Hideyuki Mizuno

Hideyuki Mizuno

Assistant Professor
Graduate School of Arts and Sciences, The University of Tokyo, Tokyo 153-8902 Japan

Assistant Professor

1. Summary of the research of the year (2015)
Elastic Moduli and Vibrational Modes Close to the Jamming Transition- From Disordered to Ordered Jammed Particulate Systems Abstract
Recent studies have well established peculiar mechanical and vibrational properties of jammed
particulate solids close to the jamming transition point. The elastic moduli follow power-law scalings withthe packing pressure, and the vibrational density of states (vDOS) exhibits a plateau regime above thecharacteristic frequency ω*. Those features can be explained by “isostaticity” coming from the marginal
stability close to the jamming transition, where the contact number is a central parameter to describe thematerial properties [1]. Previous works have paid attention mainly on “disordered” jammed systems,
where the constituent particles are packed in a random, disordered structure. In the present work, we
focus on more “ordered” jammed systems with ordered structures. We demonstrate that close to thejamming transition point, even the ordered systems exhibit the similar mechanical and vibrational
properties as those of disordered systems. Our results suggest that physics of isostaticity is valid for
disordered to ordered systems close to the jamming transition and can determine the material propertiesof marginally stable solids, regardless of their static structures.

From disordered to ordered jammed particulate systems
We have studied the jammed particulate systems. The constituent particles interact via a finite-range,
purely repulsive, harmonic potential,
which has been often employed inmany

previous

numerical

works.

Following the procedure proposed inRef. [2], we have prepared the jammed
particulate

systems

withseveraldifferent

structures,

which

are

distinguished by the value of theorientational order parameter, Q6 = 0.0,
Fig. 1: Static structure of the system for different Q6 values.
We plot the radial distribution function g(r) in (a) and the static
structure factor S(q) in (b).

0.1, 0.2, 0.3, 0.4, and 0.5.
Figure

1

shows

the

radialdistribution function g(r) and the static－ 51 －

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Ⅳ 研究業績 (2015)

structure factor S(q) for different Q6 values. In the case of Q6 = 0.0, we see the highly disorderedstructure which has been intensively studied by many previous works. On the other side, as Q6
increases towards 0.5, the system becomes more ordered state. For Q6 = 0.5, we can observe thecrystalline-like, ordered, lattice structure. In addition, S(q) shows the clear enhancement of thelong-range spatial correlation at small wavenumbers q. A main goal of the present study is to unveil themechanical and vibrational properties for those more ordered systems close to the jamming transition
point.

Power-law scalings with packing pressure, in elastic moduli, contact number, frequency ω*
Figure 2 plots the elastic moduli (bulk K and shear G moduli), excess contact number Δz = z - zc (zc = 2d
is the critical value, d =3 is the spatial dimension), and the characteristic frequency ω*, as functions of
the packing pressure p. We have well established the following power-law scalings in those quantities,
which are all independent of the static structural properties, i.e., the values of Q6:(1)
Remarkably the excess contact number Δz follows the same power-law scaling with p, independently of
Q6 values, suggesting that the physics of isostaticity can work for not only disordered systems but alsoordered ones. Indeed, in the following,
we will show the mechanical andvibrational properties are controlled by
the isostaticity, regardless of static
structures,

even

in

the

orderedsystems.
For the elastic moduli K and G, weobserve that (i) their dependences on p
are controlled by the excess contact
number Δz only, independently of Q6
values, whereas (ii) the critical valuesof Kc and Gc depend on the static
structure, the Q6 value. Particularly thezero shear modulus value of Gc = 0 is a
special feature to the “disordered”
packings, as has been discussed atsome length in Ref. [3]. On the otherFig. 2: Dependences on the packing pressure p of theside, the more ordered packing shows

quantities for different Q6 values: The (a) bulk modulus K, (b)the larger, positive, finite value of Gc.

shear modulus G, (c) excess contact number Δz = z – zc, andthe (d) characteristic frequency ω*.

The characteristic frequency ω*,
above which the vDOS shows the－ 52 －

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peculiar plateau regime, is also controlled by Δz, independently of the Q6 values. This result suggeststhat “anomalous” vibrational modes in the plateau regime are also determined by the isostaticity, for both
the disordered and ordered systems, which will be discussed next.

Vibrational modes in disordered to ordered jammed systems
We have analyzed the vibrational eigenmodes of jammed systems, in the same way as has been done
in Ref. [3]. We have calculated the vDOS g(ω), and the vibrational amplitudes (compressional/stretchingek‖, sliding ek⊥, and net ek‖net) and the mode energies (compressional/stretching δEk‖ and sliding δEk⊥) of
all the vibrational modes k. Figure 3 shows those quantities as functions of the eigenfrequency ω fordifferent Q6 values of Q6 = 0.0 to 0.5. We have already reported the results of the disordered case, Q6 =0.0, in Ref. [3]. The vDOS shows a crossover from the Debye-like scaling to the plateau behavior at thecharacteristic frequency ω*. The crossover at ω* is characterized by the competition between thecompressional/stretching δEk‖ and sliding δEk⊥ vibrational energies: δEk‖ dominates the total vibrational

Fig. 3: Vibrational eigenmodes of the system for different Q6 values. The vDOS g(ω) in (a),(e),(i),(m),the vibrational amplitudes ek‖(solid lines), ek⊥(dashed lines) in (b),(f),(j),(n), the net amplitude ek‖net in(c),(g),(k),(o), and the mode energies δEk‖(solid lines), δEk⊥(dashed lines) in (d),(h),(l),(p) are plotted
as functions of the eigenfrequency ω. The different lines indicate different packing pressures, p =4*10-3 (red), 4*10−4 (green), 4*10−5 (blue), 4*10−6 (orange), 4*10−7 (black), from right to left or from top
to bottom.

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energy above ω*, whereas δEk⊥ is comparable to δEk‖ and play a role in the total energy below ω*. Here
we make an important note that “anomalous” modes in the plateau regime can be featured by thedominant compressional/stretching energy, where the constraint in the sliding direction is negligible andthe vibrational motions show very large sliding component of ek⊥, as well observed in Fig. 3.
Remarkably those vibrational features observed in the disordered packing, Q6 = 0.0, persist to themore ordered cases up to Q6 = 0.5. We naturally expect that the vibrational modes in the Debye-likeregime at ω < ω* and the spring-dynamics regime at ω > ωh (=1) should be different between different
structures. However, here we demonstrate that the vibrational natures in the plateau regime above ω*and below ωh are independent of the static structural properties, controlled by the excess contact
number only, i.e., the isostaticity. We have also performed the eigenmode decomposition of nonaffineelastic moduli, in the same way as was done in Ref. [3] for disordered packings, and confirmed that the
eigenmode decomposition in the plateau regime is also insensitive to the static structural properties.

Conclusion
In the present work, we have studied elastic moduli and vibrational modes in marginally stable jammed
packings with several different static structures. We have showed that the peculiar features observed in
the disordered packings also persist to even more ordered particulate systems. Particularly the same
power-law scalings with packing pressure, in elastic moduli, contact number, characteristic frequency ω*,hold for the disordered to ordered systems. In addition, anomalous vibrational natures in the plateau
regime are controlled by the isostaticity, regardless of static structural properties. Our results suggest theuniversal aspect of physics of isostaticity which can explain the material properties of marginal stable
solids close to the jamming transition point, independently of their static structures.

Acknowledgement
This work is a collaboration during 2015 with Kuniyasu Saitoh (Tohoku University) and Leonardo E.
Silbert (Southern Illinois University Carbondale). A manuscript to present the results is now in
preparation.

References[1] M. Wyart, S. R. Nagel, and T. A. Witten, Europhysics Letters 72, 486 (2005).
[2] C. F. Schreck, C. S. O’Hern, and L. E. Silbert, Physical Review E 84, 011305 (2011).
[3] H. Mizuno, K. Saitoh, and L. E. Silbert, Physical Review E 93, 062905 (2016).

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2. Original papers(1) A. Nicolas, F. Puosi, H. Mizuno, and J.-L. Barrat, “Elastic consequences of a single plastic
event: Towards a realistic account of structural disorder and shear wave propagation inmodels of flowing amorphous solids”,
Journal of the Mechanics and Physics of Solids, Vol.78, p.333-351 (19pages), 2015.
(2) H. Mizuno, S. Mossa, and J.-L. Barrat, “Beating the amorphous limit in thermal conductivity
by superlattices design”,
Scientific Reports, Vol.5, p.14116 (15pages), 2015.

3. Presentation at academic conferences(1) L. E. Silbert, H. Mizuno, and M. Sperl, “Shear modulus heterogeneities in disordered
frictionless particle packings”,
American Physical Society March Meeting 2015, San Antonio, TX, USA, 2015/03/02-06.
(2) A. Nicolas, J. Rottler, F. Puosi, H. Mizuno, and J.-L. Barrat, “Local rearrangements in theflow of disordered solids: long-range elastic interactions and spatio-temporal correlations,from atomistic simulations to coarse-grained models”,
The 10th Annual European Rheology Conference, Nantes, France, 2015/04/14-17.
(3) H. Mizuno, L. E. Silbert, and M. Sperl, “Elastic moduli heterogeneities in disordered
frictionless particle packings”,
The 9th European Solid Mechanics Conference, Madrid, Spain, 2015/07/06-10.

4. Others(1) H. Mizuno, S. Mossa, and J.-L. Barrat, “Acoustic excitations and elastic heterogeneities indisordered solids”,
The highlight in the annual report 2014 of the Institut Laue-Langevin (ILL), p72-73, 2015.
(2) H. Mizuno, S. Mossa, and J.-L. Barrat, “Crystalline super-networks for super thermal
insulation”,
Minatec. Newsletter (Monthly journal of MinaTec, the Grenoble hub for nanotechnology),
Vol.37, p.1, December 2015.

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２．FIFC リサーチフェロー

Shigeru Nagase
FIFC Research
Fellow
Research
Fellow of
FIFC
1. Summary of the Research of the YearThe bonding between heavier main group atoms in sterically crowded molecules are investigated.
In addition, the interesting properties of endohedral metallofullerenes are investigated.

(a) The Multiple Bonding in Heavier Group 14 Analogues (R2E=ER2, E = Ge, Sn, Pb) of
Alkenes, Which is Stabilized by Dispersion Force Effects
Since the first successful synthesis of a double bond between Sn atoms (Figure 1), heavier
analogues of alkenes have attracted special interest in main group chemistry. The structures andbonding in [(SiMe3)2CH]2E=E[CH(SiMe3)2]2and [(SiMe3)2NH]2E=E[NH(SiMe3)2]2 (E = Ge,
Sn,

or

Pb)

and

their

dissociation

into :E[CH(SiMe3)2]2 and :E[NH(SiMe3)2]2
monomers were theoretically studied using
hybrid density functional theory (DFT) at theB3PW91 level with basis set superposition
error and zero point energy corrections. The
structures were also optimized with thedispersion-corrected B3PW91-D3 method toyield dispersion force effects. The calculations
generally

reproduced

theexperimental

structural data for the tetraalkyls with a few
angularexceptions.

Without

dispersion

corrections,thedissociationenergiesof[(SiMe3)2CH]2E=E[CH(SiMe3)2]2 were calculated to be -2.3 (Ge), +2.1 (Sn), and -0.6 (Pb) kcal/mol,which indicate that the dimeric E-E bonded structure is favored only for tin. However, whendispersion force effects are included, much higher dissociation energies of 28.7 (Ge), 26.3 (Sn), and15.2 (Pb) kcal/mol were calculated, indicating that all three E-E bonded dimers are favored.
Calculated thermodynamic data at 25 °C and 1 atm for the dissociation of the alkyls yield ΔG valuesof 9.4 (Ge), 7.1 (Sn), and -1.7 (Pb) kcal/mol, indicating that the dimers of Ge and Sn, but not Pb, arefavored. These results are in harmony with experimental data. The dissociation energies of[(SiMe3)2NH]2E=E[NH(SiMe3)2]2 without dispersion correction are -7.0 (Ge), -7.4 (Sn), and -4.8
(Pb) kcal/mol, showing that the monomers are favored in all cases. Inclusion of the dispersion
correction yields the values 3.6 (Ge), 11.7 (Sn), and 11.8 (Pb) kcal/mol, showing that dimerization isfavored but less strongly so than in the alkyls. The calculated thermodynamic data for the amido
germanium, tin, and lead dissociation yield ΔG values of -12.2, -3.7, and -3.6 kcal/mol at 25 °C and 1
atm, consistent with the observation of monomeric structures.
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Overall, these data indicate that, in these sterically crowded molecules, dispersion force
attraction between the ligands is of greater importance than group 14 element-element bonding, andis mainly responsible for the dimerization of themetallanediyls

species

Calculations

on

to

the

t

give

the

non-dissociating

dimetallenes.
distannenet( Bu2MeSi)2Sn=Sn(SiMe Bu2)2 also show that attractive
dispersion forces are key to its stability, though thebonding between the central Sn atoms has beenemphasized (Figure 2).

(b) Dispersion Force Effects on the Dissociation of “Jack-in-the-Box” Diphosphanes(R2P-PR2) and Diarsanes (R2As-AsR2)
The dissociation of sterically-crowded diphosphanes (R2P-PR2) and diarsanes (R2As-AsR2 ) (R
= [CH(SiMe3)2]2 and [NH(SiMe3)2]2) into PR2 and AsR2 radical monomers was theoreticallystudied using hybrid density functional theory at the B3PW91 and dispersion-corrected B3PW91-D3
levels. The calculations reproduced the experimental structural data for the teraalkyls with good
accuracy. Without the dispersion correction, negative dissociation energies of -10.3 and -6.5 kcal/mol
were calculated for the phosphorus and arsenic tetraalkyls, indicating that the radical monomers are
more stable. In contrast, the incorporation of dispersion force effects afforded high, positive
dissociation energies of +37.6 and +37.1 kcal/mol that favored dimeric structures. The dissociationenergies (without dispersion) calculated for the tetraamido-substituted dimer are also negative, butchanged to positive values of +29.3 and +32.5 kcal/mol upon optimization with the D3 dispersion
term. In contrast to earlier calculations, which indicated that the release of accumulated strain energy
within the tetraalkyl dimers was the driving force for dissociation to monomers (i.e. theJack-in-the-box molecular model), the present calculations show that dispersion force attractive
interactions exceed those of ligand relaxation and stabilize the dimeric structures. Single-point MP2(Second-order Møller-Plesset Perturbation Theory) calculations including dispersion effects afforded
dissociation energies of 30.4 and 30.8 kcal/mol for the tetraalkyl species, suggesting that the additionof the D3 dispersion term to the B3PW91 functional may overestimate such forces by 7-8 kcal/mol.
It is concluded that the balance of dispersion forces and entropic effects are the major determinants ofthe dissociation equilibria.
(c) (2 + 2) Cycloaddition of Benzyne to Endohedral Metakkofullerenes M3N@C80 (M =Sc, Y): A Rotating-Intermediate Mechanism
The reaction mechanism and origin of regioselectivity of (2 + 2) cycloadditions of benzyne toendohedral metallofullerenes M3N@C80 (M = Sc, Y) were investigated with density functional
calculations. The reaction was demonstrated to follow a diradical mechanism rather than a carbene
mechanism, in which the formation of the diradical intermediate is the rate-determining step.
Through rotation of benzyne moiety on the fullerene surface, the diradical intermediate on 566 site
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could isomerize to two new diradical intermediates which give rise to two distinct [5,6] and [6,6]benzoadducts, respectively. However, the diradical intermediate on 666 site only produces the [6,6]benzoadduct. The nature of the endohedral cluster not only influences the regioselectivity, but also
determines the cycloadduct geometry. For Sc3N@C80, the [5,6] benzoadduct is preferred kineticallyand thermodynamically, whereas in the case of Y3N@C80, both [5,6] and [6,6] benzoadducts arefavorable. In contrast to closed-cage benzoadducts of Sc3N@C80, Y3N@C80 affords open-cage
benzoadducts, making it the first example that the endohedral cluster could alter cycloadducts fromthe closed cage to open cage. With further analysis, it is revealed that the origin of regioselectivity
results from the local strain energy of the fullerene cage.

(d) Warning to Theoretical Structure Elucidation of Endohedral Metallofullerenes
Endohedral scandium fullerenes have attracted substantial interest since they were synthesized
and isolated in 1992. The Sc2C74 series including both Sc2@C74 and Sc2C2@C72 forms were
thoroughly investigated with density functional theory (DFT) methods including B3LYP,
CAM-B3LYP, M06-2X, wB97XD, and some other DFT methods combined with statisticalmechanics in the present work. Among all the Sc2C74 isomers, Sc2C2@Cs(10528)-C72 is the mostthermodynamically stable, and it is overwhelming at the temperature region of fullerene formation,
which is very consistent with experiments. A deviation that the B3LYP method as well as other DFT
methods without long-range corrections tends to overestimate energies of Sc2C2@C72 series was
exposed for the first time to our best knowledge, and this deviation may not only be restricted to the
Sc2C2@C72 series but also apply to other scandium carbide fullerenes Sc2C2@C2n (2n ≠72) and evenother metal carbide fullerenes. Misleading conclusions will be drawn on the basis of inaccurateenergies calculated with B3LYP method and other DFT methods without long-range corrections. As
B3LYP, BP86, PBE, etc. are fairly widely used methods in theoretical studies of endohedral
metallofullerenes, our work is an instructive warning to these studies.

(e) Other Research Subjects(1) "Synthesis and Characterization of a 1,2-Digermabenzene", (2) "Ring Expansion to
1-Bromo-1-alumacyclonona-2,4,6,8-tetraene by Insertion of Two Alkyne Molecules into the Al-C
Bonds", (3) "Theoretical Insight into the Ambiguous Endohedral Metallofullerene Er3C74: CovalentInteractions among Three Lanthanide Atoms", (4) "Reaction of a Diaryldigermyne with Ethylene",(5) "Quasi-Three-Coordinate Iron and Cobalt Terphenoxide Complexes {AriPr8OM(-O)}2 (AriPr8 =C6H-2,6-(C6H2-2,4,6-iPr3)2-3,5-iPr2; M = Fe or Co) with M(III)2(-O)2 Core Structures and thePeroxide Dimer of 2-Oxepinoxyl Relevant to Benzene Oxidation","Synthesis, (6) Synthesis,
Structure, and Reactivities of Iminosulfane- and Phosphane-Stabilized Carbones Exhibiting
Four-Electron Donor Ability", (7) "Preparation, Structural Determination, and Characterization ofElectronic Properties of Bis-Silylated and Bis-Germylated Lu3N@Ih-C80", (8) "Diverse Coordination
Modes in Tin Analogues of a Cyclopentadienyl Anion Depending on the Substituents on the Tin
Atom", (9) "Effective Derivatization and Extraction of Insoluble Missing Lanthanum－ 58 －

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Metallofullerenes La@C2n (n = 36-38) with Iodobenzene ", (10) "Calculations of the Water-Dimer
Encapsulated into C84", (11) "Selenium-Substituted Phosphaalkenes Obtained through 1,
2-Elimination of Chlorosilanes from Selenenylchlorophines" (12) "Computational Picture of Silyl
Transfer from Silylsilatranes to Arylpalladium Chloride", and (13) "Crystal Structure of
4-methybenzenecarbothioic Acid and Computational Investigations of Benzenecarbochlcogenoic
Acids (C6H5COEH and C6H5CEOH, E = S, Se, Te)".

2. Original papers(1) J. –D. Guo, S. Nagase, and P. P. Power, "Dispersion Force Effects on the Dissociation of“Jack-in-the–Box” Diphosphanes and Diarsanes", Organometallics, 34, 2028-2033 (2015).
(2) T. Yang, S. Nagase, T. Akasaka, J. M. Poblet, K. N. Houk, M. Ehara, and X. Zhao,"(2+2)
Cycloaddition of Benzyne to Endohedral Metallofullerenes M3N@C80 (M = Sc, Y): A
Rotating-Intermediate Mechanism", J. Am. Chem. Soc., 137, 6820-6828 (2015).
(3) T. Sasamori, T. Sugahara, T. Agou, J. –D. Guo, S. Nagase, R. Streubel, and N. Tokitoh,"Synthesis and Characterization of a 1,2-Digermabenzene", Organometallics, 34, 2106-2109(2015).
(4) T. Agou, T. Wasano, T. Sasamori, J. –D. Guo, S. Nagase, and N. Tokitoh, "Ring Expansion to
1-Bromo-1-alumacyclonona-2,4,6,8-tetraene by Insertion of Two Alkyne Molecules into the
Al-C Bonds", Angew. Chem. Int. Ed., 54, 9568-9571 (2015).
(5) Y. –J. Guo, H. Zheng, T. Yang, S. Nagase, and X. Zhao, "Theoretical Insight into the
Ambiguous Endohedral Metallofullerene Er3C74: Covalent Interactions among Three Lanthanide
Atoms", Inorg. Chem., 54, 8066-8076 (2015).
(6) T. Sasamori, T. Sugahara, T. Agou, K. Sugamata, J. –D. Guo, S. Nagase, and N.
Tokitoh,"Reaction of a Diaryldigermyne with Ethylene", Chem. Sci., 6, 5526-5530 (2015).
(7) P. Zhao, H. Lei, C. Ni, J. –D. Guo, S. Kamali, J. C. Fettinger, F. Grandjean, G. J. Long, S.
Nagase, and P. P. Power, "Quasi-Three-Coordinate Iron and Cobalt Terphenoxide Complexes{AriPr8OM(-O)}2 (AriPr8 = C6H-2,6-(C6H2-2,4,6-iPr3)2-3,5-iPr2; M = Fe or Co) with
M(III)2(-O)2 Core Structures and the Peroxide Dimer of 2-Oxepinoxyl Relevant to Benzene
Oxidation", Inorg. Chem., 54, 8914-8922 (2015).
(8) T. Morosaki, W. –W. Wang, S. Nagase, and T. Fujii, "Synthesis, Structure, and Reactivities of
Iminosulfane- and Phosphane-Stabilized Carbones Exhibiting Four-Electron Donor Ability",
Chem. Eur. J., 21, 15405-15411 (2015).
(9) J. –D. Guo, D. J. Liptrot, S. Nagase, and P. P. Power, "The Multiple Bonding in Heavier Group
14 Element Alkene Analogues is Stabilized Mainly by Dispersion Force Effects", Chem. Sci., 6,6235-6244 (2015).
(10) M. Kako, K. Miyabe, K. Sato, M. Suzuki, N. Mizorogi, W. –W. Wang, M. Yamada, Y. Maeda,
M. M. Olmstead, A. L. Balch, S. Nagase, and T. Akasaka, "Preparation, Structural
Determination,

andCharacterization

ofElectronic

Properties

ofBis-Silylated

andBis-Germylated Lu3N@Ih-C80", Chem. Eur. J., 21, 16411-16420 (2015).
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Ⅳ 研究業績 (2015)(11) T. Kuwabara, M. Nakada, J.-D. Guo, S. Nagase, and M. Saito, "Diverse Coordination Modes in
Tin Analogues of a Cyclopentadienyl Anion Depending on the Substituents on the Tin Atom",Dalton Trans., 44, 16266-16271 (2015).
(12) Y. Maeda, T. Tsuchiya, T. Kikuchi, H. Nikawa, T. Yang, X. Zhao, Z. Slanina, M. Suzuki, M.
Yamada, Y. Lian, S. Nagase, X. Lu, and T. Akasaka, "Effective Derivatization and Extraction of
Insoluble Missing Lanthanum Metallofullerenes La@C2n (n = 36-38) with Iodobenzene",
Carbon, 98, 67-73 (2016).
(13) Z. Slanina, F. Uhlík, X. Lu, T. Akasaka, K. H. Lemke, T. M. Seward, S. Nagase, and L.
Adamowicz, "Calculations of the Water-Dimer Encapsulated into C84", Fullerenes, Nanotubes,
Carbon Nanostruct., 24, 1-7 (2016).
(14) R. Zhao, Y. Guo, P. Zhao, M. Ehara, S. Nagase, and X. Zhao, "Warning to Theoretical Structure
Elucidation of Endohedral Metallofullerenes", J. Phys. Chem. C, 120, 1275-1283 (2016).
(15) T. Sasamori, J. M. V. Franco, J. –D. Guo, K. Sugamata, S. Nagase, R. Streubel, and N.
Tokitoh,"Selenium-Substituted

Phosphaalkenes

Obtainedthrough

1,

2-EliminationofChlorosilanes from Selenenylchlorophines", Eur. J. Inorg. Chem., 678-684 (2016).
(16) J. –D. Guo, T. Sasamori, Y. Yamamoto, H. Matsubara, S. Nagase, and H. Yorimitsu,"Computational Picture of Silyl Transfer from Silylsilatranes to Arylpalladium Chloride ", Bull.
Chem. Soc. Jpn., 89, 192-194 (2016).
(17) S. Kato, O. Niyomura, K. Tani, M. Ebihara, J. –D. Guo, and S. Nagase, "Crystal Structure of
4-methybenzenecarbothioic

Acid

and

Computational

InvestigationsofBenzenecarbochlcogenoic Acids (C6H5COEH and C6H5CEOH, E = S, Se, Te)", Bull. Chem. Soc.
Jpn., 89, 361-368 (2016).

3. Review articles(1) 山田道夫、赤阪健、永瀬茂、「不飽和直線状トリキナン構造をもつ金属内包フラーレンSc2@C66」、固体物理、50, 189-194 (2015).
(2) 鈴木光明、前田

優、永瀬

茂、赤阪

健、「金属内包フラーレンの構造決定」、日本結晶学会誌、58, 73-78 (2016).

4. Books(1) M. Yamada, S. Sato, Y. Takano, L. Feng, S. Nagase, and T. Akasaka, Endohedral
Metallofullerenes: From Chemical Reactivity to Material Performance", In Chemical Science of

π-Electron Systems (Eds. T. Akasaka, A. Osuka, S. Fukuzumi, H. Kandori, and Y. Aso),
Springer, Chapter 9, pp. 133-153 (2015).
(2) X. Lu, L. Bao, T. Akasaka, and S. Nagase, "Endohedral Metallofullerenes", In Encyclopedia of
Polymeric Nanomaterials (Eds. S. Kobayashi and Muellen), Springer-Verlag, Berlin Heidelberg,
pp. 730-741 (2015).

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３．リサーチリーダー

Shigeyoshi Sakaki
Shigeyoshi Sakaki

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

1. Summary of the research of 2015
The complex systems consisting of transition metal element(s), heavy main-group element(s), organicgroup(s) are attractive research targets in wide areas of modern chemistry. For instance, such complex
systems play important roles as metal enzymes, catalysts, photo-sensitizer, molecular switch, luminescencematerial and so on. Also, they are important research target in the physical chemistry and molecular science,
because they exhibit a variety of geometry, molecular property, bonding nature, reactivity, and catalysis.
These features attract a lot of interests in theoretical and computational chemistry. All these features deeply
relate to their electronic structures. In this regard, the theoretical and computational studies of the electronic
structures of the complex systems are indispensable in further development of chemistry.
These complex systems are challenging research targets from the point of view oftheoretical/computational chemistry, because their electronic structures are not simple but complicated inmany cases. One good example is to incorporate large electron correlation effects in theoretical calculation ofsuch system, which is still not easy even nowadays.
Our group is theoretically investigating the complex systems bearing complicated electronic structurewith electronic structure theory. In 2015, we performed several theoretical studies, as follows: (i) CASPT2
study of inverse sandwich-type dinuclear 3d transition metal complexes of ethylene and dinitrogen molecules,(ii) Theoretical Study of Pd11Si6 Nanosheet Compounds Including Seven-Coordinated Si Species
and Its Ge Analogues, (iii) Au8 Cores and Entangled Ligands of Selenolate- and Thiolate-Protected Gold
Nanoclusters Au24(ER)20 and Au20(ER)16 (E = Se, S; R = Ph, Me), (iv) Characterization of AlPO4(110)
Surface in Adsorption of Rh Dimer and Its Comparison with γ‑Al2O3(100) Surface, (v) Heterolytic
Activation of Dihydrogen Molecule by Hydroxo-/Sulfido-Bridged Ruthenium−Germanium Dinuclear
Complex, (vi) Activation of Strong Boron–Fluorine and Silicon–Fluorine σ-Bonds: Theoretical
Understanding and Prediction, and (vii) the crucial role of a Ni(I) intermediate in Ni-catalyzed carboxylationof aryl chloride with CO2.
. We wish to report summaries of them, below.
(i) CASPT2 study of inverse sandwich-type dinuclear 3d transition metal complexes of ethylene anddinitrogen molecules: similarities and differences in geometry, electronic structure, and spin
multiplicity
The spin multiplicity of transition
metal complexes has attracted a lot ofinterest recently because spin multiplicity isclosely related to single-molecule magnets,
spin-crossover complexes, spin catalysis,
and so on. In this regard, it is of
considerable interest to obtain theoreticalknowledge of how to understand spin
multiplicity and how to control it. In
general, it is said that a strong ligand fieldleads to the presence of a low-spin state andFigure 1. CASSCF-optimized geometry of Mn and Cr ISTCs ofa weak ligand field leads to the presence of ethylene－ 61 －

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a high-spin state. However, the story is not so simple in dinuclear transition metal complexes, because of thepresence of interaction between the two metal centers. Recently, inverse sandwich-type dinuclear transition
metal complexes (ISTCs) were synthesized. In ISTCs, an organic moiety is sandwiched by two metal
moieties in contrast to the usual sandwich-type complex in which a metal is sandwiched by two organic
moieties. ISTCs attract great interests in coordination chemistry, organometallic chemistry, and physicalchemistry because of their characteristic geometries, bonding natures, and molecular properties. For instance,benzene and toluene ISTCs of Cr have a septet ground state and those of V(I) have a quintet ground state,
which are unusually high spin multiplicities. In our previous theoretical study of benzene ISTCs, we foundthat the spin multiplicity of the ground state monotonically increases from a closed-shell singlet to a nonet
when going from Sc to Mn but suddenly decreases to an open-shell singlet in Fe. Hence, it is of considerable
interest to systematically investigate the spin multiplicity of ethylene and dinitrogen ISTCs of all first-row
transition metal elements and elucidate how the spin multiplicity changes along the first-row transition metalelements.
Table 1. Stable geometry and relative energies of various spin multiplicity
In this work, we (A) Dinitrogen complex
theoretically investigatedethylene and dinitrogen
ISTCs of Sc to Ni. The
spin multiplicities andcoordination structures of
inversesandwich-type(B) Ethylene complex
complexes (ISTCs) of
ethylene and dinitrogenmoleculeswith
3dtransition metal elements
(Sc
to
Ni),
(µ-C2H4)[M(AIP)]2 and(µ-N2)[M(AIP)]2 (AIPH =(Z)-1-amino-3-iminoprop-1-ene; M = Sc to Ni) were investigated by the CASPT2 method. In both ethylene
and dinitrogen ISTCs of the early 3d transition metals (Sc to Cr), sandwiched ethylene and dinitrogen ligands
coordinate with two metal atoms in an η2-side-on form and their ground states have an open-shell singlet
spin multiplicity. The η1-end-on coordination structure of dinitrogen ISTCs is considerably less stable thanthe η2-side-on form in these metals. For the late 3d transition metals (Mn to Ni), ethylene and dinitrogen
ISTCs exhibit interesting similarities and differences in spin multiplicity and structure as follows: in ethylene
ISTCs of Mn to Ni, the ground state has an open-shell singlet spin multiplicity like those of the ISTCs ofearly transition metals. However, the ethylene ligand is considerably distorted, in which the ethylene carbon
atoms have a tetrahedral-like structure similar to sp3 carbon and each of them coordinates with one metal in aµ-η1: η1 structure. These geometrical features are completely different from those of ISTCs of the earlytransition metals. In dinitrogen ISTCs of Mn to Ni, on the other hand, the ground state has a high spin
multiplicity from nonet (Mn) to triplet (Ni). The η2-side-on coordination structure of the dinitrogen ligand is
as stable as the η1-end-on form in the Mn complex but the η1-end-on structure is more stable than theη2-side-on form in the Fe to Ni complexes. All these interesting similarities and differences between ethylene
and dinitrogen ISTCs and between the early and late transition metal elements arise from the occupation ofseveral important molecular orbitals.

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Ⅳ 研究業績 (2015)(ii) Theoretical Study of Pd11Si6 Nanosheet Compounds Including Seven-Coordinated Si Species and
Its Ge Analogues:
Nanoscale metal particles have attracted a lot of interests in the last decade, because such metalPrparticles exhibit new properties, which are considerably
Pr
L
1a
Pr
1a
Pr
Si
4a
4a
different from those of bulk metals and large metal particles.
1b Si
L
Pd
4b
1a
1a
1b L
L Pd
L
Pd
Pd
2a
L
2a
One good example is the new field of catalysis by using gold
2b
Pr
5a
3a
Pd
3a
Pd 5a
Pd
Si
3b
Pd
Pr
nanoparticles, which was first found by Haruta and coworkers.
Si
Si
5b
Pr
Pr
2b
2a
Si 2a
Pd
Pr
In almost all cases, such metal particles have three-dimensional
Pr
Pd
Pd
77
33
L
66
Pr
Pr
L
L
structures. On the other hand, the reports on two-dimensional
N
N
Bu
Bu
Bu
metal plate compounds have been limited so far. Although
Scheme 1. Structure of Pd11Si6
ultrafine palladium, rhodium, and ruthenium nanoplate materials
nanosheet compound
have been reported recently, the thickness is approximately 1–2
nm, indicating that these materials are much thicker than
ii

ii

i

i

i

i

ii

i

ii

ii

tt

tt

graphene, which is one of the typical plate materials.
Considering that graphene exhibits very different properties
from those of multi-layers graphite, one can expect that veryfine nanosheet materials, like graphene, are of considerable
interest. Actually, monolayer materials of molybdenum
disulfide and boron nitride exhibit considerably different
properties from those of bulk compounds. In this regard,monolayer nanosheet compounds of metals attract a lot ofinterests and various planar clusters have been synthesized.
Figure 2. Difference density of Pd11Si6
However, the examples have been limited. Recently, much nanosheet compound from Pd(0), SiMe2,
largerpalladiumnanosheetcompounds,
thatis, and MeCN. Blue; decrease in density,
Pd11(SiiPr)2(SiiPr2)4(CNR)10 (1 for R=tBu and 2 for orange; increase in density
R=2,4,6-Me3-C6H2) were synthesized by Nagashima, and coworkers, as shown in Scheme 1. These
completely new compounds are of considerable interest. In the present theoretical work, we investigated thePd11 monolayer nanosheet compounds Pd11(SiMe)2(SiMe2)4(CNMe)10 1Si and 2Si, and their Ge analogues
1Ge and 2Ge with the DFT method, where compounds 1Si and 2Si are models of 1 and 2, respectively. All
Pd atoms are somewhat positively charged and the electron density is accumulated between the Pd and Si
atoms, indicating that a charge transfer (CT) occurs from the Pd to the Si atoms of the SiMe2 and SiMegroups. Negative regions of the Laplacian of the electron density were found between the Pd and Si atoms. A
model of a seven-coordinated Si species, that is, Pd5(Pd-SiMe), is predicted to be a stable pentagonal
bipyramidal molecule. Five Pd atoms in the equatorial plane form bonding overlaps with two 3p orbitals of
the Si atom. This is a new type of hypervalency. The Ge analogues have geometry and an electronic structure
similar to those of the Si compounds. But their formation energies are smaller than those of the Si analogues.
The use of the element Si is crucial to synthesize these nanoplate compounds.
(iii) Au8 Cores and Entangled Ligands of Selenolate- and Thiolate-Protected Gold Nanoclusters
Au24(ER)20 and Au20(ER)16 (E = Se, S; R = Ph, Me)Gold nanoclusters protected by organic ligands attract much interests as a building block of novel
functional materials such as catalysts, photonics, and molecular electronics, because metal nanoclusters
exhibit unusual physicochemical properties and chemical reactivity different from bulk metals. Among them,thiolate-protected gold clusters, which are represented with a general Aun(SR)m formula, have been widely－ 63 －

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known. In those compounds, an Aun core is surrounded by organothiolate (SR) ligands. In many cases, theAun core has a highly symmetrical geometry with a closed-shell singlet ground state. Recently, novel
thiolate-protected gold clusters Au20(SR)16 and Au24(SR)20 (R = CH2CH2Ph) have been synthesized. Though
their crystal structures have not been reported yet, experimental reports suggest that the Au8 core issurrounded by four organothiolate ligands such as Au3(SR)4 and Au5(SR)6. This type of Au8 core has neverbeen observed before. Very recently, the first X-ray analysis of a similar selenolate-protected Au nanoclustercompound Au24(SeR)20 (R = Ph) 1-SePh was successfully made. Very recently, the first X-ray analysis of asimilar selenolateprotected Au nanocluster compound Au24(SeR)20 (R = Ph) 1-SePh was successfully made.
1-SePh consists of an Au8 core with two Au3(SeR)4 and two Au5(SeR)6 staple-like chain ligands. Despite ofthese interesting geometries, no theoretical study has been presented on these clusters.
In
this
work,
we
theoretically investigated thegeometries and the electronic
structuresof
Au24(SeR)20
1-SeR, Au20(SeR)16 2-SeR (R =Ph and Me; Scheme 2). The
geometries
andelectronic
structuresofselenolate-protected
Au Scheme 2. Structures of Au (ER) and Au (ER) (E = S or Se; R=Ph) .
24
20
20
16
nanoclusters, Au24(SeR)20 and
Au20(SeR)16, and their thiolate analogues are theoreticallyinvestigated with DFT and SCS-MP2 methods, to elucidate theelectronic structure of their unusual Au8 core and the reason why they
have the unusual entangled “staple-like” chain ligands. The Au8 coreis understood to be an [Au4]2+ dimer in which the [Au4]2+ species has
a tetrahedral geometry with a closed-shell singlet ground state. The
SCS-MP2 method successfully reproduced the distance between two Figure 3. Potential energy surface
X1-X2
distanceof[Au4]2+ moieties, but the DFT with various functionals failed it, against
Au24(SeR)20
suggesting that the dispersion interaction is crucial between these two[Au4]2+ moieties. The SCS-MP2-calculated formation energies of these nanocluster compounds indicate thatthe thiolate staple-like chain ligands are more stable than the selenolate ones, but the Au8 core more strongly
coordinates with the selenolate staple-like chain ligands than with the thiolate ones. Though Au20(SeR)16 has
not been reported yet, its formation energy is calculated to be large, suggesting that this compound can besynthesized as a stable species if the concentration of Au(SeR) is well adjusted. The aurophilic interactions
between the staple-like chain ligands and between the Au8 core and the staple-like chain ligand play animportant role for the stability of these compounds. Because of the presence of this autophilic interaction,
Au24(SeR)20 is more stable than Au20(SeR)16 and the unusual entangled ligands are involved in thesecompounds.
(iv) Characterization of AlPO4(110) Surface in Adsorption of Rh Dimer and Its Comparison with
γ‑Al2O3(100) Surface
Metal elements of groups 9 and 10 such as Pt, Pd, and Rh are used now in many three-way catalysts
for automobiles. Particularly, these metals play crucial roles in NO−CO and NO−hydrocarbon reactions.
Considering that these metals are not abundant on the earth, it is of considerable importance to reduce the－ 64 －

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EFermiDOS

content of these metals in catalysts. In general, these metals are used as dispersed nanoparticles combinedwith the surface of the support to suppress sintering and maintain dispersion of small metal particles.
Actually, almost all excellent state-of-the art catalysts consist of metal nanoparticles and appropriate supports.
Recently, Machida and co-workers found that the use of tridymite-type aluminum orthophosphate (AlPO4) asa support can markedly decrease the quantity of Rh in the three-way catalyst because thermally stable andhighly dispersed Rh nanoparticles are anchored well on the phosphate surface. Considering that AlPO4 is arobust and cheap material, their finding is of considerable importance in constructing a low-cost but effective
catalyst. To elucidate the reasons this AlPO4 exhibits such an excellent anchoring effect, it is necessary toascertain where the Rh adsorption occurs, how strong the interaction between the Rh particle and the surface
is, and to clarify the origin of the interaction.
Adsorption of Rh dimer on AlPO4(110)and γ-Al2O3(100) surfaces was theoretically
Isokated LU band
investigated by periodic DFT calculation with a slab
Df-AlPO4nh
model to elucidate characteristic features of the
AlPO4 surface in comparison with the γ-Al2O3
Eq-AlPO4nh
surface. The adsorption at the PO site is the mostfavorable in both nonhydrated and hydrated AlPO4
surfaces, which is consistent with the experimental
finding. The adsorption at the AlO site is the least
favorable. The adsorption energy at the PO site ofBand energy (eV)the AlPO4 surface is considerably larger than that at
the γ-Al2O3 surface. One important reason is that the Figure 4. Change in band structure of
deformation energy of the γ-Al2O3 surface is much non-hydrated AlPO4 by the interaction with Rh2.
larger than that of the AlPO4 surface. Bader charge
analysis, difference electron density map, and projected density of states (p-DOS) clearly disclose that the
charge transfer (CT) occurs from the Rh dimer to the AlPO4 surface (Figure 4). This CT is stronger than in
the adsorption on the γ-Al2O3 surface. The lowest unoccupied band (LU band in conduction band) plays acrucial role as an electron-acceptor orbital in this CT interaction. The LU band of the AlPO4 exists at a lower
energy than that of γ-Al2O3. Therefore, the CT from the Rh dimer to the AlPO4 surface is considerably larger
than that to the γ-Al2O3 surface. These results show that the presence of the isolated LU band at a low energy
and the flexible AlPO4 structure are important factors for the anchoring effect, which achieves outstanding
thermal stability of the supported Rh nanoparticles on the AlPO4 surface and therefore enables a reduction inquantity of Rh in the three-way catalyst using AlPO4.
(v)
Heterolytic
ActivationofDihydrogen
MoleculebyHydroxo-/Sulfido-Bridged
Ruthenium−Germanium Dinuclear Complex.
Heterolytic H−H σ-bond activation of dihydrogen molecule (H2) with transition metal complex is oneof the most important research subjects
inbiochemistry
andinorganic
chemistry, because the heterolytic
activation of H2 is involved as a key
step in hydrogen metabolism byhydrogenases. To explore and mimic its Scheme 3. Reaction scheme of H2 activation by Ru-Ge
dinuclear complex
catalysis, many experiments have been
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carried out to synthesize good models of [NiFe]-hydrogenase, and the activation reactions of H2 with suchhydrogenase models as Ir−Ir, Rh−Rh, Mo−Mo, W−Ir, W−Ru, Ru−Ni, and Fe−Ni dinuclear complexes havebeen reported. Recently, Matsumoto, Tatsumi, and their co-workers synthesized a hydroxo-/sulfido-bridged
Ru−Ge dinuclear complex [Dmp(Dep)Ge(μ-S)(μ-OH)Ru(PPh3)]+(BArF4)− (Dmp = 2,6-dimesitylphenyl, Dep= 2,6-diethylphenyl, ArF4 =3,5-(CF3)2C6H3) and reported its interesting reactions (Scheme 3), as follows: (1)This complex performs σ-bond activation of H2 at room temperature to afford H2O and[Dmp(Dep)Ge(μ-S)Ru(H)(PPh3)]+(BArF4)−, which is similar to the activation reaction of H2 by hydrogenase,and (2) addition of H2O to the product induces the reverse reaction to afford H2 and the original Ru−Ge
complex, indicating that the reversible reaction is successfully performed by this Ru−Ge complex.
In this theoretical work, we investigated the H−H σ-bond activation of H2 to afford H2O promoted by
the hydroxo-/sulfido-bridged Ru−Ge dinuclear complex [Dmp(Dep)Ge(μ-S)(μ-OH)Ru(PPh3)]+ (1).
Heterolytic activation of dihydrogen molecule (H2) by hydroxo-/sulfido-bridged ruthenium−germanium
dinuclear complex [Dmp(Dep)Ge(μ-S)(μ-OH)Ru(PPh3)]+ (1) (Dmp = 2,6-dimesitylphenyl, Dep =2,6-diethylphenyl) is theoretically investigated with the ONIOM(DFT:MM) method. H2 approaches 1 toafford an intermediate [Dmp(Dep)(HO)Ge(μ-S)Ru(PPh3)]+-(H2) (2). In 2, the Ru−OH coordinate bond isbroken but H2 does not yet coordinate with the Ru center. Then, the H2 further approaches the Ru center
throughatransition
state
TS2−3
to
affordadihydrogen
σ-complex2+[Dmp(Dep)(HO)Ge(μ-S)Ru(η -H2)(PPh3)] (3). Starting from 3, the H−H σ-bond is cleaved by the Ru andGe−OH moieties to form [Dmp(Dep)(H2O)Ge(μ-S)Ru(H)(PPh3)]+ (4). In 4, hydride and H2O coordinate with
the Ru and Ge centers, respectively. Electron population changes clearly indicate that this H−H σ-bondcleavage occurs in a heterolytic manner like H2 activation by hydrogenase. Finally, the H2O dissociates fromthe Ge center to afford [Dmp(Dep)Ge(μ-S)Ru(H)(PPh3)]+ (PRD). This step is rate-determining. The
activation energy of the backward reaction is moderately smaller than that of the forward reaction, which isconsistent with the experimental result that PRD reacts with H2O to form 1 and H2. In the Si analogue[Dmp(Dep)Si(μ-S)(μ-OH)Ru(PPh3)]+ (1Si), the isomerization of 1Si to 2Si easily occurs with a small
activation energy, while the dissociation of H2O from the Si center needs a considerably large activationenergy. Based on these computational findings, it is emphasized that the reaction of 1 resembles well that ofhydrogenase and the use of Ge in 1 is crucial for this heterolytic H−H σ-bond activation.
(vi) Activation of Strong Boron–Fluorine and Silicon–Fluorine σ-Bonds: Theoretical Understanding
and Prediction
The σ-bond cleavage by transition-metal complexes, such as oxidative addition and σ-bond metathesis,is the first step in almost all homogeneous catalytic reactions. To date, the B-F bond in boranes and Si-F
bond in silanes have been alien to such bond activation reactions, precluding their direct catalytictransformation. This is because B-F and Si-F σ-bonds are two of the strongest σ-bonds (bond dissociationenergies of B-F and Si-F σ-bonds are 183 and 129 kcal mol-1, respectively) owing to strong bonding
interaction between electropositive atom and electronegative fluoride. Activation of these σ-bonds by atransition metal, if readily achieved, would open a new door to synthesis of novel organic fluoroboron andfluorosilicon compounds, which are potentially valuable functional materials. Recently, Braunschweig andco-workers made a remarkable breakthrough when they reported the first example of B-F σ-bond activation
via oxidative addition. In their reaction, the B-F σ-bond of BF3 is cleaved by a platinum(0) bis(phosphine)complex.
Herein, we report a detailed theoretical study on B-X σ-bond activation (X=F, Cl) and similar Si-F σbond activation by a Pt0 complex. Our purposes are to elucidate the reason why the strong B-F σ-bond can be－ 66 －

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easily cleaved by a Pt0 complex under mild conditions and to present theoretical prediction how to activate
the similarly strong Si-F σ-bond of SiF4 by a Pt0 complex. The oxidative addition of BF3 to a platinum(0)bis(phosphine) complex [Pt(PMe3)2] (1) was investigated by density functional calculations. Both the cis andtrans pathways for the oxidative addition of BF3 to 1 are endergonic (∆G°=26.8 and 35.7 kcal mol-1,
respectively) and require large Gibbs activationenergies (∆G°‡ =56.3 and 38.9 kcal mol-1,
respectively). A second borane plays crucial roles inaccelerating the activation; the trans oxidative
addition of BF3 to 1 in the presence of a second BF3molecule occurs with ∆G°‡ and ∆G° values of 10.1 Figure 5. Geometry and energy changes in the B-F
and -4.7 kcal mol-1, respectively. ∆G°‡ becomes very σ-bond cleavage by Pt(0) complex in the presence ofsmall and ∆G° becomes negative. A charge transfer the second BF3(CT) occurs from the dissociating fluoride to thesecond non-coordinated BF3. This CT interaction stabilizes both the transition state and the product. The B-F
σ-bond cleavage of BF2ArF (ArF=3,5-bis(trifluoromethyl) phenyl) and the B-Cl σ-bond cleavage of BCl3 by
1 are accelerated by the participation of the second borane. The calculations predict that trans oxidative
addition of SiF4 to 1 easily occurs in the presence of a second SiF4 molecule via the formation of a
hypervalent Si species.
(vii) Reasons Two Nonstrained C−C σ‑Bonds Can Be Easily Cleaved in Decyanative [4 + 2]
Cycloaddition Catalyzed by Nickel(0)/Lewis Acid Systems. Theoretical Insight
The selective activation of nonstrained inert C−C
σ-bonds has attracted much attention because of its powerful
and wide application to organic syntheses and catalytic
reactions. This process is not only helpful for the constructionof complex molecular skeletons from simple starting materials
but also satisfies atom economy. However, the process still
faces tremendous challenges due to the inertness of thenonstrained C−C σ-bond, considering that the C−C σ-bond Scheme 4. Ni0/LA-catalyzed [4 + 2]
cleavage is more difficult than C−H σ-bond cleavage because cycloaddition of oarylcarboxybenzonitrile
with alkyne
both sp3 orbitals of two carbon atoms extend well toward eachother in the C−C σ-bond and thereby an incoming metal centercannot interact well with these sp3 orbitals.
In the present work, we theoretically investigated the full catalytic cycle of the Ni0/LA-catalyzed [4 +2] cycloaddition of oarylcarboxybenzonitrile with alkyne (Scheme 4) by density functional theory (DFT).
Two constrained C−C σ-bonds are cleaved in a novel nickel(0)/LA-catalyzed decyanative [4 + 2]
cycloaddition of o-arylcarboxybenzonitrile with alkyne, where LA represents a Lewis acid such as
methylaluminum bis(2,6-ditert-butyl-4-methylphenoxide). The catalytic cycle of this reaction issystematically investigated here by DFT method to clarify the reasons two nonstrained C−C σ-bonds are
successfully cleaved in this reaction. DFT calculations indicate that this reaction occurs via the oxidative
addition of the C−CN σ-bond of o-arylcarboxybenzonitrile to the Ni(0) center, alkyne insertion into theNi(II)−aryl bond, C−C coupling between the vinyl carbon and the carboxyl carbon atoms, and β-aryl
elimination followed by reductive elimination. One LA interacts with the cyano nitrogen atom of
o-arylcarboxybenzonitrile to accelerate the oxidative addition by stabilizing the unoccupied σ* + π* C−CN
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antibonding orbital. One more LA interacts with the carbonyl oxygen of o-arylcarboxybenzonitrile. This LA
enhances the electrophilic nature of the carbonyl carbon to accelerate the C−C coupling, because this step
occurs through the nucleophilic attack of the vinyl carbon at the carbonyl carbon atom. The second C−C
σ-bond activation occurs via β-aryl elimination, the transition state of which is stabilized by the interaction
between LA and the carbonyl oxygen atom. These results lead to the clear conclusion that the presence of
two LA molecules is crucial to achieve the dual C−C σ-bond cleavages. The reasons LA accelerates theoxidative addition of the C−CN σ-bond to the nickel(0) center and the C−C coupling followed by the β-aryl
elimination are discussed in detail.
Original Papers(1) Wei Guan, Shigeyoshi Sakaki, Takuya Kurahashi, and Seijiro Matsubara,“Reasons Two Nonstrained C-C σ-Bonds Can Be Easily Cleaved in Decyanative [4+2]Cycloaddition Catalyzed by Nickel(0)/Lewis Acid Systems. Theoretical Insight”
ACS Catalysis, 5, 1-10 (2015)..
(2) Noriaki Ochi, Tsuyoshi Matsumoto, Takuya Dei, Yoshiaki Nakao, Hirofumi Sato, Kazuyuki
Tatsumi, Shigeyoshi Sakaki,"Heterolytic Activation of Dihydrogen Molecule by Hydroxo-/Sulfido-Bridged Ruthenium–
Germanium Dinuclear Complex. Theoretical Insights”
Inorg. Chem., 54, 576–585 (2015).
(3) Hisako Hashimoto, Yuto Odagiri, Yasuhiro Yamada, Nozomi Takagi, Shigeyoshi
Sakaki,and Hiromi Tobita,“Isolation of a Hydrogen-Bridged Bis(silylene) Tungsten Complex: A Snapshot of aTransition State for 1,3-Hydrogen Migration”
J. Am. Chem. Soc., 137, 158−161 (2015).
(4) Hajime Kameo, Tatsuya Kawamoto, Didier Bourissou, Shigeyoshi Sakaki, and Hiroshi Nakazawa,“Evaluation of the sigma-Donation from Group 11 Metals (Cu, Ag, Au) to Silane, Ger-mane, andStannane Based on the Experimental/Theoretical Systematic Approach”
Organometallics, 34, 1440−1448 (2015).
(5) Nozomi Takagi, Kazuya Ishimura, Masafuyu Matsui, Ryoichi Fukuda, Toru
Matsui,Takahito Nakajima, Masahiro Ehara, and Shigeyoshi Sakaki,“How Can We Understand Au8 Cores and Entangled Ligands of Selenolate- andThio-late-Protected Gold Nanoclusters Au24(ER)20 and Au20(ER)16 (E = Se, S; R = Ph, Me)?
A Theoretical Study”
J. Am. Chem. Soc., 137, 8593−8602 (2015).
(6) K. Kido, K. Kasahara, H. Sato, S. Sakaki,“A molecular level study of selective cation capture by a host-guest mechanism for 25, 26, 27,
28-tetramethoxycalix[4]arene in MClO4 solution (M=Na, K)”
A Mol. Simu., SI. 41, 881-891 (2015).
(7) Masafuyu Matsui, Masato Machida, Shigeyoshi Sakaki,“Characterization of AlPO4(110) Surface in Adsorption of Rh Dimer and Its Comparison withgamma-Al2O3(100) Surface: A Theoretical Study”
J. Phys. Chem. C, 119, 19752-19762 (2015).
(8) Hajime Kameo, Shigeyoshi Sakaki“Activation of Strong Boron-Fluorine and Silicon-Fluorine sigma-Bonds: Theoretical
Understanding and Prediction”
Chem. Eur. J., 21, 13588-13597 (2015).
(9) Yue Chen, Yusuke Sunada, Hideo Nagashima, Shigeyoshi Sakaki,“Theoretical Study of Pd11Si6 Nanosheet Compounds Including Seven-Coordinated Si Spe-cies and
Its Ge Analogues”
Chem. Eur. J., 22, 1076–1087 (2015).
(10) Shinichi Yamabe, Shoko Yamazaki, and Shigeyoshi Sakaki,,“A DFT Study of Hydride Transfers to the Carbonyl Oxygen of DDQ”
Int. J. Quant. Chem., 115, 1533–1542 (2015).
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Ⅳ 研究業績 (2015)(11) Masayuki Nakagaki and Shigeyoshi Sakaki“CASPT2 study of inverse sandwich-type dinuclear 3d transition metal complexes of eth-ylene
and dinitrogen molecules: similarities and differences in geometry, electronic structure, and spin
multiplicity”
Phys. Chem. Chem. Phys, 17, 16294-16305 (2015).
3. Presentation at academic conferences(1) Yue Chen, Masayuki Nakagaki, Shigeyoshi Sakaki,“Bonding Nature, Reactivity and Catalysis of M-M Multiple Bond: Theoretical Study”
The 6th JCS(Japan-Czech-Slovakia)-Joint Symposium, Oct.11-14, 2015, Somlenice, Slovakia,(Invited)(2) Shigeyoshi Sakaki“Theoretical understanding of catalysis by transition metal complex with unusual valence”
X Pacifichem2015, Dec. 15 – 20, Honolulu, USA. (Invited)(3) Shigeyoshi Sakaki“Theoretical Study of Complex System Consisting of Transition Metal Element(s)”,The Seven-th Asia-Pacific Confernece on Theoretical and Computational Chemistry, Jan. 25 to 28,
2016, Kaoshiung, Taiwan. (Plenary)(4) 榊 茂好“遷移金属元素とケイ素化学種の相互作用と反応過程の理論研究: 面白さと難しさ”.
第１９回ケイ素化学シンポジウム 2015 年 10 月 23-24 日 琵琶湖ラフォーレ、守山 (Invited)(5) 榊 茂好“複合金属微粒子の構造と電子状態”
分子研・研究会「触媒の分子科学」2016 年 3 月 9-10 日、岡崎
(6) 榊 茂好
“理論化学・計算化学の未来：展望と期待”
計算分子科学研究拠点 第６回研究会 2016 年 3 月 14-15 日、岡崎
(7) S. Aono, S. Sakaki“Isomerization of ruthenium(II) sulfur dioxide complex in crystal; Theoretical study with QM/MM
approach”
The Seven-th Asia-Pacific Confernece on Theoretical and Computational Chemistry, Jan. 25 to 28,
2016, Kaoshiung, Taiwan.
4. Others(1) Theoretical and Computational Study of a Complex System Consisting of Transition Metal
Element(s): How to Understand and Predict Its Geometry, Bonding Nature, Molec-ular Property,
and Reaction Behavior (Award Article).
Shigeyoshi Sakaki, Bull. Chem. Soc. Jpn., 88, 889–938 (2015).

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HOMOLUMO !Ÿ!2$5 kF - HOMO−LUMO ƌ&ƅ$1ń¢ Sij &|y!Š"!2
ThermalActivation(kRISC)S1

Reverse Intersystem
Crossing

Flu orescen ce(kF)

Ph osp h olescen ce(kP)

R ad iation lessTran sition (knr)

ΔES T

T1

R ad iation lessTran sition (knr‘)

S0
D elayed 	
 flu orescen ce（α-Ph osp h olescen ce）(kF)

Figure 1. M echanism of TADF related with

Figure 2. BCzT designed in

S 0 , S 1 , and T 1 .

the present study.

 s0ΔEST 6Ï2%' Sij 6ÏkF 6Ã2%' Sij 6Ã2çŢ1Sij &%'RkpS?\&ƍ2"%$2

!Þ(2)'Ÿķ$-&!

ƀł°ĒÄfpenRµij 'ƅ$1ń¢"Ç$ěƍ%25!'$"6
/"%ĝë2&"RkpS?\ƍ'Ðß,032&!3%ĝë$0Ē§sŧƟĦ6ģ%þţ%Ũť¢Ä BCzT (9-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9’-phenyl-9H,9’H-3,3’-bicarbazole) 6 Figure 2 %Ŀ&¢Ä& DFT ťŉ (CAM -B3LYP/cc-pVDZ)%/2"
´&Ri9Inİ'$1÷3

13%/

ΔEST 6t2"!ƙÉƖ

0.29-0.33 eVƚqÿ! S0−S1 Ĭìƌ&ƀł°ĒÄfpenR6Ń"%/1 S1
ł'ġ!2+&¢Ä'¢ÄƑŚł«6ų.

Ĕż%$

MpjƂ¢STp´&Ri9Inİ9BL^Np"$

0&ħŶÌƀ

1Ö&@jY2 &¢Ä6ÉƐ%¶îDPEPO (bis(2-(diphenylphosphino)phenyl)ether oxide) 6`JRĈ"2 OLED 6š

483 nm Ķ&ÁƂƇÄªĭ6ĢÈ"4äĉ&Ǝĵ"32 5- 7.5 %& 3-4 !2 21.7 %&6ſî460 nm &¬ÆĶƙ387 nm ©ųƚ&ŝƇÄ²
ĭ' 300 K %95.6 %!

【文 献 】 1) W. Helfrich and W. G. Schneider, Phys. Rev. Lett., 14, 229 (1965). 2) A. Endo, M. Ogasawara,
A. Takahashi, D. Yokoyama, Y. Kato, and C. Adachi, Adv. Mater., 21, 4802 (2009). 3) K. Shizu, H. Noda, H.
Tanaka, M. Taneda, M. Uejima, T. Sato, K. Tanaka, H. Kaji, and C. Adachi, J. Phys. Chem. C, 119, 26283(2015).

ƞƜ Ůü

－ 71 －

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Ⅳ 研究業績 (2015)(1) Naoki Haruta, Tohru Sato, and Kazuyoshi Tanaka“Reactivity Index for Diels-Alder Cycloadditions to Large Polycyclic Aromatic Hydrocarbons
Using Vibronic Coupling Density”
Tetrahedron Lett. 56, 590-594 (2015).
(2) Takuya Matsumoto, Kazuo Tanaka, Kazuyoshi Tanaka, and Yoshiki Chujo“Synthesis and Characterization of Heterofluorenes Containing Four-coordinated Group 13
Elements: Theoretical and Experimental Analyses and Comparison of Structures, Optical
Properties and Electronic States”
Dalton Trans. 44, 8697-8707 (2015).
(3) Yuichi Hirai, Takayuki Nakanishi, Yuichi Kitagawa, Koji Fushimi, Tomohiro Seki, Hajime Ito,
Hiroyuki Fueno, Kazuyoshi Tanaka, Toshifumi Satoh, and Yasuchika Hasegawa“Luminescent Coordination Glass: Remarkable Morphological Strategy for Assembled Eu (III)Complexes”
Inorg. Chem. 54, 4364-4370 (2015).
(4) Furitsu Suzuki, Katsuyuki Shizu, Hisafumi Kawaguchi, Shinya Furukawa, Tohru Sato,
Kazuyoshi Tanaka, and Hironori Kaji“Multiscale Simulation of Charge Transport in a Host Material, N, N’-Dicarbazole-3,5-benzene(mCP), for Organic Light-Emitting Diodes”
J. Mater. Chem. C 3, 5549-5555 (2015).
(5) Daisuke Sakamaki, Soichiro Yano, Toshiyuki Kobashi Shu Seki, Takuya Kurahashi, Seijiro
Matsubara, Akihiro Ito, and Kazuyoshi Tanaka“A Triphenylamine with Two Phenoxy Radicals Having Unusual Bonding Patters and a
Closed-Shell Electronic State”
Angew. Chem. Int. Ed. 54, 8267-8270 (2015).
(6) Shintaro Iwamoto, Yuu Inatomi, Daisuke Ogi, Satoshi Shibayama, Yukiko Murakami, Minami
Kato, Kazuyuki Takahashi, Kazuyoshi Tanaka, Nobuhiko Hojo, and Yohji Misaki“New Tris- and Pentakis-Fused Donors Containing Extended Tetrathiafulvalenes: New Positive
Electrode Materials for Reachargeable Batteries”
Beilstein J. Org. Chem. 11, 1136-1147 (2015).
(7) Masashi Uebe, Akihiro Ito, Yuichiro Kameoka, Tohru Sato, and Kazuyoshi Tanaka“Fluorescence Enhancement of Non-Fluorescent Triphenylamine: A Recipe to Utilize
Carborane Cluster Substituents”
Chem. Phys. Lett. 633, 190-194 (2015).
(8) Katsuyuki Shizu, Hiroki Noda, Hiroyuki Tanaka, Masatsugu Taneda, Motoyuki Uejima, Tohru
Sato, Kazuyoshi Tanaka, Hironori Kaji, and Chihaya Adachi“Highly Efficient Blue Electroluminescence Using Delayed-Fluorescence Emitters with Large
Overlap Density between Luminescent and Ground States”
J. Phys. Chem. C 119, 26283-26289 (2015).
(9) Takayuki Maegawa, Yasuyuki Irie, Hiroaki Imoto, Hiroyuki Fueno, Kazuyoshi Tanaka, and－ 72 －

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Kensuke Naka
“para-Bisvinylhexaisobutyl-Substituted T8 Caged Monomer: Synthesis and Hydrosilylation
Polymerization”
Polym. Chem. 6, 7500-7504 (2015).
(10)Liangchun Li, Tsukasa Matsuo, Daisuke Hashizume, Hiroyuki Fueno, Kazuyoshi Tanaka, andKohei Tamao“Coplanar Oligo(p-phenylenedisilenylene)s as Si=Si Analogues of Oligo (p-phenylene
vinylene)s: Evidence for Extended π-Conjugation through the Carbon-Silicon π-Frameworks”
J. Am. Chem. Soc. 137, 15026-15035 (2015).
(11) Ryohei Kurata, Kazuyoshi Tanaka, and Akihiro Ito“Isolation and Characterization of Persistent Radical Cation and Dication of 2,7-Bis(dianisyl
amino) pyrene”
J. Org. Chem. 81, 137-145 (2016).
(12) Megumi Kobayashi, Naoki Hayakawa, Tsukasa Matsuo, Baolin Li, Takeo Fukunaga, Daisuke
Hashizume, Hiroyuki Fueno, Kazuyoshi Tanaka, and Kohei Tamao“(Z)-1,2-Di(1-pyrenyl)disilene: Synthesis, Structure, and Intramolecular Charge-Transfer
Emission”
J. Am. Chem. Soc. 138, 758-761 (2016).
(13) Akihiro Ito, Masashi Uebe, Kazuki Takahashi, Hiroshi Ishikawa, Daisuke Sakamaki, Hiroyasu
Sato, Takashi Matsumoto, and Kazuyoshi Tanaka“Synthesis and Characterization of 6,13-Diamino-Substituted Pentacenes”
Chem. Eur. J. 22, 2165-2170 (2016).
(14) Hirotaka Uji, Kazuyoshi Tanaka, and Shunsaku Kimura“O2-Triggered Directional Switching of Photocurrent in Self-Assembled Monolayer
Composedof Porphyrin- and Fullerene-Terminated Helical Peptides on Gold”
J. Phys. Chem. C 120, 3684-3689 (2016).
ƟƜ śĄ(1) ĴvqŒ, ŇƆ®x, ō]lPBĈý&¾ľ"Éĳ¬&,&įŮ¬Æ,vď»ĕĸ, ō]lPBƗ¢Ä−ĆėoħėX;]iPSĈý&þēé−(ś, Hp>dH
p, 2015).
(2) ĴvqŒapjĪį¬Æ ň 2 ĩƙsƚ(ĸũ$0)%ũ, ¬Æ·, 2015).
(3) ĴvqŒapjĪį¬Æ ň 2 ĩƙtƚ(ĸũ$0)%ũ, ¬Æ·, 2016).
Ơ Ɯ Ő Ŭ (1) JKĩCh\=n “JNVn” 03Ƙ(­ś)¬Æ, 71, No. 1, 21-26 (2016).

－ 73 －

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Ⅳ 研究業績 (2015)ơƜ ÆĶŠ(1) ĂĴĺĚoŜ æ,oĴvqŒ, ÂęƏİ¬¨±è%Ë2öƑĻ}ĳÊÜŤČ, āćEn[gpN¬Æ 2015 ÛĂÅÛ, Ċ, 2015 Û 5 ą 28-29 ā(2) Ŝ æozÓqƁoĴvqŒ, HBlZh\=Ukn% 2ú Jahn-Teller ªč"Ĕż¥å, āćEn[gpN¬Æ 2015 ÛĂÅÛ, Ċ, 2015 Û 5 ą 28-29 ā(3) ƓĴœÃoŜ æoĴvqŒ, öƑĻ}ĳÊÜŤČ%/2j]kn& Ƅ£>Vj
Ap¥å, āćEn[gpN¬Æ 2015 ÛĂÅÛ, Ċ, 2015 Û 5 ą 28-29 ā(4) ċć ĥoŜ æoĴvqŒ, 3 ŌŘƕĀ9cn% 2ŝêĶĮ"öƑĻ}ĳ,
āćEn[gpN¬Æ 2015 ÛĂÅÛ, Ċ, 2015 Û 5 ą 28-29 ā(5) Akihiro Ito and Kazuyoshi Tanaka, “Hetero[1n]cyclophanes Containing Nitrogen and/or Boron
as Bridging Atoms, 10th International Symposium on Macrocyclic and Supramolecular
Chemistry” (ISMSC-2015), Strasbourg, France, 2015 Û 6 ą 28 ā-7 ą 2 ā(6) Ryohei Kurata, Akihiro Ito, and Kazuyoshi Tanaka, “Preparation and Characterization of
2,7-Bis(dianisylamino)pyrene, 16th International Symposium on Novel Aromatic Compounds”(ISNA16), Madrid, Spain, 2015 Û 7 ą 5-10 ā(7) Masashi Uebe, Akihiro Ito, and Kazuyoshi Tanaka, “Synthesis of Triphenylamine Derivatives
Containing Carboranes and Their Electronic Properties” 16th International Symposium on
Novel Aromatic Compounds (ISNA16), Madrid, Spain, 2015 Û 7 ą 5-10 ā(8) Akihiro Ito, Soichiro Yano, Masashi Uebe, Ryohei Kurata, and Kazuyoshi Tanaka, “Electronic
Properties of Boraazacyclophanes” 16th International Symposium on Novel Aromatic
Coumpounds (ISNA16), Madrid, Spain, 2015 Û 7 ą 5-10 ā(9) ĴvqŒ, ťŉŁÆ%¾Ɨ¢ÄĈýŨť, ň 64 ¼Ɨ¢ÄŦŮ,
³, 2015 Û 9
ą 15-17 ā(10) Ŝ æozÓqƁosŷÍ¿oŜâğoĴvqŒ, ŝƇÄ²ĭ¸s6Ĺõ¢ÄŨť: ŝêRi\=Uj9cnūÎƛň 26 ¼¾ľĆė¬ÆŦŮƛċÒƛ2015 Û 9 ą 24-26 ā(11) sŷÍ¿oŜâğoĴvqŒ, @jahn¹Ć?iF9ipj9cn¢Ä&¶î"ƑÄĪêƛň 26 ¼¾ľĆė¬ÆŦŮƛċÒƛ2015 Û 9 ą 24-26 ā(12) ĴÚosŷÍ¿oļƆřqƁoŜâğoĴvqŒ, `<ō¯Ä"ņō¯Ä6Ć
2HBl\8n&¶î"ƑÄĪê&ĐŦƛň 26 ¼¾ľĆė¬ÆŦŮƛċÒƛ2015Û 9 ą 24-26 ā(13) ƗĖqŵosŷÍ¿oŜâğoĴvqŒ, 9cW¾6Ć2_nNLnūÎ&¶î"ƑÄĪêƛň 26 ¼¾ľĆė¬ÆŦŮƛċÒƛ2015 Û 9 ą 24-26 ā(14) sŷÍ¿oƗĖqŵoÕÔµoŜâğoĴvqŒ, @jahn¹Ć?iF9ip
j9cn¢Ä&¶î"ƑÄĪêƛň 26 ¼¾ľĆė¬ÆŦŮƛċÒƛ2015 Û 9 ą 24-26
ā－ 74 －

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Ⅳ 研究業績 (2015)(15) ĂĴĺĚ,oŜ æoĴvqŒ, \lnQ:9ŴžįŮ&óàƢ¢ÄÀá6Ŕí±èê, ň 26 ¼¾ľĆė¬ÆŦŮƛċÒƛ2015 Û 9 ą 24-26 ā(16) ĴvqŒ, CNT &ƈÑê"ŏăŴž&ƍ, ň 50 ¼\hpknoTWOgp]oCh\=nHnbI<d, Ċ, 2016 Û 2 ą 21 ā(17) Katsuyuki Shizu, Motoyuki Uejima, Tohru Sato, Kazuyoshi Tanaka, Chihaya Adachi, andHironori Kaji, “Molecular Design for Highly Efficient Delayed Fluorescence Emitters by
Visualizing Radiative and Nonradiative Decays”, āć¬Æň 96 ĂÅÛ, Ĵŷ, 2016
Û 3 ą 24- 27 ā
６． その他(1) ƃCipnDc@joVPRmpBĈŖî{đ% 2ŰĤđĽŅŕ&,&ťŉ¬Æ, đĽŅŕËű, ƃØîƊĲđ¦żLnNp, 2015 Û 12 ą 17 ā.
(2) ƃÃÆŀ~ůqŧéĽŅLnNpHnbI<d òãŰĤĶê¢ÄĈý&įŮ¬ÆŨť, ŀ~ůqŧéĽŅLnNp, 2016 Û 2 ą 5 ā.
(3) Úî 27 ÛÜ(ň 31 ¼)þĈýoþñş¤ĳĽŅ% 2ŰĤÎƑêƗ¢Ä, đĽŅŕËű, ƙqŲƚıĲƋĶŁÆĽŅð, 2016 Û 3 ą 8 ā.

－ 75 －

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Ⅳ 研究業績 (2015)

５．博士研究員

嶺澤 範行
嶺澤
範行
理化学研究所

計算科学研究機構

研究員

理化学研究所 計算科学研究機構 研究員
1. 今年度の研究の要約
今年度は、(1)PRODAN の分子内電荷移動反応の自由エネルギー解析および(2)スピン反転型時間依存
密度汎関数法 (SF-TDDFT) による非断熱分子動力学シミュレーション手法の開発を行った。

【PRODAN の分子内電荷移動反応の自由エネルギー解析】

溶液における光化学反応のメカニズムを理解するうえで、電子励起状態の自由エネルギーは重要な役割を与える。私は過去の研究において、励起状態の電子状態計算である TDDFT 法と、溶液の積分方程式理論 (RISM) と組み合わせた計算方法を提案している[1]。この論文では、励起状態の自由エネルギーおよびその解析的な微分を使って、励起状態プロトン移動反応を自由エネルギー面で解析を行った。この研究の発展として、励起状態の電子状態が基底状態のそれとは大きく異なる、
分子内電荷移動反応をとりあげた。この反応の場合、自由エネルギーで記述するためには、励起状態に対応した溶媒和を明示的に取り込むことが必要不可欠であることを示した[2]。
本年度の研究では、その応用として 6-propionyl-(N,N-dimethylamino)naphthalene (PRODAN) 分子(図 1) を対象とした。この分子は、電子供与性のジメチルアミノ基と電子吸引性のプロピオニル基をもち、分子内電荷移動状態からの蛍光が確認されている。
電荷移動状態における分子構造として、平面型 (PICT) ある
いはジメチルアミノ基がねじれた構造 (TICT) のいずれかが考えられる。PRODAN 分子に対して、メタノール溶液中における分子内電荷移動反応について自由エネルギー面によ図 1: PRODAN 分子

る解析を行った。過去の研究では、電荷移動状態の溶媒和を明示的に取り込む必要があることを示されている[2]。分子が大きく、計算コストがかかるが、同程度の精度を得られる自由エネルギーの補正を加える[2]ことで解決した。

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Ⅳ 研究業績 (2015)

図 2 に、孤立分子およびメタノール溶液中の PRODAN 分子のエネルギー曲線を示した。
計算条件として、TD-CAMB3LYP/DH+(d)を採用した。気相中のポテンシャルエネルギー曲
線 (Gas) は、ねじれに対して吸熱的である。
溶液中では、補正がない自由エネルギー(LR) では平面型 (PICT) だけが見られ、ねじ
図 2: PRODAN 分子の電荷移動状態のれに対して吸熱的である。対照的に、補正項

エネルギー曲線を加えた 自由エネル ギー曲線 (cLR) では
PICT および TICT のいずれも安定な構造をあたえる。両者の間には反応障壁が存在するため、おそらく前者が有利であると考えられる。この反応障壁は溶媒の極性に依存することが予想される。したがって、PICT と TICT の生成比や蛍光寿命について、現在の計算手法で定性的にではあるが議論できると考えている。

【SF-TDDFT 法による非断熱分子動力学シミュレーション手法の開発】
光励起後の分子の動的過程は、蛍光や燐光といった発光だけでなく、無輻射遷移による基底状態への緩和や化学反応など様々な経路をたどる。これらの複雑で競争的な過程を説明し、光機能材料などの新規分子設計に寄与することが、理論化学計算には求められている。中でも無輻射遷移では、
エネルギーの近接した複数のポテンシャル面が関与し、それらの間の遷移が重要な役割を果たす。
近年、超高速の時間分解スペクトルによる測定が可能となり、励起状態の分子の反応過程が追跡可能となりつつある。したがって、理論計算においてもこうした実験結果を説明するために実時間に対応した動的過程を解析する手法が求められている。
過去の研究で、スピン反転型時間依存密度汎関数法 (SF-TDDFT) が励起状態と基底状態のポテ
ンシャル面の交差が定量的に記述できることを報告した[3]。本研究では、方法論の自然な拡張として、SF-TDDFT 法を非断熱分子動力学シミュレーションと組み合わせた。その結果、電子励起状態からの緩和過程の詳細を明らかにすることが可能となった。本研究では、非断熱分子動力学シミュ－ 77 －

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Ⅳ 研究業績 (2015)

レーションのアルゴリズムとして Tully [4] の fewest switch surface hopping (FSSH) の手法を採用した。この方法は、状態間の遷移の計算に非断熱カップリングが必要とするが、今回 SF-TDDFT レベルの解析的なもの[5]を実装した。SF-TDDFT 計算および断熱分子動力学シミュレーションは電子状
態計算プログラム GAMESS を用い、独自の FSSH プログラムと連結した。
テスト計算として、アゾメタン (CH3-N=N-CH3) の Z→E の光異性化を取り上げた。計算レベル
は、テスト段階のため SF-BHHLYP/3-21G とやや低くしてある。図 3 に示したように、二成分の緩和が見られた。また、それぞれの成分に対応する代表的なトラジェクトリーを図 4 に示した。速い成分 (<80 fs) は Z 体から交差領域に速やかに到達し、基底状態への遷移に一度で成功している。それに対し、遅い成分 (150-250 fs) は円錐交差での一度目の遷移に失敗し、いったん E 体を形成している。その後、E 体から交差領域に到達し、基底状態への遷移に成功している。
従来のポテンシャル面の解析では、励起状態の極小点や反応障壁あるいは円錐交差の同定にとどまり、遷移のしやすさや遷移後の過程は説明できない。本研究で採用した非断熱分子動力学シミュレーションは、ポテンシャ
図 3: アゾメタンの S1 状態の population

ル面の解析を補完する貴重な情報をあたえて

(a)

(b)
図 4: 典型的なトラジェクトリーにおける C-N=N-C のねじれ角(a)速い成分および (b)遅い成分－ 78 －

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Ⅳ 研究業績 (2015)

いる。今後の予定として、プログラムの効率化と大規模分子系への応用が期待される。

【参考文献】

1.

Minezawa, N. Excited-State Free Energy Surfaces in Solution: Time-Dependent Density Functional
Theory/Reference Interaction Site Model Self-Consistent Field Method. J. Chem. Phys. 2013, 138,
244101.

2.

Minezawa, N. State-Specific Solvation Effects on the Intramolecular Charge Transfer Reaction in
Solution: A Linear-Response Free Energy TDDFT Method. Chem. Phys. Lett. 2014, 608, 140-144.

3.

Minezawa, N.; Gordon, M. S. Optimizing Conical Intersections by Spin-Flip Density Functional
Theory: Application to Ethylene. J. Phys. Chem. 2009, 113, 12749-12753.

4.

Tully, J. C. molecular dynamics with electronic transitions. J. Chem. Phys. 1990, 93, 1061-1071.

5.

Zhang, X.; Herbert, J. M. Analytic Derivative Couplings for Spin-Flip Configuration Interaction Singles
and Spin-Flip Time-Dependent Density Functional Theory. J. Chem. Phys. 2014, 141, 064104.

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Ⅳ 研究業績 (2015)

Takuya Saito
Takuya Saito
FIFC Fellow
FIFC Fellow
1. Summary of the research of the year
Driven anomalous diffusion in polymer stretchingLinear polymer suspended in solution takes a fluctuating random coil. We tracked one end called tagged
monomer, which undergoes the anomalous diffusion until the characteristic relaxation time. In this study, weinvestigated driven anomalous diffusion in polymer stretching by pulling tagged monomer.
(i)

Force constant

To see the fluctuation characteristics in highly driven situation, we
checked the fluctuation-dissipation relation that holds in equilibrium
state. If the force is enough weak, the polymer can retain theequilibrium shape. But, if the force is strong, the polymer getslargely deformed and forms the non-equilibrium shape. We firstcarriedoutthemolecular

dynamics

simulations

under

non-equilibrium condition. Repeating the stretching trials, weestablished the average drift and the positon variance. Examining theratio of the variance to the average drift, we observed that the ratio
deviates from the FDR.
We then constructed the theoretical stochastic descriptions tointerpret the FDR deviations on the basis of the mode analysis. Evenin the stretching regime, the initial configuration fluctuations remain
eventually leading to the deviation.
(ii)

Fig.

Velocity constantPulling one end with constant velocity is fairly feasible inexperiments. The generalized Langevin equation formulation

1.

Snapshotsofpolymerstretching in MD simulation. One
end begins to be pulled at t=0.

discussed at the force constant suggests analogous relations, inwhich the momentum fluctuations at constant velocity are expected to show the similar results to those atconstant force. Indeed, we confirmed the analogous results, which show the normalized ratio of the
momentum deviates from the FDR at the high velocity.
The velocity constant, however, makes it difficult to theoretically derive the tagged monomer dynamics
from the microscopic viewpoint. Assuming the decoupled modes, we proposed the equation of stochastic
motion in momentum space. We first discussed the mode analysis in equilibrium and stretching. Combining
them qualitatively reproduces the FDR deviations.
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Fig. 2. Numerical results of <p(t)> (left) and the normalized ratio v<Dp^2>/(k_BT<p>)(right) in polymer stretching at constant velocity.

Driven anomalous diffusion in branched polymer
Developing analyses of branched polymers are inevitable for better understanding of biopolymer
behavior. One of expected examples is proteins, where folded conformations are often regarded as branchedpolymers. The spectral dimension associated with the density of state is known as the way to see theconnectivity.
We developed our anomalous diffusion theory by including the branched polymer with the spectral
dimension in addition to the Flory exponent and dynamical exponents on the basis of the scaling or mode
analysis. Compared with the linear one, the diffusion exponents get smaller as the connectivity increase
more.

Polymer in athermal noise
Recently, the polymer characteristics in athermal or active noise generated by the energy source havebegun to be recognized as the important subjects. If the motion of equation for the objects suspended insolution is written by the Langevin equation, thermal noise is related to the frictional kernel through thefluctuation-dissipation relation. Athermal noise no longer satisfies that. Many theoretical works has reported
the unique anomalous diffusion by adopting exponential decay correlation of the noise. In the study, wedeveloped the scaling theory including the exponential decay, but not relying on the noise detail. In addition,
we discussed the general polymerized objects with arbitrary connectivity, excluded volume effects anddissipation mechanism in the presence of the athermal noise.

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2. Original papers(1) Takuya Saito, and Takahiro Sakaue,“Driven anomalous diffusion: An example from polymer stretching”
Phys. Rev. E 92, 012601(2015).
3. Presentation at academic conferences(1) Takuya Saito“Driven Anomalous Diffusion in Polymer Stretching”
The 13th Fukui Center seminar,
Fukui Institute for Fundamental Chemistry, Kyoto, Sep. 29, 2015.
(2) 齋藤拓也, 坂上貴洋
“駆動される高分子の標識されたモノマーの異常拡散”
日本物理学会 2015 秋季大会, 関西大学 千里山キャンパス, Sep 17, 2015
(3) 齋藤拓也、坂上貴洋“伸張させる条件に依存した高分子の揺らぎの特徴”
日本物理学会第 71 回年次大会, 東北学院大学 泉キャンパス, Mar 22, 2016
4. Others(4) Takuya Saito and Takahiro Sakaue“Driven Anomalous Diffusion in Polymer Stretching”
The 13th symposium of Fukui Institute for Fundamental Chemistry, Kyoto, Feb. 05, 2016.

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Mitsusuke Tarama
Mitsusuke
TaramaMitsusuke
TaramaFIFC
Fellow
FIFC
Fellow
FIFC
Fellow

Summary
researchof theyear
1.1. Summary
of ofthetheresearchof theyear
Reciprocating
motionof active
deformableparticles
Reciprocating
motionof active
deformableparticles

Activemattermatteris isanan
objectpossesses
machinery
to convert
potential
energyActiveobjectthatthatpossesses
machinery
to convert
potential
energyto tokineticenergy
energyandandconsequently
consequently
exhibits
movementby breaking
symmetry.
is a broadkinetic
exhibits
movementby breaking
symmetry.
It is Ita broadconceptincluding
includingboth
bothbiologicalartificial
systems.
Well-studied
activeparticles
concept
biologicalandandartificial
systems.
Well-studied
activeparticles
are arerigidones,
ones,which
whichhave
haveprescribedprescribed
undeformableshape,
as self-propelledcamphorrigid
undeformableshape,
suchsuch
as self-propelledcamphorparticles
colloids
as aswell
as bacteria.
Therealsoalso
existexist
deformableactiveparticles
particlesand
andactive
activecolloids
well
as bacteria.
Theredeformableactiveparticles
thatthetheactivemovement.
Shape
deformation
is ofis basic
thatchangechangetheir
theirshape
shapeduring
duringactivemovement.
Shape
deformationof basic
importancecells
andandmicro-organisms
likelikeeukaryotes.
Besides,
artificial
activeactive
importanceforforliving
livingcells
micro-organisms
eukaryotes.
Besides,
artificial
particles
accompaniedbyshapedeformationarerealisedinliquiddropletsandvesicles.
For Forparticles accompanied by shape deformation are realised in liquid droplets and vesicles.
suchparticles,
variousdynamical
stateshavehave
beenbeen
obtained
eveneven
for anfor an
suchactive
activedeformable
deformableparticles,
variousdynamical
statesobtained
isolatedsingleself-propelledobject.
The
theoretical
study
of
such
activeparticlesarebriefly
isolated single self-propelled object. The theoretical study of such active particles are briefly
dividedOne
is aisdetailed
modelingof eachspecific
example,whichwhich
dividedinto
intotwo
twoapproaches.
approaches.
One
a detailed
modelingof eachspecific
example,enablesandandpropertiesof thesystem.
Besides,sincesince
the theenablesusustotoclarify
clarifythethemechanisms
mechanisms
propertiesof thesystem.
Besides,
examplesofactiveparticles
range
from
biologicaltoartificial
systems,itisalso
importantexamples of active particles range from biological to artificial systems, it is also important
totodevelop
to toelucidate
universal
featuresof miscellaneous
activeactive
developgeneralgeneraldescriptions
descriptions
elucidate
universal
featuresof miscellaneousparticles.
Weareinterested
inthelatteraspectandhavepushedforwards
thedevelopment
of ofparticles. We are interested in the latter aspect and have pushed forwards the developmenta general description of active deformable particles.
a general description of active deformable particles.
Quite recently reciprocating motion has been observed in several different systems. By
Quite recently reciprocating motion has been observed in several different systems. By
reciprocating motion, we refer to a motion of a particle that moves back and forthreciprocating
motion, we refer to a motion of a particle that moves back and forth
periodically along a straight line. One of such systems is an oily droplet floating on aqueous
periodicallyalong
a straightline.droplet,
One ofchemicalsuch systems
is an takeoily droplet
floatingaqueoussolution.
On thesurfaceof thereactionsplace thatcauseonselfsolution. On
surfaceof theit exhibits
droplet, achemical
reactionsplacebeing
thataffectedcause selfpropulsion.
In a thecertaincondition,
reciprocating
motiontake
without
propulsion.
Inacertaincondition,itexhibitsareciprocating
motionwithout
being
affectedby the boundary wall [1]. The second example is a vertically vibrated system of a waterby thefloatingboundarywall [1].
The[2].
seconda verticallyvibratedsystemof aiswater
dropleton viscous
fluid
Amongexample
various is
dynamical
states,a parameterregiondropletfloating
on viscous
fluida [2].
Among various
states,around.
a parameterregion is
found
where
a dropletundergoesreciprocating
motiondynamical
without turning
The third
found wherea dropletundergoesa reciprocating
without
turningaround. The third
exampleis a living
cell which
migratesby blebbingmotion[3]. We
note thata run-and-reverse
exampleisalivingcellwhichmigratesbyblebbing
[3].
We
note
that
a
run-and-reverse
motion has also been observed in some swimming bacteria having front-rear asymmetry[4].
motion
has
also
been
observedinsomeswimming
bacteria
havingfront-rearasymmetry
However, the velocity in the forward motion is different from that in the reverse motion, [4].
However,
the thatvelocityin the forward
motionis different
fromthat inhere,
the wereversemotion,unlikethe case
we consider
in the present
study.
As the last
examplementionunlikethe case that
we consider
the present
study.have
As thelastobtained
example inhere,
we mention
thatreciprocating
motionsof aninisolated
domainbeen
numerical
simulationsof a set ofmotions
reaction-diffusion
equationsdomain
with global
in two dimensions
that reciprocatingof an isolated
havecoupling
been obtainedin numerical[5].
These areofstrong
implications
for whichthe reciprocating
in inhomogeneous
simulations
a set ofreaction-diffusion
equationswith globalmotion
coupling
two dimensions
media
is a genericmotility
in self-propelled
soft systems.
Our aim of
this researchis to[5]. These
are strong
implications
for whichthe reciprocating
motionin homogeneousdevelopsystematic
study
of
the
reciprocating
motionofactivedeformableparticles
media is a generic motility in self-propelled soft systems. Our aim of this researchin is tohomogeneous
media andto clarify
its reciprocating
origin by focusing
on thedevelop systematic
studyof themotionofshape
activedeformation.
deformable particles inhomogeneous media and to clarify its origin by focusing
the account
shape deformation.
By takingoninto
the second- andthird-mode
deformations,asas the andBy taking into accountwell
the secondcentre-of-mass
we haveasintroduced
third-mode velocity,
deformations,well as thea nonlinearly-coupledequationsof motion
centre-of-mass velocity, we haveintroduced
among
them
from
symmetry
considerations.
a nonlinearly-coupled equations of motion
By analysing the equations numerically in aamong them from symmetry considerations.
By analysing the equations numerically in a
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two-dimensional space, we found two route to the reciprocating motion. One is a direct
appearance from a motionless elliptically-deformed particle. Theoretical analysis revealed
that this transition is characterised by the Hopf bifurcation of the trial solution of FitzHughNagumo type equations. The other is more complicated; There is a solution where theparticle moves in a straight line with the speed oscillating in time. There also exists its
mirror symmetric solution that moves in the opposite direction along the same line. These
solutions are represented by limit cycles in the phase space, e.g. the Poincare space of themagnitudes of the velocity and the third-mode deformation. They merge via a saddle point
located at the origin of the space, which represents to the trivial motionless solution, to forma large limit cycle around the origin. See Fig. 1. The resulting limit cycle solution
corresponds to the reciprocating motion. This bifurcation from the pair of the oscillatory
Fig. 1: Trajectory of the centre-of-mass in real rectilinear motion to the reciprocating motion
space (dashed line) with some snapshots of is characterised by gluing bifurcation. In boththesecond-mode
deformation
the particle (gray solid lines) of (a) the cases,
oscillatory rectilinear motion and (b) the determines the axis of motion in thereciprocating motion. (c) Time evolution of homogeneous space. The superposition of thethe magnitude and angle of the centre-of- second-mode deformation and the third-mode
mass velocity and the second- and third- deformation breaks the front-rear symmetrymode deformations of the reciprocating of the particle shape, which couples to the
motion. (d) Attractor in the v ̄-s ̄3 space ofcentre-of-mass velocity vector to achieve thethe reciprocating motion (solid line) and that
periodic back-and-forth oscillation along theof the oscillatory rectilinear motion (dashedline), where the dotted line corresponds to axis.
the attractor of the oscillatory rectilinear
motion that moves in the opposite direction.
The arrows indicate the time-evolution
direction. The figure is taken from M.
Tarama and T. Ohta, Europhys. Lett. 114,
30002 (2016).

The results of this study have recently
been published in Europhys. Lett. 114, 30002(2016): Mitsusuke Tarama and Takao Ohta,"Reciprocating motion of active deformableparticles”.

References:[1] Tanaka S., Sogabe Y. and Nakata S., Phys. Rev. E, 91 (2015) 032406. [2] Ebata H. and Sano M., Sci.
Rep., 5 (2015) 8546. [3] Fujiwara H., Nishigami Y. and Ichikawa M., private communication.[4] Theves M.,
Taktikos J., Zaburdaev V., Stark H. and Beta C., Biophys. J., 105 (2013) 1915; Mitchell J. G., Pearson L. andDillon S., Appl. Environ. Microbiol., 62 (1996) 3716.

Model of a crawling cell

The migration of a biological cell is classified into two groups. One is a
swimming motion in a fluid phase like the motion of bacteria andchlamydomonas, which are two typical examples of swimmers characterised as
pusher and puller, respectively. The other is a crawling motion on a substrate.
Such crawling motion is found in keratocyte and Dictyostelium cells. These cells
exhibit characteristic shape deformation. Keratocyte cells take a crescent shapeand moves with the front in the convex side. On the other hand, Dictyostelium
cells tend to take triangular shape with the front wider and the rear narrower.
See Fig. 2.
Based on symmetry consideration of
migration and shape deformations, we haveformulated phenomenologically the dynamics
of a crawling cell in two dimensions. Forces－ 84 －

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are introduced to change the cell shape, which then induce migration of the cell on asubstrate. For time-independent forces we show that not only a stationary motion but also alimit cycle oscillation of the migration velocity Fig. 2: Stationary shapes of a crawling celland the shape occurs as a result of nonlinear
subjected to constant deformation forces
coupling between different deformation modes.
that have similar characteristics as that of(a) Dictyostelium cell moving to the left
Besides, time-dependent forces are generated inand (b) keratocyte cell migrating upwards.
a stochastic manner by utilizing the so-called
The figure is taken from T. Ohta et al.
coherence resonance of an excitable system.
Physica D 318-319, 3-11 (2016).
The present coarse-grained model has aflexibility that it can be applied, e.g., both to keratocyte cells and to Dictyostelium cells,
which exhibit quite different dynamics from each other. The key factors for the motile
behavior inherent in each cell type are identified in our model.
We have proposed that the correlation between the deformations and the migration
velocity plays an important role in the cell crawling. Such correlation exists even without
the nonlinear coupling between the second- and third-mode deformations. The nonlinear
coupling yields more persistent motion. That is, the cell tends to migrate without largechanges of the direction for the same intensity of the random noises as that in the linear
case. Similar dynamics was also observed in the experiment of Dictyostelium cells by
Maeda et al. [5]. They have made a systematic comparison of the motility in a starved
condition and a vegetative condition. A cell in a starved condition migrates at a larger
velocity and elongates in the direction parallel to the migration direction. Its trajectory ismuch more persistent than in a vegetative condition.
The results obtained in this study are summarized in the paper published as in theOriginal papers (1).
References:[5] Y.T. Maeda, J. Inose, M.Y. Matsuo, S. Iwaya, M. Sano, PLoS One 3 (2008) e3734.

2. Original papers(1) Takao Ohta, Mitsusuke Tarama, and Masaki Sano,“Simple model of crawling cell”
Physica D 318-319, 3-11 (2016).
3. Presentation at academic conferences(1) Mitsusuke Tarama, and Takao Ohta,“Oscillatory motion of active deformable particles”
8th International Conference Engineering of Chemical Complexity, IAS, Technische
Universität München, Garching, Müchen, Germany, 23 Jun., 2015 (poster).
(2) Mitsusuke Tarama, and Takao Ohta,“Oscillation of active deformable particles”
International Symposium on Fluctuation and Structure out of Equilibrium 2015 (SFS2015),
Inamori Hall, Shiran-kaikan, Kyoto University, Kyoto, Japan, 21 Aug., 2015 (poster).
(3) Mitsusuke Tarama, and Takao Ohta,“Reciprocating motion of active deformable particles”
Hierarchical Dynamics in Soft Materials and Biological Matter, Kyoto University, Kyoto,－ 85 －

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Japan, 24 Sep., 2015 (poster).
(4) Mitsusuke Tarama,“Active deformable droplet in external flow field”
Workshop on "Aspects of motions in biofluid problems", RIMS, Kyoto University, 26 Oct.,
2015 (oral).
(5) 多羅間充輔,“アクティブソフトマターの非線形ダイナミクス”
第５回ソフトマター研究会, 東北大学 青葉山キャンパス, 17 Dec., 2015 (oral:
invited).
(6) Mitsusuke Tarama and Takao Ohta,“Oscillatory dynamics of active deformable particles”
Pacifichem 2015: Self-organization in Chemistry (#165) [3A], Honolulu, Hawaii, 18 Dec.,
2015 (oral).
(7) 多羅間充輔,“一様空間中における自発的な往復運動の発現”
アクティブマター研究会 2016, 九州大学 箱崎キャンパス 国際ホール, 22 Jul., 2016
(oral).
(8) 多羅間充輔,“アクティブマターの往復運動への分岐”
日本物理学会第 71 回年次大会, 東北学院大学 泉キャンパス, 22 Mar., 2016 (oral).

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4. Others(1) Mitsusuke Tarama“Nonlinear dynamics of active deformable particles”
山本研セミナー, 京都大学大学院工学研究科, 22 Apr., 2015.
(2) Mitsusuke Tarama“Nonlinear dynamics of active deformable particles”
菊池研セミナー, 大阪大学 サイバーメディアセンター 大規模計算研究部門, 10
Jul., 2015.
(3) Mitsusuke Tarama“Nonlinear dynamics of active deformable particles in external flow field”
R 研セミナー, 名古屋大学大学院理学研究科物理学教室 R 研, 20 Jan., 2016.
(4) Mitsusuke Tarama“Nonlinear dynamics of active deformable particles”
Seminar in the group of Prof. Pierre Sens, Institute Curie, Paris, France, 11 Feb., 2016.
(5) Mitsusuke Tarama“Nonlinear dynamics of active deformable particles in an external flow field”
Seminars “Makroskopische Eigenschaften komplexer Fluide”, Universität Bayreuth,
Germany, 25 Feb., 2016.
(6) Mitsusuke Tarama“Nonlinear dynamics of active deformable particles”
Seminar in the group of Prof. Markus Bär, Physikalisch-Technische Bundesanstalt, Berlin,
Germany, 1 Mar., 2016.

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Yoshio Nishimoto
FIFC
Fellow
FIFC Fellow
1. Summary of the research of the year
Development of the FMO-DFTB Method
I’m developing a large-scale quantum-mechanical method, called FMO-DFTB,1 these days.
FMO-DFTB is a combined method between the fragment molecular orbital approach and thedensity-functional tight-binding method.
The first development is FMO-DFTB3.2 Considering the recent progress of the DFTB method, it is ofgreat importance to make FMO-DFTB applicable to polarized or biological systems. The inclusion of thethird-order correction modifies both the internal energy and the electrostatic potential (ESP) contributions infragment calculation. FMO-DFTB3 reproduced relative stabilities and the optimized structures of threepolyalanine (α-helix, β-sheet, and extended) isomers obtained with the corresponding full (e.g., without
fragmentation) DFTB calculation. FMO-DFTB3 was applied to optimizing a nano flake of cellulose 1β,
consisting of 10 944 atoms, and a good agreement with the experimental structure was obtained. For acellulose sheet containing 1368 atoms, FMO-DFTB was 43.5 times faster than the corresponding full
DFTB3 calculation. The binding between sheets and chains in cellulose was elucidated, and two dispersion
models were compared. This study has been published on Chemical Physics Letters.2
In addition, the fully analytic gradient of FMO-DFTB has been developed.3 The FMO approach is nota fully variational method, one has to include the orbital response contributions in calculating the derivativeof the total energy with respect to nuclei. The previous FMO-DFTB has ignored the contributions, but theymust be properly taken into account to perform molecular dynamics (MD) simulations; otherwise energy
may not be conserved in NVE ensemble. In order to obtain the fully analytic gradient, although solving thecoupled-perturbed equation is seemingly a straightforward approach, one has to solve 3Nat, where Nat is thenumber of atoms in the whole system, response equations per iteration, and they depend on the size of theentire system. Therefore, the self-consistent Z-vector (SCZV)4 method was employed instead. The accuracyof the implemented analytic gradient was demonstrated on water clusters and a polypeptide and is reasonably
high. For instance, Figure 1 shows the difference between analytic and numerical FMO-DFTB3 gradients for(H2O)64. The error of the analytic gradient, red filled circles, is rather small. The root-mean-square andmaximum deviations of gradient are 0.000 002 and 0.000 006 a.u./Bohr with the response contributions,while they are 0.000 140 and 0.000 657 a.u./Bohr otherwise. The cost for SCZV is similar to the monomer
self-consistent-charge step. The radial distribution functions (RDFs) obtained with FMO-DFTB are found tobe similar to those from conventional DFTB, while the computational cost is greatly reduced: 73.26 and 0.68
s with full DFTB and FMO-DFTB, respectively, showing a speed-up factor of 108 with FMO-DFTB. As apossible application, FMO-DFTB/MD was applied to 100 ps MD simulations (one million step) of liquidhydrogen halides ((HX)1000; X = F, Cl, Br, and I). FMO-DFTB calculation takes 1.8 s per MD step, while full－ 88 －

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Figure 1. Differences between analytic and numericalFigure 2. X-X radial distribution functions,

FMO-DFTB3 gradients for (H2O)64. Red filled and blackshown with black solid (X = F), red dotted (Cl),empty circles indicate the values (gradient errors) withblue dashed (Br), and purpose dashed-dot (I)and without the response terms.

lines.

DFTB does 1816 s. The RDFs obtained with the MD simulation are plotted in Figure 2. The method chosen
in the study (FMO-DFTB2 with the UFF dispersion correction) gives reasonable RDFs of the hydrogen
halides. FMO-DFTB/MD looks like a promising tool for QM/MD simulations of large systems, considering
its low computational scaling and high parallel efficiency. This study is published has been published on the
Journal of Physical Chemistry Letters.3
More recent developments, combination between FMO-DFTB and PCM, were summarized, and themanuscript was submitted.

Development of Excited-State Methods with DFTB
I completed two developments in the time-dependent version of DFTB (TD-DFTB). The first one isthe extension of the previous TD-DFTB2 formalism5 to the recent DFTB36 method, named TD-DFTB3.7
Regarding the formulation, one additional term that comes from the second-order derivative of thethird-order energy with respect to the density matrix is needed in computing excitation energies. In
computing the analytic gradient with the Z-vector method, the third-order derivative of the third-order energy
with respect to the density matrix is required. This term was assumed to be zero in TD-DFTB2. Since thethird-order derivative term does not appear in Hartree-Fock, the new term may be viewed as a
pseudo-exchange-correlation functional for DFTB. Improvement of DFTB3 for typical small molecules over
DFTB2 in adiabatic excitation energy is not notable. Nevertheless, DFTB3 is supposed to be superior to
DFTB2 for polar and hydrogen bonded systems, so it is still early to conclude that TD-DFTB3 does not
improve excited state properties. Therefore, the absorption and fluorescence energies of cresyl violet, whichcontains one positive charge, in explicit water molecules have been calculated as a practical test example.
The ten structures generated in the study consist of 323-404 atoms (cresyl violet plus 97 to 124 watermolecules), so TD-DFT calculation for the systems is rather challenging in terms of the computational cost.
The calculated excitation energies are summarized in Table 1. Although the absorption energies were
overestimated relative to the experimental result,8 the agreement of the TD-DFTB3 fluorescence energy with－ 89 －

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Table 1. Experimental (ref. 8) and calculated absorption and fluorescence energies (unit in eV) for cresyl violet
and oscillator strengths. Calculated energies and oscillator strengths in water are the averages of 10geometries. Values in parentheses represent lower and upper bounds of 10 energies.
Excitation energies
MethodAbsorption

Fluorescence

Oscillator strength
Absorption

Fluorescence

TD-DFTB2 (in vacuum)

2.46

2.10

0.452

0.200

TD-DFTB3 (in vacuum)

2.50

2.15

0.429

0.187

TD-DFTB2 (in water)

2.40 (2.35/2.44)

1.93 (1.80/2.03)

0.427

0.175

TD-DFTB3 (in water)

2.46 (2.43/2.49)

1.96 (1.86/2.09)

0.442

0.157

Experiment (in water)

2.12

1.96

N/A

N/A

the experiment was fairly promising.
In addition, (TD-)DFTB/PCM9 has been developed. In particular, the analytic gradient of
TD-DFTB/PCM excitation energy has not been available in any program packages. The benchmark
calculation in this study shows that TD-DFTB/PCM is comparable with TD-DFT/PCM using GGA
functionals such as PBE and BLYP. However, these methods underestimate absorption and emission energies,
compared with experiment. This should be attributed to the lack of long-range corrections. It has beenchallenging for DFTB to treat biological systems unless fractional occupation numbers or explicit solvent
molecules are used, because of the band-gap problem for DFTB and GGA functionals. Solute-solvent
electrostatic interactions alleviate the band-gap problem, and thus it is possible for us to apply DFTB to
realistic biological systems. In this study, (TD-)DFTB/PCM has been applied to a DNA-TOTO complex,
PDB ID: 108D, which consists of 619 atoms, full excited-state calculations with DFT or wavefunction
methods are very challenging. Minima on S0 and excited-state potential energy surfaces were successfully
obtained using TD-DFTB/PCM, and it is predicted that the enhancement of fluorescence energy of TOTO is
attributed to the prohibition of rotation of TOTO when it is intercalated into the DNA.
All the developed methods are implemented in GAMESS-US and will be available in the next official
release of it.
References
1. Nishimoto, Y.; Fedorov, D. G.; Irle, S. J. Chem. Theory Comput. 2014, 10, 4801-4812.
2. Nishimoto, Y.; Fedorov, D. G.; Irle, S. Chem. Phys. Lett. 2015, 636, 90-96.
3. Nishimoto, Y.; Nakata, H.; Fedorov, D. G.; Irle, S. J. Phys. Chem. Lett. 2015, 6, 5034-5039.
4. Nagata, T.; Brorsen, K.; Fedorov, D. G.; Kitaura, K.; Gordon, M. S. J. Chem. Phys. 2011, 134, 124115.
5. Niehaus, T. A.; Suhai, S.; Della Sala, F.; Luigi, P.; Elstner, M.; Seifert, G.; Frauenheim, T. Phys. Rev. B
2001, 63, 085108.
6. Gaus, M.; Cui, Q.; Elstner, M. J. Chem. Theory Comput. 2011, 7, 931-948.
7. Nishimoto, Y. J. Chem. Phys. 2015, 143, 094108.
8. Kreller, D. I.; Kamat, P. V. J. Phys. Chem. 1991, 95, 4406-4410.
9. Nishimoto, Y. J. Phys. Chem. A 2016, 120, 771-784.
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2. Original papers(1) Yoshio Nishimoto, Dmitri G. Fedorov, and Stephan Irle
“Third-order density-functional tight-binding combined with the fragment molecularorbital method”
Chem. Phys. Lett. 636, 90-96 (2015).
(2) Yoshio Nishimoto"Time-dependent density-functional tight-binding method with the third-order expansionof electron density”
J. Chem. Phys. 143(9), 094108 (2015).
(3) Yoshio Nishimoto, Hiroya Nakata, Dmitri G. Fedorov, and Stephan Irle
“Large-Scale Quantum-Mechanical Molecular Dynamics Simulations Using
Density-Functional Tight-Binding Combined with the Fragment Molecular Orbital
Method”
J. Phys. Chem. Lett. 6(24), 5034-5039 (2015).
(4) Yoshio Nishimoto“DFTB/PCM Applied to Ground and Excited State Potential Energy Surfaces”
J. Phys. Chem. A 120(5), 771-784 (2016).
3. Presentation at academic conferences(1) Yoshio Nishimoto“Time-dependent density-functional tight-binding method with the third-order expansion
term”
The 9th Annual Meeting of Japan Society for Molecular Science (3P114), Tokyo, September
18, 2015(2) Yoshio Nishimoto“Method Developments for the Time-Dependent Density-Functional Tight-Binding(TD-DFTB) Method”
The 96th CSJ Annual Meeting (4B4-38), Kyoto, March 27, 2016
4. Others(1) Yoshio Nishimoto“Method Developments for the Time-Dependent Density-Functional Tight-Binding(TD-DFTB) Method” The 13th symposium of Fukui Institute for Fundamental Chemistry,
Kyoto, Feb. 5, 2016.

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Miho Isegawa
Miho Isegawa
FIFC Fellow
FIFC Fellow(1) Mechanistic difference of copper(I) and copper(II) catalysis in boron conjugation addition
The sysnthesis of optically active boron compounds are crucial in pharmaceutical applications, because
the carbon-boron bond can be replaced by such as carbon-carbon, carbon-nitrogen, and carbon-oxygen bonds. For
the carbon-boron bond formation, the catalytic function of the cooper(I) has been well examined, however, thecatalytic function of copper(II) has not been addressed.
Recently, Zhu et al. 6 have reported copper(II)-based strategy for the catalytic asymmetricβ-borylation.
The enantiomeric excess of the reaction in scheme 1 shows high enantioselectivity (ee = 94%) using copper(II)catalysis with chiral ligand and diethylether as a solvent. In contrast, the copper(I) catalysis with the same ligand
and THF solvents shows no selectivity. Here thedielectric constant of THF is close to the diethylether,and it is expected that the both solvents ofdiethylether and THF do not coordinate to the coppersite. These facts imply that copper(I) and copper(II)gives different reaction mechanism in the process of

Scheme 1. Enatioselevtive reaction for the formation ofcarbon-boron bond formation.

alcohol.

The reaction given in scheme 1 can bedivided into three processes. The first is formation of LCu-B(pin) catalysis. This reaction is described as
metathesis process in which copper-boron bond formation and boron-boron bond cleavage simultaneously takes
place. The second step is enantioselective process with the carbon-boron bond formation and the process whichis the most focused on in this study. The third step is hydroxylation process which takes place stereoselectively.
Our purpose in this study is to elucidate the mechanistic difference of copper(I) and cooper(II) catalysis
in the boron conjugation addition. In order to reveal thereaction mechanism, it is crucial to locate the transition
and global/local minima. The transition state is estimatedusing artificial force induced reaction (AFIR) simulation
which are one of powerful methods to detect theapproximate geometry of transition state. Thus, obtained
approximate transition state is refined by full QM
calculation with conjunction of implicit solvation model(SMD). To predict the dominant product in the

Figure 1. Functional groups given by blue are treatedenantioselective process, one needs to know the relative

by ONIOM low level (PM6) and the rest of parts arestability of the most stable transition state for each R-

treated by high-levels (M06-L). The attractive artificial

and S- form. To detect the most stable transition state,

force was applied into atoms circled by red.

we applied multi-component AFIR method.

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Ⅳ 研究業績 (2015)(2) Reaction mechanism of H2 and O2 activation of [NiFe] core
Hydrogen molecule is promising energy resource in our near future as alternative fuel of fossil fuel.
Therefore, the construction of the catalytic system which can efficiently produce hydrogen is crucial toattack to the energy problem.
Recently, Ogo et al. succeeded to synthesize organometallic
compound which is able to catalyze the activation of hydrogen molecule(Figure 2 ). This catalysis is made by nickel and iron both of which areearth abundant metal, therefore the derivative of this catalysis can be a
candidate for the realistic application. As more details, this catalysis
works in the polar organic solvent and the hydrogen bonding cleavage isachieved by added strong base (MeONa). In addition, the notable point isthat both hydride transfer and electron transfer is possible in the hydride
binding complex as same as [NiFe]H2ase. On the other hands, thedifference from [NiFe]H2ase is that the hydride binding site is Fe center
rather than Ni center.

Figure 2. Experimentally proposed

The main purpose of this study is to characterize the electronic
structure of all of intermediates and reveal the reaction mechanism ofreaction mechanism for H2 activation
by [NiFe] core.

hydrogen molecule activation based on density functional theory. For thelocation of the transition state, we employed artificial force induced reaction (AFIR) approach.

(3) O2 activation of [NiFe] core
The O2 activation is possible using analogous catalysis to that used in H2 activation. Figure 2 shows
the catalytic cycle experimentally suggested by Kishima et al. The only difference between catalysis which
activates hydrogen molecule and oxygen molecule is the ligands which directly bind to the iron center. The
ligands used in the O2 activation has the character of strong electron donation to iron site, which allows theelectron moving to the electron of d-orbital to the π* molecular orbital of oxygen molecule orbital. In
contrast, the ligand which can activate H2 shows the character of electron
withdrawing, therefore the more electron poor condition is realized iniron site for H2 activation. In the catalysis for O2 activation, the O2 binds
Fe site withη2 fashion according to the X-ray structure. The preferenceof the iron site is consistent with the catalysis in the H2 activation. This isworthwhile to examine carefully.
In this study, catalytic process is examined dividing into two
process, (1) O2 binding process (2) O2 bond cleavage process. The
starting compounds for both of processes are well characterized with
spectroscopic measurement. We explore all of possible binding patterns
including different spin multiplicity including experimentally undetected
species.

Figure 3. Experimentally proposed
reaction mechanism for O2 activation
by [NiFe] core.

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Satoshi Suzuki
Satoshi Suzuki
Research Fellow
1. Summary of the research of the year
1.1

Exploration of Quenching Pathways of Multiluminescent Acenes Using the GRRM
Method with the SF-TDDFT Method

The quenching pathways were investigated for three types of multiluminescent acene derivatives,
which show environment-dependent fluorescence. Spin–flip time dependent density functional
theory (SF-TDDFT) combined with the Global Reaction Route mapping (GRRM) strategy is
employed to locate minimum-energy conical intersections (MECIs). The energies and geometries ofthe MECIs relative to the Franck–Condon (FC) state control the difference in fluorescence behavior
among the three derivatives. For the molecule with a phenyamide moiety, a MECI with energy
lower than the FC state with large geometrical change from V-type to flat structure provides anefficient internal conversion (quenching) pathway in solution. For the same molecule, in a solid,
this large geometrical change is inhibited, and the second MECI, with an energy lower than FC but
higher than the first MECI requiring only a small geometry change of CH out-of-plane bending,contributes to the quenching. The molecule with the napthaleneimide moiety has only one
low-energy MECI that requires large geometrical change from the V-type to flat structure. Although
this MECI provides the quenching pathway in solution, in the solid, this large motion is inhibited,
and the molecule will stay in the excited state and emit. The molecule with an anthraceneimide
moiety has no conical intersection lower than the FC state, and no quenching pathway is available
in solution or solid. In addition, in this molecule, at the local minimum of the excited state, thedipole transition to the ground state is allowed, and this molecule prefers emission rather thaninternal conversion.

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1.2 ビスジアルキルアミノアントラセン類における凝集誘起発光(AIE)の起源
9,10-bis(N,N-dialkylamino)anthracene(BDAA) はアルキルアミノ基で置換されたアントラ
セ ン であ り、 その シン プル な分 子構造に も かか わ らず凝集誘 起発光(aggregation-induced
emission:AIE) を起こす。多くの蛍光分子では凝集により発光性は低下する。AIE は非蛍光性の分子が凝集により蛍光性を持つようになる。一連の BDAA において、大きなストークスシフトが観測され、自己吸収が起こりにくいことが AIE の一因であると実験的に示唆された。
まず、大きなストークスシフトがどのような構造変化によって起こるのかを計算によって確認した。
また、BDAA が溶液中で光りにくい原因は溶液中では内部転換による失活が起こりやすいのではないかという過程のもと、（気相中での）円錐交差を計算した。内部転換は円錐交差周辺で起こりやすく、もし円錐交差がエネルギー的に到達不可能であれば内部転換が起こりにくく、溶液中でも光りやすいと考えられる。さらに、液相と固相での発光性の差を議論するために ONIOM法を用いた円錐交差探索を行った。
A)ストークスシフトの原因
9,10-bis(N,N-dimethylamino)anthracene(BDAA-methyl)の基底状態での安定構造と励起状態での安定構造を計算した。基底状態ではアミノ基がアントラセンに直交する構造が安定であり、syn 体と anti 体が存在する。励起状態では syn 体 anti 体どちらから構造最適化をスタートしても、一つのアミノ基が平面になる共通の Local Minimum に落ち込むことが示唆された。この構造ではアミノ基はアントラセンに直交している。また、二つのアミノ基が平面になるが、アントラセン部分に対して直交していない構造も励起状態の Local Minimum として存在することがわかった。この二種類の Local Minimum はエネルギー的にはほぼ同程度で、間にあるバリアーも低いため、共存しうる。いずれの Local Minimum からの発光だとしても蛍光波長は実験値を再現するため、これらの構造のいずれかからの起こると考えられる。

B)気相中での円錐交差
BDAA-methyl の円錐交差を CASSCF/6-31G(d)レベルで計算した。この系では芳香環の大きな歪みを含む円錐交差が存在し、そのエネルギーはフランクコンドン状態に比べて 50ｋJ/mol 程度
安定である。つまり、フランクコンドン状態からエネルギー的には MECI へは到達であり、それがこの分子が内部転換しやすいことを示唆している。一方で、芳香環の折れ曲がりがあることから
このような構造は凝集時には周辺からの立体制約を強く受けると予想される。円錐交差が立体制約を受けることで凝集時に内部転換しづらくなり結果的に発光しやすくなるものと考えられる。

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C)固相中での円錐交差
固相中での立体的な制約を見積もるために固体中でも MECI の構造最適化を行い比較した。固相のモデリングには ONIOM 法を採用した。励起状態の分子が基底状態の分子に囲まれているモデルの円錐交差を ONIOM(CASSCF/6-31G:PM6)レベルで計算する。立体的制約が主たる AIE の原因であることを前提としているので、いわゆる MechanicalEmbedding で励起状態の分子と環境との相互作用は記述できると考えて良い。CASSCFの電子状態を GAMESS で PM6 計算を Gaussian09 で行い、構造最適化は GRRM プログラ
ムを呼ぶようなインターフェースを作成した。これを用いて固相中の9,10-bispiperidylanthracene(BDAA-piperidyl)の円錐交差を計算した。参照として気相での円錐交差も計算した。
BDAA-piperidyl についても BDAA-methyl 類似の円錐交差が低エネルギー領域に存在する。
この円錐交差も BDAA-methyl の場合同様、フランクコンドン状態に比べてかなり安定である。
一方、この構造に対応する固相中での円錐交差を計算するとエネルギーは遥かに不安定化し、フランクコンドン状態よりも 100ｋJ/mol 以上も高エネルギーとなる。

BDAA-piperidyl の気相中での円錐交差構造－ 96 －

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一方、変位の比較的小さい、アントラセン部分の面外変角による円錐交差も存在するが、こちらは気相中でも固相中でもエネルギーが高く内部転換には関わらないと考えられる。以上のこと
からこの分子における固相での発光しやすさについて、定性的には説明ができた。

2. Original papers(1) S.Suzuki, S. Maeda, K. Morokuma
Exploration of Quenching Pathways of Multiluminescent Acenes Using the GRRM
Method with the SF-TDDFT Method
J. Phys. Chem. A, 119 pp 11479–11487 (2015)(2) S.Sasaki, S.Suzuki, W.M.C. Sameera, K. Igawa, K. Morokuma, G. Konishi,
Highly twisted N,N-dialkylamines as a design strategy to tune simple aromatichydrocarbons as steric environment-sensitive fluorophores
J. Am. Chem. Soc., accepted
3. Presentation at academic conferences(1) 環境依存発光を示すアセンの消光経路探索
会 2015 大阪

◯鈴木聡

諸熊奎治

理論化学討論

4. Others－ 97 －

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Akhilesh Kumar Sharma
Akhilesh Kumar Sharma
Research Fellow
Research Fellow
1. Summary of the research of the year
Computational Insights on the Mechanism and the Origin of Enantioselectivity in
Fe-Catalyzed Cross-Coupling Reaction
Transition metals are being used in homogenous catalysis for a long time for variety of transformations,
including cross-coupling reactions and formation of asymmetric compounds. Cross-coupling reactions areimportant and versatile tool to synthesize variety of compounds of industrial and pharmaceutical importance.
The most popular coupling reactions are Pd-catalyzed, as evident from the 2010 noble prize in Chemistry fordeveloping these reactions. The efforts for development of new methods involving non-toxic and readily
available metals for coupling reactions are increasing nowadays. The Fe can be very important in this regard,as it is non-toxic, readily available and is known to catalyze many enzymatic processes. The research interestfor the development of Fe catalyzed reactions is increasing. The mechanistic understanding of Fe–catalyzed
reactions is important for further development in this field.
Recently, M. Nakamura and coworkers have reported first Fe-catalyzed enantioselective
cross-coupling reaction between aryl Grignard reagent (ArMgBr) and organic halide (R-Cl) (Scheme 1a).
They proposed that the reaction proceed through out-of-cage mechanism (Scheme 1b). On the basis ofradical probe studies radical pathway was proposed. The mechanism of the reaction is not established andthere is no clear understanding on the origin of enantioselectivity. We have studied the mechanism ofreaction using DFT methods. The AFIR method as implemented in GRRM program is used to explore
potential energy surface of the reaction.
P

MgBrClP

PhMgBr

Cl

II X

Fe

2PP

X = Ph or Cl

COOR
S1

Ph

P
P

P
P

II X

Fe

2PX

P

Cl

P
In-Cage
Mechanism

2PP
tBu

P
P
PhMgBr +

Me
Cl

COOR'

Me

P

Fe(acac)3
3 mol %

PtBu
6 mol %

THF, 0°C

Me
Ph

COOR'

COOR

(a)

Ph

P
Me tBuR=+

COOR Out-of-Cage
Mechanism
COOR

P

P1

III X

Fe

3PPX

P1

1P
Ph

90:10 er

Racemic

I

Fe X

Cl

Me
P

COOR
S2

Ph

3PPX

Me

tBu

=

P

III

Fe
X

2PP
3PPX

Ph

4PPR

(b)

Scheme 1. (a) Fe-catalyzed enantioselective cross-coupling reaction. (b) The proposed in-cage andout-of-cage mechanism.
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The different Fe-catalyzed coupling reactions involving phosphine ligands are proposed to go throughFe(II) species. We studied the thermodynamics of generation of Fe(II) species from reagents. We found thatthe energy of Fe(I) and Fe(II) differs only by a small amount (2.7 kcal/mol). The possibility of coordinationof solvent (THF) molecules to Fe and Mg are also explored. MC-AFIR method is used for exploring
different conformational transition states and intermediates in different steps. The different spin states of theintermediates involved in the reaction are also considered. It is found that for Fe(I) (1P, 1X), Fe(II) (2PP , 2PX)
and Fe(III) (3PPX, 3PPR, 4PXR) the lowest energy spin states are quartet, quintet, and quartet respectively.
The reaction involves three important steps, viz., Fe-catalyzed atom transfer reaction leading to
generation of alkyl radical, C-C bond formation and transmetalation. Among the different possible Fe(II)species, [Fe(PP*)Ph2] (2PP) is found to be of lowest energy. However, the reaction starting from [Fe(PP*)Ph2]
is less likely, as the activation barrier for biphenyl formation is less from the Fe(III) species (3PPX and 4PPR)in comparison to forward reaction through the proposed in-cage or out-of-cage reaction mechanism (Scheme1b). It is in agreement with experimental method which requires slow addition of Grignard reagent. The C-C
coupling from 3PPX is found to have higher activation barrier than coupling from 2PP (Scheme 1b). Hence, thereaction through in-cage mechanism is less likely in comparison to out-of-cage mechanism.
The activation barrier for C-Cl activation through other lower energy Fe(II) species, [Fe(PP*)PhCl] ishigh (24.0 kcal/mol). Hence, the reaction through Fe(II) species is less probable. As the reaction involves
Fe(I), Fe(II) and Fe(III) species, we also considered C-Cl activation from Fe(I) and Fe(III) species.
Interestingly the activation barrier for the C-Cl activation by Fe(I) is found to be very low.
C-Cl Homolytic
Clevage

Cl

COOR 4 4.2 (-8.7)
S1

COOR

4 0.0

P
Cl
S1

P
2XX +

COOR

S2
P
P

I
Fe
1X

Cl

COOR

MgBrCl

P

P

II

Cl

+

Ph

Fe

COOR
S2

P
COOR

P
PhMgBr

P
2PX

Cl

Ph

P1

Cl

II

Fe

P

S2

(0.0)
1X

P

COOR

P

II Cl

Fe
4XXR Cl-20.2 (-35.2) -19.3 (-33.7)

I

Fe Cl

C-C Bond
Formation

Transmetallation / Fe-C Coordination

4
PhMgBr -24.0 (-27.1) XXR
5 -29.0

P

II

Fe

Cl
Cl

5 -38.3

P

III ClFe
Ph

4 -33.4

MgBrCl(-27.0)2XXP-30.6 (-43.7)

P(-36.4)

2PX
II

Fe

Ph

S2

COOR
P1

4 -42.8(-59.5)
4PXR
COOR

Cl
P

4PXR

(a)

Ph

COOR

P

COOR

(-49.2)

III PhFeCl

4 -67.5

PP(-68.0)
I

Fe Cl

(b)

Figure 1. (a) The catalytic cycle based on computational results. (b) Free energy profile at B3LYP-D3BJ for
the preferable mechanism in Fe-catalyzed coupling reaction.
The most probable mechanism according to our calculation is given in Figure 1. In the first step C-Cl
activation occurs through atom transfer mechanism leading to generation of 2XX and S2. The active species
for C-Cl activation is Fe(I), not Fe(II) as proposed in literature (Figure 1). As the activation barrier for this－ 99 －

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step is very small, the kinetic resolution of substrate could not be observed. The next step can betransmetalation or Fe-C coordination. The Fe-C coordination from 2XX is found to be thermodynamicallyunfavorable. Activation barrier for transmetalation is low and it converts 2XX to lower energy intermediate
2PX. Lower concentration of Grignard reagent diminishes the possibility of further conversion of 2PX to 2PP
by transmetalation. The C-C coupling occurs through Fe(II) intermediate (2PX) as proposed by M. Nakamuraand coworkers. It occurs by inner sphere mechanism. It involves first coordination of radical species S2 to
2PX (Fe(II) species) leading to formation of Fe(III) intermediate 4PXR, followed by reductive elimination. The
calculations for delineating factors responsible for origin of stereoselectivity are in progress. Both Fe-C bondformation and C-C bond formation step could be enantioselectivity determining.

2. Original papers(1) W. M. C. Sameera, Akhilesh Kumar Sharma, Satoshi Maeda, Keiji Morokuma,“Artificial Force Induced Reaction Method for Systematic Determination of Complex
Reaction Mechanisms”
Chem. Rec. 2016, (Accepted).
3. Others (Presentation at symposium)(1) A. K. Sharma, W. M. C. Sameera, M. Nakamura and K. Morokuma“Computational Insights on the Mechanism and the Origin of Enantioselectivity in
Fe-Catalyzed Cross-Coupling Reaction” The 13th symposium of Fukui Institute for
Fundamental Chemistry, Kyoto, Feb. 5, 2016.

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Ⅳ 研究業績 (2015)

Pedro J. CASTRO
Pedro
J. Castro
Postdoctoral Fellow

Postdoctoral Fellow
1.

Research activities during FY2015 (October 2015 – March 2016)

Once the matter is excited with electromagnetic radiation a large number of deactivation pathways competewith each other to decay to the ground state. These deactivation routes can take place through radiative orradiationless processes. As a consequence, some compounds exhibit phenomena such as fluorescence,
phosphorescence and photochromism. These photochemical properties have a large amount of applications
in different fields, from electronic devices devolvement to health care. Therefore, the understanding of themechanisms leading to these phenomena guides to the rational design of photofunctional compounds. We
have attempted to study these compounds from a static and dynamic point of view by combining methods
based on TD-DFT and Trajectory Surface Hopping (TSH) approach. We have used TD-DFT and spin-flip(SF)TD-TDFT in order to describe energy and the electronic structure of the excited states. We haveautomatically explored the potential energy surfaces using the global route reaction mapping (GRRM)
method via artificial force induced reactions (AFIR). The minimum energy conical intersections (MECI)
were optimized using GRRM-MSX algorithm. The S1/S0-MECI were calculated using either MCSCF or
using the lowest triplet (T1) as reference via (SF)TD-DFT in order to describe the wavefunction for S1 and S0
in a balanced way.
2.

ResumeA. Non-adiabatic dynamic on the Photochemistry of 4,4-difluorobut-2-enal using TD-DFT and
TSH approaches.

The photochemical reactions of small molecules occur upon irradiation by ultraviolet or visible light, andthey are a very important chemical process in Earth’s atmosphere, in the atmospheres of other planets, and ininterstellar media. Small unsaturated carbonyl compounds play an important role in the chemistry of thepolluted troposphere. The fluorinated aldehydes are very reactive under the sunlight driving to species which
trigger more atmospheric reactions. This work is concerned a theoretical study of the photochemistry of
difluoro-crotonaldehyde. We report the photochemical reaction paths starting from the cis-keto isomer. The
initial excitation populates the S3(ππ*), the main deactivation channels follow non-adiabatic pathways via－ 101 －

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S1/S0 conical intersections. The S1 can own different natures before the crossing with the S0, so, three main
reactions pathways can take place: cis-trans isomerization, Norrish type II reaction (γ-hydrogen abstraction)and fluorine photodissociation, when S1 has a ππ*, nπ* and σFπ* nature, respectively. The minimum energy
point on S0 for cis-keto (A) belongs to Cs symmetry point group. Therefore, S3(ππ*) is populated ingeometries near to planarity.

The initial relaxation takes place close to Cs point group until one point of the seam-S3(ππ*)/S2(σπ*),wherein a fraction of the population can be transferred to σπ* state which is relaxed toward a local minimumon S2(σπ*). However, due to the inertia of the nuclei acquired during the relaxation along ππ* state, the mostof population follow S2(ππ*) until an in-place local minimum belonging to Cs characterized by large C-C
central distance. Nevertheless, this stationary point corresponds to a saddle point when the all 3N-6 degrees
of freedom are taken into account. Therefore, once populated this TS-S2(ππ*), the C-C central distance isaround 1.45 Å, so the twisting coordinate becomes easier to be accessed. Following this coordinate, a pointof the seam-S2(ππ*)/S1(nπ*) is reached, whereas MECI belonging to this seam is 96º twisted and keeps C-C
central distance equal to 1.45 Å. At this moment, the system could follow S1(ππ*) until an point of the seamS1(ππ*)/S0, whose the MECI is 92º twisted and the C-C central distance is 1.48 Å, or follow S1(nπ*) to comeback to Cs symmetry in order to reach MECI-S1(ππ*)/S0, or what is more reasonable, to reach the seamS1(nπ*)/S0 from partially twisted geometries which could leads even directly to a trans-enol compound (N).
The preferred deactivation channel is the cis-trans isomerization (56.3% of trajectories and 127 fs inaverage), followed for the fluorine photodissociation reaction which is the fastest deactivation channel(23.8% and around 77 fs), while the γ-hydrogen abstraction was the less probable (17.5% and 123 fs inaverage). A very small amount of trajectories (around 0.4%) were non-reactive during 300 fs or they
followed other reaction pathways as Norrish type I reaction (α-cleavage) in 189 fs (in average).
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B. Computational study of the non-adiabatic decay of avobenzone
The raising level of awareness regarding the harmful effects of solar radiation has resulted in an increase in
the production and consumption of sunscreens. These commercial products contain ultraviolet (UV) filtersthat absorb, reflect, or scatter UV radiation preventing sunburn, photoaging, even skin diseases such as skincancer. These compounds are incorporated into not only sunscreens but also a number of personal careproducts and even in plastics, varnishes, and clothes to enhance their light stability. Avobenzone belongs to
the family of dibenzoilmethane (DBM), it is the most commonly used organic UVA filter. It exists insunscreens in the enol form which absorbs strongly in the UVA range. However, under sunlight irradiation
tautomerization occurs to the keto form, resulting in the loss of UV protection. The loss of UVA protection is
attributed to the enol → keto phototautomerism because keto form absorbs in the UVC range.
O

OH
H

H3CO

O

O

tBut

Enol form
Dominant

H H

H3CO

tBut

Keto form

Non-degradative pathways

Degradative pathways- cis-trans isomerization- Norrish type I reaction
a-cleavage- Norrish type II reaction

The ground state was explored by using AFIR (γ = 400 kJ) in GRRM package. Around 120 equilibriumgeometries were located and classified according the dihedral angles. After removing mirror images andisomers respect to the substituents on the benzene rings, the geometries found are shown in the next picture:
Enol-2: on the right side
O

H

O

O

2-tTT
0.00

H3CO

Enol-1: on the left side

2-NCE3

CE2

H

O

O

2-cTT
18.32

H3CO

H

2-NCE2-A

HO

2-NCE2-B
O

O
H3CO

H

2-NCE1O

H

2-NCE1

2-tCT
17.73

O
H3CO

H3CO

H

O H

2-tCC
21.08

O

H

H3CO

2-tTC
15.62

H3CO

1-NCE2-B

1-NCE3
O

O

1-cTT
18.62

O

1-NCE2-C

O

O
H3CO

H

H3CO

2-cCC
21.74

H
O

H3CO

H

1-tCT
17.22

1-NCE1-B

1-tTC
15.71

O

O
H
O

O
H3CO

H3CO

1-cTC-B
20.02

H

O

H

1-cCT
17.64

O

O H

O

1-cTC-A
20.16

1-NCE1-A

O
H

O

2-cCT
17.66

H

O

H
O

H3CO

H3CO

2-cTC-B
19.61

O

O

CE1

2-NCE2-C
O

O
H3CO

2-cTC-A
19.79

H

O

1-tTT
0.00

H3CO

1-NCE2-A

H

H3CO

1-tCC
21.29

H
H

O
H3CO

H

1-cCC
22.10

The absorption spectrum was simulated in gas, cyclohexane, methanol and acetonitrile. The cross-sections
were based on TD-B3LYP/cc-pVDZ energies. To include the solvent effect was used cLR-PCM with theslow component equilibrated for the ground state. Each absorption spectrum was generated using an
ensemble of 300 geometries generated using Wigner distribution of non-coupled harmonic oscillator alongnormal coordinates around the global minimum for CE1 (chelated enol) isomer at the ground state.
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Then, two CE and two NCE (non-chelated enol) minima on S1 were located; the solvent effect plays animportant roll in the relative energies of those stationary points as shown below:

Two MECIs (CE-MECI and NCE-MECI) were located along the seam-S1(ππ*)/S0. The CE-MECI and NCEMECI are located 8.75 and 5.97 kcal·mol-1 lower than the excitation energy in gas phase, so they areaccessible. One transition state connects the CE-S1(ππ*) with the CE-MECI-S1(ππ*)/S0 imposing one barrierof 2.27 kcal·mol-1. At March-2016, this research project is not finished, so the future work implies to study
the different pathways to decay to S0, and the keto-enolization reaction.

3. List of publications
Pedro J. Castro and Keiji Morokuma. “Non-adiabatic dynamic on the Photochemistry of 4,4-difluorobut-2enal using TD-DFT and TSH approaches”. In preparation.

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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】 金属錯体の化学的性質や反応を知る上で中心金属の電子状態を知る事は極めて重要である。
特に d8 平面４配位型金属錯体に関して、配位子の作る平面上の dx2-y2 軌道エネルギーが配位子との電子反発によって高くなり、８つの電子は残る４つの d 軌道を占有する事が一般に知られている。
古くから、この配位子平面に直交する dz2 軌道の方向での中心金属と他分子との相互作用について理論研究が行われており、水分子との相互作用は最も重要なものの１つと考えられてきた。
d8 平面４配位型金属錯体が全体として正電荷を持つ場合、z 軸上の水分子は O 原子を中心金属へ向けた構造（O 配向）をとる事が実験、理論研究から示唆されている 1。例として[Pt(pyridine)4]Cl2・
3H2O 結晶などが挙げられるが、これは水素結合が電子的に富んだ領域と正に誘起された部位の静電相互作用に由来するという一般的理解に反しない。一方、全体で中性電荷となる金属錯体の場合、
過去の MP2 計算によれば、水分子の H 原子が電子不足の d8 中心金属へ向いた構造（H 配向）がエ
ネルギー的に優位であると予測されており、これは一般的理解とは逆方向の水素結合を意味する。
この存在は近年、trans-PtCl2(NH3)(N-glycine)・H2O 結晶における中性子散乱実験で立証された 2。
これらの実験、理論研究を踏まえて、中性および電荷を持った d8 平面４配位型金属錯体のモデル系として、Pt2+を中心金属とした trans-PtCl2(NH3)(N-glycine) 1a、[Pt(NH3)4]2+ 1b、[Pt(CN)4]2- 1c 錯体に対し、その z 軸上の水分子との相互作用について気相中での２つの配向の違いを明らかにした。
更に dz2 軌道の影響を調べるため、電子分布の広がりの小さい Pd2+を中心金属とした類似化合物 2a、2b、2c に対しても同様に、水分子の２つの配向における相互作用の違いを比較、検討した。また周囲の環境が与える影響に関しても焦点を置き、３D-RISM-MP2 法によって水溶媒中での振る舞いの違いを検討した。
【方法】 金属錯体と z 軸上の水１分子を QM 領域として扱い、水分子（QM）の２種類の配向に対して次のようにモデル構造を決めた。O 配向では水の O 原子が z 軸上に存在するように、また H
配向では H 原子と O 原子が z 軸上に位置するように束縛条件を加えた上で、3D-RISM-MP2 計算を行い、構造を最適化した。Pt は６０個の内殻電子を、Pd は２８個の内殻電子を Hay-Wadt ECPに置き換えた LANL2TZ(f)を基底関数に選び、残る原子は 6-31++G**基底を用いた。これによって得た金属錯体と水分子の内部座標は固定し、中心金属と水の O 間の距離を変化させる事で気相中のエネルギーおよび水溶媒中の自由エネルギーの振る舞いを調べた。その際により大きな基底関数として水の O と配位子の Cl に aug-cc-pTVZ を、残る配位子に cc-pTVZ を用いて 3D-RISM-MP2 計
算を再度行って、BSSE を補正した。
３D-RISM-SCF 計算については、溶質の電子密度から溶媒平衡分布を定める際に、溶質周囲の静電ポテンシャルを求める必要があるが、本研究では（１）式のように溶質周囲の領域では波動－ 105 －

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関数から直接計算を、溶質から遠く離れた領域では点電荷近似計算を行い、swithing 関数 Sw(x)の導入によって２つを滑らかに繋げる事で、対応する Fock 行列を計算している。
aχ µ* (r ′) χν (r ′)QµνVes (x) = ∑ Pµν Sw (x )∫ dr ′+ {1 − Sw (x )}∑
r′ − xµ ,ν
a Ra − x 



（１）

この three-regions 3D-RISM-SCF 法に対して MP2 レベルでの自由エネルギーおよび勾配ベクトルの計算を行えるように式の導出と GAMESS におけるプログラム化を行った。3【結果】 Pt 錯体と水分子の相互作用系に対して得られた H 配向と O 配向のモデル構造を図１に示す。但し、一部の錯体での全自由度に対する構造最適化は目的の H 配向または O 配向の構造とは異なる構造に辿り着くため、H 配向に関しては水の H と O 原子が z 軸上に、O 配向に関しては
水の O 原子が z 軸上に存在するように拘束条件を加え、更に cyano 錯体の O 配位に関しては金属-O 原子間の距離を glycine 錯体で得られた値になるように制限を加えてモデル構造を得た。

図１：H 配向、O 配向に対する glycine 錯体、ammine 錯体、cyano 錯体のモデル構造

図２：H 配向、O 配向に対するモデル構造からの金属-O 原子距離に沿った気相中エネルギー曲線－ 106 －

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図３：H 配向、O 配向に対するモデル構造からの金属-O 原子距離に沿った水中自由エネルギー曲線

H 配向と O 配向の相対安定性について、glycine 錯体の場合は気相中と水中で定性的な変化はな
いが、ammine 錯体と cyano 錯体の場合は大きく異なる事が図２と３の比較から分かる。ammine
錯体では気相中で O 配向が H 配向よりも大きな安定性を示すものの、水中ではその差がなくなり、
特に Pt では H 配向の方が若干ながら安定となる。一方、cyano 錯体の場合は気相中でも水中でもO 配向が H 配向よりも安定であるものの、O 配向の相対安定性は気相中に比べて水中では大きく減少している。また Pt と Pd の違いについて、H 配向は Pd よりも Pt の方が相対安定性は増加し、
O 配向は Pd よりも Pt の方が相対安定性は減少している事が計算結果から示されている。
この H 配向と O 配向の相対安定性の違いについて調べるため、錯体-水分子間相互作用について
エネルギー分解解析を行った（表１）。解析の結果、glycine 錯体の H 配向の安定化には電子相関（分散）エネルギーが大きく寄与している事、ammine 錯体の O 配向の安定化には静電エネルギーが大きく寄与している一方で H 配向の安定化には分散エネルギーが寄与する事、cyano 錯体の H
配向の安定化には静電エネルギーと分散エネルギーの両者が寄与している事が分かった。また Ptと Pd の相違として、分散エネルギーはあまり異ならないが、静電エネルギーにおいて Pt の方がPd よりも H 配向を安定化する一方で O 配向を不安定化する事が分かった。これは Pt の方が Pd
よりも dz2 軌道の広がりが大きい点を考慮すれば妥当な結果である。また電子移動エネルギーについて、期待していた程には O 配向の安定化に大きく寄与していない事も分かった。しかしながら、H 配向と O 配向では錯体-配位子間の電子移動に対して逆の効果を与える事が電荷分布解析の結果から判明し、H 配向では静電的効果から d 軌道エネルギーが下がるので配位子→金属への電荷移動が増大し、更に一部の電子が錯体→水へ移動する傾向がある点と、O 配向では静電的効果から d 軌
道エネルギーが上げるので配位子→金属への電荷移動が減少し、更に微量ながら水→錯体へ電荷移動する傾向がある点も判明した。
また気相中と水中のエネルギー曲線の違いは主に溶媒和自由エネルギーが原因となっている事も分かった。その大きさは Pt と Pd であまり変わらないが、ammine 錯体と cyano 錯体の場合、H配向と O 配向の間で顕著な差がある。ammine 錯体の場合は O 配向よりも H 配向の方が溶媒和自由エネルギーによる安定化が大きく、cyano 錯体の場合は H 配向よりも O 配向の方が大きい。
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表１：水中における錯体-水分子間のエネルギー分解解析

図４：H 配向→O 配向に対する溶媒和構造と溶媒和自由エネルギー分布の変化－ 108 －

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これは ammine 錯体と cyano 錯体の間で全電荷の符号が異なる事から生じており、ammine 錯体
では配位子周囲の水は O 原子を向ける傾向があるのに対し、cyano 錯体では H 原子を向ける傾向がある事が水分子の分布関数から理解できる（図４）。この配位子周囲の水の向きと大きな静電安定化を稼ぐ事が出来る位置に H 原子を持ち、更に錯体電荷移動を誘起するのは、ammine 錯体の場合は H 配位であり、cyano 錯体の場合は O 配位である事が分かった。
このように気相中では H 配向と O 配向で大きな静電エネルギーの違いがあるような電荷系であっても、水中では配位子周囲の溶媒効果によって、その静電エネルギーの優位性は大きく相殺される傾向があり、特に Pt 錯体になると ammine 錯体のように正電荷を持つ系であっても H 配向が生じ得る事が分かった。
[1] : J. Kozelka, J. Berges, R. Attias, J. Fraitag, Angew. Chem. 2000, 112, 204.
[2] : S. Rizzato, J. Berges, S. A. Mason, A. Albinati, J Kozelka, Angew. Chem. 2010, 49, 7443.
[3] : S. Aono, T. Mori, S. Sakaki, J. Chem. Theory Comput. 2016, 12, 1189.

2. 論文(1) Shinji Aono, Toshifumi Mori, and Shigeyoshi Sakaki,“3D-RISM-MP2 Approach to Hydration Structure of Pt(II) and Pd(II) Complexes:
Unusual H‑Ahead Mode vs Usual O‑Ahead One”
J. Chem. Theory Comput. 12 (3), 1189-1206 (2016).
3. 学会発表(1) 青野信治、榊茂好「QM/MM法によるRu(II)-SO2錯体の結晶内異性化反応の理論的研究」
第9回分子科学討論会 東京 2015/9/19 4E03
(2) Shinji Aono, Shigeyoshi Sakaki「Unusual H2O interaction with Pd(II) and Pt(II) complexes through H atom;
3D-RISM-SCF/MP2 Study」
The 15th International Congress of Quantum Chemistry 2015/6/10 poster III.16(3) Shinji Aono, Shigeyoshi Sakaki「Isomerization of ruthenium(II) sulfur dioxide complex in crystal;
Theoretical study with QM/MM approach」
The 7th Asia-Pasific Conference of Theoretical and Computational Chemistry
2016/1/27 O17D
4. その他(1) 「QM/MM法によるRu(II)-SO2錯体の結晶内異性化反応の理論的研究」
京都大学第13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
2016/2/5 P30－ 109 －

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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【緒言】ジピリジルアミン(dpa)を配位子とする錯体は、金属-金属結合を有する二核及び三核錯体として広く研究されている(スキーム 1)。Cr(II)の三核錯体は axial 位の配位子の違いにより、Cl 錯体では 2 つの Cr-Cr
結合が等価な対称構造が 1、N3 錯体では一方が長くもう一方が短い非対称構造が 2 報告されている。このことから三核錯体における金属結合は多中心結合であり、その結合性や電子・スピン状態は二核錯体とは大きく異なると考えられる。また過去の多くの二核錯体の研究で多重金属結合における多参照性の重要性が報告されてきたが、三核錯体の研究例は密度汎関数法によるものが主であり、多参照性計算による理論研究は行われておらず、電子状態の理解が十分でない。
本研究では、多参照理論に基づいた高精度計算法である DMRG-CASSCF/CASPT2 法を用いて多中心多重金属結合を有する錯体の電子状態の解明を試みた。
【計算方法】構造最適化には DFT(B3PW91)法と CASPT2 法を用い、分子軌道の生成には通常の
CASSCF 法を、エネルギー計算には DMRG-CASSCF/CASPT2 法を用いた。また局在化軌道(LMO)
を用いた CASCI 法によりスピン分布に関する解析及び２つの金属結合の結合次数を求めた。
CASSCF の active space には空軌道である dx2-y2 軌道を除く d 軌道(12 電子 12 軌道)を用いた。遷
移金属の内殻電子は Stuttgart-Dresden-Bonn の ECP で置き換え、原子価軌道には triple zeta 基
底関数を用いた。その他の原子には DFT 法では cc-pVDZ を DMRG-CASPT2 法では C,H 原子には DZ 基底を N,Cl 原子には DZP 基底を用いた。
【結果及び考察】DFT 法を用いた構造最適化を行った結果、Cl 錯体、N3 錯体の双方で２つの Cr-Cr
結合長の長さが等しい対称な安定構造が得られた。その Cr-Cr 結合長はそれぞれ 2.464Å 及び 2.461Å
であり、対称構造を持つ Cl 錯体の実験値 2.365Å よりも約 0.1Å 長い。Cl 錯体において Cr-Cr 結合長を変化させたポテンシャル曲線を図 1 に示す。

図 1.Cr-Cr 結合長に対するポテンシャル曲線。 図 2.Cr-Cr 結合長の非対称ポテンシャル曲線。
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DMRG-CASSCF 法では DFT 法よりも結合長が過大評価されたが、DMRG-CASPT2 法では 2.40Å 付
近で極小になり、実験値に近い結果が得られた。2 つの Cr-Cr 結合長の差を変数としたポテンシャ
ル曲線を図 2 に示す。いずれの計算方法においても２つの金属結合間距離の相違が大きくなるに従いエネルギーの単調な不安定化が見られたが、DMRG-CASPT2 法では他の計算法に比べエネルギーの不安定化が半分以下である。
N3 錯体においても Cl 錯体同様に、DMRG-CASPT2 法で対称構造では Cr-Cr 結合長 2.38Å で極小となった。実験値を起点にした非対称構造のポテンシャル曲線を図 3 に示す。先に長い Cr-Cr 結合を最適化した結果 2.51Å と実験値に近い値が得られた。その後、短い Cr-Cr 結合の最適化を行うと、DFT 法及び CASSCF 法では非対称構造が大きく不安定で対称構造へと収束するのに対し(図 3a)、DMRG-CASPT2 法では 2.27Å で極小になり、2 本の結合長が 0.24 Å 異なる非対称構造が得られた。
この構造は非対称構造よりも不安定であるが、そのエネルギー差は 1kcal/mol と小さい。

図 3.N3 錯体の非対称構造の Cr-Cr 結合長のポテンシャル曲線。
Cl 錯体の基底状態である５重項状態の CASSCF 自然軌道を図 4 に示す。三核錯体においても二核錯体と同様に、σ型とδ型が１つπ型が２つの計４つの結合性軌道を有する。結合性軌道の占有数はσ軌道が 1.45, ２つのπ軌道が 1.19,δ軌道が 1.04 であり多配置性が非常に大きいことが示唆される。同じ配位子をもつ二核錯体 Cr2(dpa)4 の占有数はそれぞれ、σが 1.65,πが 1.55,δが 1.16 であることから、二核錯体と三核錯体との相違はπ結合で最も大きい。また三核錯体では二核錯体とは異なり、中心の Cr 原子の軌道を含まない非結合性軌道が４つ存在する。非対称構造ではこれらの非結合性軌道の代わりに、結合長の長い側の末端の Cr 原子に局在化した d 軌道が自然軌道として得られる。スピン状態間のエネルギー差を表１に示す。
非結合性軌道 φ5-φ8 だけでなく φ4 及び φ9 軌道の占有数も

表 1 スピン状態の相対エネルギー１に近いにもかかわらず７重項状態は５重項状態に比べてスピン多重度ΔE (kcal/mol)

非常に不安定である。これは後述するスピン密度の分布と

11

31.9

深く関係している。

9

18.7

7

9.3

5

0.0

3

8.3

1

14.1

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表 2 Cr 原子 d 軌道の電子及びスピン分布
Cr1
X=Cl (sym)φ9 (0.96)

φ10 (0.81)

φ11 (0.81)

φ12 (0.52)
X=N3 (sym)
X=N3 (asym)

φ5 (1.00)

φ6 (1.00)

φ7 (1.00)

electron 3.99
spin

4.00

3.99

4.01

3.99

3.27 −2.54 3.27

electron 3.99
spin

Cr3

3.27 −2.55 3.27

electron 3.99
spin

Cr2

4.01

3.99

2.74 −2.36 3.61

φ8 (1.00)
表 3 2 つの Cr-Cr 結合の結合次数φ1 (1.48)

φ2 (1.19)

φ3 (1.19)

φ4 (1.04)

Cr1-Cr2

Cr2-Cr3

X=Cl (sym)

0.634

0.634

X=N3 (sym)

0.706

0.706

X=N3 (asym)

0.948

0.465

図 4. 対称構造の Cr3(dpa)4Cl2 の CASSCF 自然軌道。
括弧内は占有数を表す。
局在化軌道を用いた CASCI 法を行い、各構造における金属原子のスピン密度を求めた値を表 2に示す。対称構造では末端の Cr 原子は 3.27 のスピンを、中央 Cr 原子は末端 Cr とは逆向きスピン
2.54 をもち、系全体として５重項をとる。これらの値は二核錯体の反結合性軌道の占有数から見積もられるラジカル性(2.09)よりも相当程度大きい。また非対称構造になると、結合長の長い離れたCr 原子はスピンが増加、より短い結合長をもつ２つの Cr 原子はスピンが減少するが依然として３
つの Cr 原子すべてが大きなスピンをもっていることがわかる。
自然軌道の占有数からは 3 つの金属原子に非局在化した結合次数しか得られないため、局在化軌
道の密度行列を基に２原子間の金属結合に分割した結合次数を表３に示す。自然軌道を用いた Cl
錯体の金属結合の全体の結合次数は 0.90 であるが実際の２原子間の結合は 0.63 とさらに小さいことがわかる。また、N3 錯体の対称構造と非対称構造における結合次数を比較すると、片側の結合次数の増加ともう一方の減少は同程度であり、弱い結合は強い結合のおよそ半分の結合次数である。
本研究において、密度汎関数法では定性的にも不十分であった三核錯体の金属結合に関して、
DMRG-CASPT2 法を用いて、金属結合長変化に対して非常になだらかなポテンシャル曲面を明らかにし、局在化軌道を用いた解析によって、その電子構造について特徴的なスピン分布や金属結合の結合次数を明らかにした。
【文献】[1] F. A. Cotton et al., J. Am. Chem. Soc. 1997, 119, 10223.
[2] Y. Turov, J. F. Berry, Dalton Trans., 2012, 41, 8153.

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2. 論文(1) Masayuki Nakagaki, Shigeyoshi Sakaki“Inverse Sandwich-Type Dinitrogen Complexes of Hetero-Dinuclear 3d Metals:
Theoretical Prediction of Characteristic Features of Geometry and Spin Multiplicity”
Submitting to Phys. Chem. Chem. Phys.

3. 学会発表(1) Masayuki Nakagaki, Shigeyoshi Sakaki

CASPT2 Study of Inverse Sandwich-Type Dinuclear 3d Transition Metal
Complexes of Ethylene and Dinitrogen Molecules
The 15th International Congress of Quantum Chemistry, Beijing, China 2015/6/8-13
I.144 poster(2) Masayuki Nakagaki, Shinji Aono, Shigeyoshi Sakaki
Electronic Structures and Intermolecular Interactions of Co(II) Complexes:
Important Factor of Spincrossover
Novel Computational Methods for Quantitative Electronic Structure Calculations, Kobe,
2015/6/16-20 P28 poster(3) 中垣雅之, 中谷直輝, 長谷川淳也, 榊茂好「ジピリジルアミン三核錯体の電子構造：三中心多重金属結合の多参照性電子状態」
第 9 回分子科学討論会 2015 東京 東京 2013/9/16-19 2P107 ポスター

4. その他(1) 中垣 雅之, 村岡 貴子, 上野 圭司, 榊茂好
モリブデン及びタングステン-シリレン錯体の反応機構:
金属原子及び溶媒による反応選択性
第13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 2016/2/5(2) 中垣 雅之，榊 茂好
逆サンドイッチ型錯体の電子構造:
スピン状態の支配要因と異核錯体の特異な電子状態
特別シンポジウム「未来への架け橋：分子科学の最前線と将来展望」福岡 2016/3/5－ 113 －

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Shuwei TangSPR Fellow
ShuweiTang
SPR Fellow
1. Summary of the research of the year
Theoretical Study of Aromatic C-H σ-Bond Activation by Ni(0), Pd(0), and Pt(0) Alkene
Complexes: Concerted Oxidative Addition to Metal Center vs. Oxidative Addition
Across to M-Alkene Moiety

The hydroarylation of un-activated alkenes and alkynes through direct C-H activation ofaromatics by transition metal is one of attractive reactions for preparing alkylarenes andalkenylarenes. Recently, remarkable improvements have been succeeded in this catalytichydroarylation of un-activated alkenes. For instance, Nakao and coworkers reported thatnickel(0) complex of monophosphine was capable of performing hydroarylation of unactivated alkenes with high selectivity, as shown in Scheme 1. Hartwig, Einsenstein, andcoworkers made exciting progress on this topic. They successfully applied a nickel(0)complex with N-heterocyclic carbene ligand, IPr {IPr = (1,3-Bis2,6-diisopropylphenyl)1,3-dihydro-2H-imidazol-2-ylidene}, to hydroarylation of an un-activated alkene under
mild conditions to afford a mixture of linear and branched alkylarenes. Very recently,
Nakao and coworkers reported that a combination of a nickel(0) carbene complex and the
Lewis acid directly activates the aromatic C-H bond of N, N-dimethylbenzamide to
introduce the alkyl group to the phenyl group with good to excellent yields and selectivity.
Scheme 1

The reaction mechanism of the C-H activation/functionalization of aromatics has been
firstly investigated by Eisenstein and coworkers, in which the H transfer from aromatics toalkene followed by reductive elimination was proposed based on DFT computation, as
shown in Scheme 2. This C-H activation reaction is completely different from the usual
concerted oxidative addition to low-valent metal center.
Scheme 2－ 114 －

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In this work, we theoretically investigated the C-H activation reaction of benzene withnickel(0), palladium(0), and platinum(0) complexes, using density functional theory (DFT),
where benzene, propene, and IMes (1,3-dimesitiylinidazol-2-ylidene) were employed asmodels of aromatic compound, alkene, and carbene ligand, respectively, to simplify thesystem. Our purposes here are to provide theoretical answers to above mentioned questions;for instance, to elucidate the reaction mechanism, to make comparison of reactivity in the
C-H activation reaction among nickel(0), palladium(0), and platinum(0) complexes, todisclose the reason why the bulky carbene ligand is used in the catalytic system bycomparing the reactivity among IMes, carbodicarbenes such as C(NHC)2 and C(NHCMe)2, trimethylphosphine (PMe3), dicyclohexyl{2',4',6'-triisopropyl-(1,1'-biphenyl)-2yl}phosphane (X-Phos), and cyclic alkyl amino carbine such as CAAC and CAAC-K3(Scheme 3).
Scheme 3－ 115 －

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Because Ni0(IMes)(propene)2 1-Ni is more stable than other possible reactant
complexes such as Ni0(IMes)(propene)(benzene) 2-Ni and Ni0(IMes)(benzene)2, 1-Ni wastaken as an energy reference in this study. 1-Ni has a Y-shaped structure in which two
propenes coordinate with the nickel center through a C=C bond, as shown in Figure 1. Thisis a typical three-coordinated d10 complex. The C=C double bond is considerably elongated(1.399 Å) compared to that (1.330 Å) of free propene, indicating the strong π-backdonation is formed between nickel and propene. The substitution of benzene for one ofpropenes occurs to afford 2-Ni, which is 14.5 kcal/mol above 1-Ni. In 2-Ni, the C=C bondof benzene is somewhat elongated to 1.420 Å compared to that (1.392 Å) of free benzene
due to the π-back-donation from the nickel center to the benzene. The Ni-C(IMes) bond
(1.948 Å) is also moderately longer than in 1-Ni (1.933 Å).
To undergo the subsequent C-H activation reaction, 2-Ni must be converted to anintermediate 3-Ni, in which the C-H bond of benzene interacts with the nickel center. In 3Ni, the C-H bond (1.106 Å) is elongated relative to that (1.089 Å) of free benzene,
suggesting that some bonding interaction is formed between the nickel and the C-H bond.
As going from 2-Ni to 3-Ni, a transition state TS2/3-Ni is located at 1.2 kcal/mol above 2Ni. In TS2/3-Ni, the benzene coordinates with the nickel center in an η3-manner, in which
the ipso-carbon is 2.677 Å distant from the nickel center but another adjacent carbon andhydrogen atoms are close to the nickel center (2.237 and 2.596Å, respectively). Carefulgeometry optimization starting from TS2/3-Ni confirms that it indeed connects twointermediates through anticlockwise and clockwise rotations of the benzene ring. Startingfrom 3-Ni, the C-H bond of benzene is cleaved by direct transfer of a hydrogen atom fromthe benzene to the propene, to afford a nickel(II) propyl phenyl intermediate
Ni(IMes)(propyl)Phyenyl) 4-Ni through a transition state TS3/4-Ni. The Gibbs activationenergy is 30.8 kcal/mol relative to 1-Ni. In TS3/4-Ni, nickel, propene, migrating H (H1,hereafter) and ipso-carbon (Cipso) are almost on one plane. The H1 atom is 1.767 Å distantfrom the ipso carbon, 1.488 Å from the Ni atom, and 1.675Å from the carbon of the C=C
double bond of propene, suggesting that the hydrogen atom is moving from benzene topropene, keeping a bonding interaction with the Ni atom. The rather short Ni-Cipso distanceof 1.951 Å indicates that the Ni-phenyl bond is almost formed in TS3/4-Ni. This TS3/4-Ni isessentially the same as the transition state of H-transfer from benzene to ethylene reported
recently by Eisenstein and coworkers. 4-Ni has a typical T-shape structure, which isreasonable because this is three-coordinate d8 Ni(II) complex with NHC, propyl, andphenyl ligands. 4-Ni is 4.8 kcal/mol more stable than TS3/4-Ni but much less stable than 1Ni by 24.5 kcal/mol. The C-H bond of the propyl group approaches the nickel center to－ 116 －

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form an agostic C-H interaction, where the Ni-H distance is 1.935 Å and the C-H distanceis 1.185 Å. This interaction is formed in this complex because Ni(II) has a d8 electron
configuration and the empty dσ orbital expands toward the C-H bond. The Ni-Cipso distanceis 1.947 Å, which is similar to that in TS3/4-Ni. This agostic interaction stabilizes 4-Ni bycharge-transfer (CT) interaction from the C-H bond to the nickel center. Considering thatthe oxidative additions of phenyl chloride, benzyl chloride, and benzonitrile to a nickel(0)complex have been experimentally reported and theoretically analyzed, we tried to locate
such a stable nickel(II) hydride phenyl propene complex but failed to optimize it despite a
lot of efforts. It is concluded that the usual concerted oxidative addition is difficult in thisreaction system.

Figure 1. Changes in Gibbs energy (in kcal/mol) at 298.15K and geometries in the Ni(NHC)-promoted
C-H σ-bond activation of benzene. Several hydrogen atoms are omitted for clarity. The bond lengths are
given in Å.

C-H σ-Bond Activation by Pd(0) and Pt(0) Analouges
To get better understanding of the C-H σ-bond activation by metal(0)-alkene complex,
we investigated the C-H activation of benzene by similar palladium(0) and platinum(0)complexes. The geometrical features of the platinum(0) and palladium(0) NHC propene
complexes seem essentially the same as those of the Ni(0) analogue, despite several
differences are observed between them. However, the most significant difference for the CH activations activated by Pd or Pt in comparison with Ni is that the C-H σ-bond activation
occurs through transition state TS3/4-Pd or TS3/4-Pt to afford an intermediate－ 117 －

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Pt(IMS)(H1)(ohenyl)(propene) 4-Pd or 4-Pt. In TS3/4-Pt, the Pt-H1 and Pt-Ph distances are
1.663 Å and 2.159 Å, respectively, which are longer than those of TS3/4-Ni. Important
geometrical changes are found in the position of the H1 atom; the C-H1 distance of thebenzene moiety is less elongated and the C-H1 distance between propene and benzene isconsiderably longer than in TS3/4-Ni, indicating that the H1 atom does not approach the C
atom of propene in the Pt reaction system. In 4-Pt, the H1 and Ph groups are bound with thePt atom. It is concluded the concerted oxidative addition occurs in the Pt reaction system.
The similar geometry changes are found in the Pd reaction system. It is worthy of note that
only the C-H activation by the nickel(0) complex occurs in the different mechanism fromthe concerted oxidative addition. The Gibbs activation energy (∆Gº‡) is 30.4 kcal/mol in the
Pt reaction system and 33.6 kcal/mol in the Pd reaction system relative to 1-Pt and 1-Pd.
The higher activation energy of the Pd system than that of the Pt system is reasonablebecause the Pd d orbital exists at lower energy than the Pt d orbital. After the C-H
activation, the alkene insertion into the Pt-H bond occurs through a transition state TS4/5-Pt
to afford a platinum(II) propyl phenyl complex 5-Pt. The ∆Gº‡ value is very small (3.7
kacal/mol for the TS4/5-Pt and 3.9 kcal/mol for TS4/5-Pd relative to the intermediates 4-Pt
and 4-Pd), indicating that propene is easily inserted into the Pt-H and Pd-H bonds. In TS4/5Pt, the C-H distance between the propene and the H1 is 1.571 Å and the Pt-H distance ismoderately elongated to 1.697 Å, suggesting that this transition state is similar to 4-Pt. In
5-Pt, the C-H bond distance of the propyl group is 1.185 Å and the Pt-H distance is 1.935
Å, indicating the presence of the agostic interaction between the C-H of the propyl groupand the Pt(II) center like in Ni. 5-Pt is slightly less stable than 4-Pt and much less stable
than 1-Pt. The similar geometrical features are found in the Pd reaction system.

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Figure 2. Changes in Gibbs energy (in kcal/mol) at 298K and geometries in the Pt(NHC)promoted C-H σ-bond activation of benzene. Several hydrogen atoms are omitted for clarity.
The bond lengths are given in Å.

Important orbital interaction in the aromatic C-H bond activation by
Ni(NHC)(propene) complex
To understand the reaction mechanism, the knowledge of orbital interaction in thereaction is indispensable. We evaluated electron populations of several important MOs ofNi(NHC), propene, and benzene moieties in the reaction. Figure 3 shows these MOs andtheir population changes (in |e| unit) against the C(aryl)-H(active) distance. Apparently, theelectron populations of the Ni 3d orbitals considerably decrease, which contributes to theNi oxidation state change from 0 to +II. The H atomic population decreases around TS2/3Ni, which is consistent with the proposal that this C-H activation is understood as the
proton-transfer. The electron population of the HOMO (π MO) of the propene moiety
monotonously decreases but that of the LUMO (π* MO) increases, indicating that thepropene participates in the C-H π-bond cleavage. The population of the π* (LUMO) of
benzene moiety increases, while that of the HOMO of benzene changes little around thetransition state but starts to decrease as going from the transition state to the product. These
results suggest that the HOMO of benzene participates little in the C-H π-bond cleavage but
it contributes to the CT from benzene to the Ni(II) center which is formed in the late stageof the reaction. In the Pt reaction system, the electron population of the Pt 5d orbitals also
decreases with the elongation of the C-H distance. It is notable that the H atomic population
increases in TS2/3-Pt unlike in TS2/3-Ni. The electron population of the HOMO of propene－ 119 －

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does not change very much and that of the LUMO considerably decreases unlike in the Nicase, representing that the propene participates in the C-H σ-bond cleavage in a completely
different manner from that in the Ni reaction system. The electron population of the LUMO
of benzene increases in the reaction, indicating that the CT occurs from the Pt 5d orbital to
the LUMO. A similar finding is observed in the Pd reaction system.

Figure 3. The dependence of electron contributions (in |e|) on the C(aryl)-H(active) distance in the
C-H activation process of M/NHC complex (M=Ni, Pt).

The above differences in population changes relate to the difference in reaction
mechanism between the Ni and Pt reaction systems. In the oxidative addition to metal
center only, the CT mainly occurs from the metal d orbital to the C-H σ*-MO as crucial
interaction. Hence, the Pt d orbital population considerably decreases and that of the
LUMO of benzene considerably increases. Though propene does not participate directly inthis reaction, the CT from the Pt d orbital to the propene π* MO becomes weaker, whichleads to the decreasing of the electron population of the LUMO of propene. The HOMO ofpropene does not participate in the coordinate bond with the Pt(0) atom and its contribution
to the reaction is not large, which will be discussed below. In the oxidative addition of theC-H bond to the Ni(0)-propene moiety, the CT occurs from the Ni d orbital to the LUMO ofbenzene to induce the C-H σ-bond cleavage. This feature is common between the Pt and Ni
reaction systems. At the same time, the HOMO of benzene containing the H 1s orbital starts
to overlap with the propene HOMO (π MO) in an anti-bonding way because both aredoubly occupied, while it interacts with the LUMO of propene in a bonding way because－ 120 －

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the propene LUMO is at higher energy than the HOMO of benzene, as shown in Scheme 4.
Scheme 4

The antibonding overlap between the propene HOMO and the benzene HOMO
corresponds to exchange repulsion, which induces the decrease in the electron populationsof both HOMOs, which is certainly seen in Figure 4. This is the origin of the difference
between the Pt and Ni reaction system.

Figure 4. Important orbital overlap in TSs catalyzed by M/NHC (M=Ni, Pd, Pt).

Effects of Various Ligands on the Aromatic C-H Bond Activation by Ni(0) Complex
Unveiling the ligand effects on the C-H activation reaction can provide valuable
information about what ligand should be used in this type of C-H activation of aromatics.
As summarized in Figure 5, the activation barrier against the nickel(0) benzene propene
complex does not relate with the tendency of lone pair MO energy, suggesting that theelectronic nature is not primarily important in this C-H cleavage process. However, it
should be noted that the bulky ligand decreases the activation barrier; for instance, theactivation barrier is smaller in the more bulky CAAC-K3 ligand than in the less bulky
CAAC-k0. Also, the activation barrier by X-Phos is smaller than that by PMe3 and that ofC(NHC-Me)2 is smaller than that of C(NHC)2, as shown in Figure 9. This is interesting
because the result is against our expectation that the bulky ligand suppresses the reaction in
general.

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Figure 5. The dependence of activation barriers in TSs on the orbital energy of lone-pair electron indifferent ligands.

To clarify the reason why bulky ligands decrease the activation barriers, we madecomparisons of TS structure among various ligands, as shown in Figure 6. The C-C
distance between propene and benzene is much shorter in the case of CAAC-k3 than in the
CAAC-k0. The similar trend can be found in other comparisons. These results indicate thatthe bulky ligand pushes benzene and propene away and thereby the distance between
benzene and propene becomes short in the nickel(0) propene benzene complex. Suchgeometry is favorable for the H transfer from benzene to propene.

－ 122 －

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Figure 6. Comparison of activation energy and structures of TSs for the C-H activation process of indifferent Ni-Ligand moiety. Several hydrogen atoms are omitted for clarity. The bond lengths are givenin Å.

2. Original papers
Shuwei Tang, Yoshiaki Nakao, and Shigeyoshi Sakaki, “Theoretical Study of Aromatic C-H
σ-Bond Activation by Ni(0), Pd(0), and Pt(0) Alkene Complexes: Concerted Oxidative
Addition to Metal Center vs. Oxidative Addition Across to M-Alkene Moiety”, inpreparation.
3. Presentation at academic conferences－ 123 －

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Shuwei Tang, Yoshiaki Nakao, and Shigeyoshi Sakaki, “Theoretical Study of Aromatic C-H
σ-Bond Activation by Ni(0), Pd(0), and Pt(0) Alkene Complexes: Concerted Oxidative
Addition to Metal Center vs. Oxidative Addition Across to M-Alkene Moiety”, 第 3 回 中
尾 T CREST 合同研究会について, kyoto, July 25, 2015.

－ 124 －

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Hong Zheng
Hong ZHENGSPR Fellow
SPR Fellow
1. Summary of the research of the year
Characteristic Features of Transmetallation of Pd(II)-Ph Complex with Cu(I)-alkyl
Complexes: Theoretical Study
Recently a new kind of reductive cross-coupling of arylalkene with aryl bromide by Pd/Cu catalysis
has been experimentally succeeded, as shown in Scheme 1. Being different from conventional cross-coupling
reaction which requires pre-synthesis of organometallics, this reaction needs only one step and pre-synthesisof organometallics is not needed but it is supplied by insertion of alkene into metal-hydride. The proposed
reaction mechanism consists of cycle Pd and cycle Cu (Scheme 1b). Firstly, the Cu hydride 10 reacts with an
aryl-alkene complex 2 to afford a Cu(I)-alkyl complex 1. Then 1 reacts with a three-coordinated Pd bromide
through transmetallation reaction (step b). Afterward, reductive elimination occurs in the transmetallation
product 7 to give the target molecule 4. The transmetallation between Pd(II) and Cu(I) complexes is rear andbelieved to be the most important step in this cross-coupling reaction. However, the reaction mechanism is
not clear and thus theoretical investigation is indispensable.

Scheme 1. Reductive cross-coupling of arylalkene with aryl bromide and proposed reaction mechanism.
In this work, detailed investigations on the transmetallation between PdBrPhPCyp3 andCu(NHC)(CHMePh) complexes were performed. Three types of transmetallation mechanism were
investigated and compared with the experimental results. The electronic processes of these three mechanisms
were analyzed to understand the important factor of this reaction.
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Reaction between PdBrPhPCyp3 and Cu(NHC)(CHMePh). Although four-coordinated Pd complex
6 exists in the reaction cycle, it is the three-coordinated Pd complex participates in the transmetallationaccording to experimental observation. Complexes 6 and 1 firstly form a weak contact adduct RAD (Figure1). Then one PCyp3 ligand is dissociated and AD1 is obtained. There are two possible transmetallation
mechanisms, inversion and retention mechanisms. The inversion mechanism includes linear and bridging
cases (Scheme 2a and b). In inversion mechanism, the aryl-alkyl group CHMePh becomes planar intransition state (TSL and TSB) and its conformation changes in product. One Pd-Br-Cu bridge exists in thebridging case but does not in the linear case. In retention mechanism, the CHMePh group changes its
orientation in TSR but the conformation is kept (Scheme 2c).

Scheme 2. Inversion and retention mechanisms in transmetallation.
The inversion mechanism with linear case occurs from AD2 through TS1L (Figure 1). AD2 is obtained
from AD1 with small geometrical change. The crucial geometrical change in TS1L is the CHMePh group
becomes planar: BA around C in AD2 is 345° but in TS1L is 358°. The Pd-Cu distance dcreases to 2.529 Å
in TS1L but the Cu-C distance changes little. Then, BA around C decreases to 338° and the Pd-C bond isformed in an intermediate INTL. Hence, the conformation of CHMePh is changed. However, the Cu atom
coordinates with the phenyl group of CHMePh in INTL and the Pd center temporally becomes
four-coordinated. Then, the Cu atom is moving toward Br atom and the Cu-Br distance becomes shorter in
TS2L and finally the Cu-Br bond is formed in P1aL.
The inversion mechanism with bridging case needs only one transition state (TSB), as shown in Figure 1.
The geometry of CHMePh group is more product like in TSB than that in TS1L since BA around C is 349°
and Pd-C distance (2.179 Å) is close to the value in P1B (2.117 Å). The Cu-Br is also somehow formed in
TSB. The geometrical difference between P1L and P1B is the orientation of Pd complex: Pd-C and Cu-Br
bonds are almost conplanar in P1L but perpendicular in P1B.
In the retention mechannism, the CHMePh group changes its orientation to contact with Pd in TS1R.
The Pd-C and Cu-Br distances decreases by about 0.4 Å but Cu-C changes little in TS1R. However, TS1R is
an isomerization TS connnecting with an intermediate INTR, in which the Pd-Cu distance and ∠Pd-Br-Cu－ 126 －

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angle decrease very much and the CHMePh group rotates backward. Then transmetallation occurs throughTS2R. In TS2R, the Cu-C bond is broken and the CHMePh group moves toward Pd, resulting in muchsmaller Pd-C and Cu-Br distances. Finally the transmetallation product P1B is obtained in which theconformation of CHMePh group does not change.

Fig 1. Geometrical parameters of complexes in transmetallation mechanisms between PdBrPhPCyp3 andCu(I)(CHMePh). The bond distances are represented in Angstrom. BA around C represents the sum of threebond angles around active carbon of CHMePh group.
The energy changes are exhibited in Figure 2. the formation of the weak contact adduct RAD ismoderately exothermic with a relative Gibbs energy of -4.0 mol/mol, and the dissociation of PCyp3 needs
27.7 kcal/mol. AD1 is only 0.6 kcal/mol lower than AD2 since the geometrical difference between AD1 andAD2 is very small. In the inversion mechanism with linear case, TS1L is 0.3 kcal/mol lower than AD2 in
Gibbs energy but 0.8 kcal/mol higher in potential energy, meaning the transfer of CHMePh occurs without
energy barrier. The intermediate of this pathway is only 3.3 kcal/mol lower than AD2 since Cu-C bond isvery weak but Cu-Br bond is not formed yet. In the inversion mechanism with bridging case, despite ofstronger Pd-C and Cu-Br bonds in TSB, TSB is not favorable for transmetallation due to a large activation－ 127 －

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energy of 40.5 kcal/mol. The most important transition state in the retention mechanism is TS2R, whose
activation energy is 37.3 kcal/mol. Therefore, the inversion mechanism with linear case is the most favorable
mechanism among the three mechanisms and further reductive elimination starts from P1L. TS2L and thetransition state of reductive elimination TSE are lower than TS1L and herein TS1L is the most importanttransition state in this pathway.

Fig 2. Energy changes (in kcal/mol) of three mechanisms.
Electronic process. In the inversion mechanism with linear case, small charge transfer occurs in thereactant AD2 (Figure 3a): the populations of Pd and Ph have similar changes as going from AD2 to P1L. The
PdPh fragment and PCyp3 increase by 0.100 e in total, while that of Cu and CHMePh decrease by 0.018 e
and 0.071 e, respectively. Since the interaction between Pd and CHMePh becomes stronger in TS1L, the
PdPh fragment and PCyp3 onbtain more populations from Cu atom. Then, the charge transfer from Cu
complex to Pd complex further increases to a larger extent in INTL, in which both Cu and CHMePh donate
electrons to PhPh and PCyp3. The population of Br atom increases little as going from AD1 to INTL sinse its
bonding feature does not change and it is distant from Cu. As the coordination between Cu and the phenylgroup of CHMePh disappears and Cu-Br bond is formed from INTL to TS2L, the population of PdPh and Br
decrease by 0.061 e and 0.097 e, respectively, while that of Cu increases by 0.181 e. The population of PCyp3
increases by 0.050 e, which is compensated by the change of CHMePh from INTL to TS2L. In the inversion
mechanism with bridging case, the population of CHMePh decreases and that of PCyp3 and PdPh increase as
going from AD1 to P1B (Figure 3b). The population of Cu decreases by around 0.1 e from AD1 to TS1B, andthen this change is compensated by Br atom at P1B since Cu-Br is formed.

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Fig 3. Important population changes from seperated Pd(II)Ph and Cu(I)-CHMePh complexes to thegeometries of inversion/retention mechanisms. Ph is the phenyl group of Pd(II)Ph complex.
Different population changes are found in the retention mechanism. Firstly the population of PdPhfragment decreases and that of CHMePh increases little as going from AD1 to TS1R (Figure 3c). This isbecause the orientation of CHMePh changes but the Pd-C distance increases a little in TS1R. The populationof Pd and Ph increases and that of CHMePh decreases as going from TS1R to INTR, suggesting stronger
interaction between Pd and Cu complexes in INTR. Then, the population of CHMePh decreases by 0.224 efrom INTR to TS2R, which is mainly compensated by the population increases of Ph and PCyp3. The
population of Cu decreases by 0.064 e from INTR to TS2R because the Cu-C bond is broken but Cu-Br bondis still weak in TS2R. The population increase of Pd (0.086 e) approximately corresponds to the population
decreases of Cu and Br from INTR to TS2R. However, in the P1R complex the population of Cu returns to
the value in AD1 because the Cu-Br bond is formed, while that of Pd returns to value in INTR and that of Br
also decreases a little.
In conclusion, in the transmetallation reaction between PdBrPhPCyp3 and Cu(NHC)(CHMePh), theinversion mechanism with linear case is more favored than other mechanisms thanks to smaller activationenergy. This is in agreement with the experimental results. The most important change in inversion TS is
CHMePh becomes planar. The charge transfer is found to be significant in transmetallation. The populationof PCyp3 increases during this reaction, implying strong trans-influence of PCyp3. These results provide
good understanding of transmetallation between PdBrPhPCyp3 and Cu(NHC)(CHMePh) and are valuable forour future investigations of transmetallations with different PR3 and alkyl groups.

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2. Original papers(1) Hong Zheng, Kazuhiko Semba, Yoshiaki Nakao, Shigeyoshi Sakaki,“Characteristic Features of Transmetallation of Pd(II)-Ph Complex with Cu(I)-alkyl
Complexes: Theoretical Study” In preperation.
3. Others(1) Hong Zheng, Kazuhiko Semba, Yoshiaki Nakao, Shigeyoshi Sakaki,“Characteristic Features of Transmetallation of Pd(II)-Ph Complex with Co(I)- andCu(I)-alkyl Complexes: Theoretical Studies” CREST「新機能創出を目指した分子技術の構築」領域平成 27 年度第 2 回領域会議, Kyoto, December 5, 2015

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Nishamol Kuriakose
Nishamol Kuriakose
Research Fellow
Research Fellow
1. Summary of the research of the year
Rhodium (I) Complex with Anionic Aluminum Ligand: Bonding Nature and reactivity
Isolation and stabilization of highly reactive species and its use in the transformation process are an
important area of research. In this regard low valent element heterocycles of group 13 are widely recognized
for its potential in important chemical reactions. The characteristic features of these heterocyclic species are
the presence of a lone pair and a vacant π-orbitals at the element centre which in turn leads to its bifunctional
nature of nuleophicity and electrophilicity. Transition metal complexes with such group 13 element
heterocycles lead to interesting complexes due to the strong σ-donating ability of these ligands. In transition
metal complexes these ligands can coordinate with the metal centre as reactive ligands or as supporting
ligands. One interesting example reported is the transition metal complex with anionic boryl ligands, which
are successfully employed in catalytic borylation reaction and other functionalization reactions. Higher
analogues of group 13 anionic multidentate pincer ligands and its transition metal complexes are less studied.
Many theoretical investigations have been performed to understand the electronic properties of Group 13
element analogue of N-heterocyclic carbene (Arduengo-type carbene) bearing a negative charge. Recently
Nakao and co-workers synthesized a rhodium complex with an alanyl pincer-type ligand through the
reduction of a rhodium/aluminum heterobimetallic complex. In this complex the aluminum acts as a Z-type
ligand. We have performed theoretical calculation to understand the metal ligand bond interaction in
Rh-complex with Z-type ligand.
The optimized geometry of the experimentally obtained complexes is shown in Figure 1. We haveconducted a series of theoretical calculations with DFT method to understand the bonding nature of thesecomplexes. The complex 1a and 1b has a similar trigonal pyramidal structure and 1c has a five coordinatedtrigonal bipyramidal structure. In order to obtain the frontier molecular orbitals of the anionic aluminum
ligand, we have considered a model aluminum ligand L1 of PAlP, in which H atoms are substituted for PiPr2
moieties (See Figure 2a). In L1 the Al-N3 possesses an elongated bond of 2.337Å and the other Al-N bonds
possesses a shorter bond length of 2.015 Å. The Mayer’s bond order corresponding to the AlN1, AlN2 andAlN3 bonds are 0.603, 0.603 and 0.283 respectively. These values are consistent with the observed Al-Nbond length in the ligand moiety. The HOMO is a lone pair orbital located on the aluminum center and theempty 3p orbitals on the Al are found at LUMO + 9, LUMO+40 and LUMO+41 (Figure 2b). Since the two
Al-N bonds are not purely covalent Al can be considered to have only two electrons which suggest a formal+1 charge on the Al atom. The molecular orbitals of the L1 ligands shows the presence of six electrons oneach N atoms N1 and N2 (see Figure 3), therefore the N1 and N2 can considered to have a formal negative
charge.

Considering these features, L1 can be represented as a canonical form of diamido–Al+ [Figure 2c,－ 131 －

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2d].

Figure 1.

The optimized geometry of rhodium complexes 1a, 1b and 1c with selected bond lengths (Å) andbond angles (°); the experimental values are given inside the parenthesis; H atoms have been omitted forclarity.

Figure 2.

Geometry, electron distribution, and canonical form of a model of anionic aluminum ligand L1.

Figure 3.

Molecular orbitals of the anionic aluminum ligand L1.

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The Kohn-Sham orbitals of the Rh-complexes shows significantly large bonding overlap between the Rh
d and the Al lone pair orbitals [Figure 4(a-c)]. This suggests that a large covalent bonding interaction isformed between the Rh and Al atoms in these complexes. Because the d orbital (-8.5 eV) of a neutral[Rh(nbd)] is at lower energy than the Al valence orbital (-4.7 eV) of PAIP, the Rh-Al bond is polarized asRhδ- and Al δ+.

Figure 4.

The molecular orbital involving Rh-Al interaction in 1a, 1b and 1c.

In 1a, the position of the C=C double bond of norbornadiene coordinating is above the molecular plane.
Similar arrangement is observed for the case of 1b also. This can be due to the geometrical constraint by the
Al-N(Ph)-CH2-P chain structure which induces the PiPr2 moieties to take positions below the molecularplane with the PRhP angle of 141.5° and 111.6°, respectively (Figure 1). When the PRhP angle is 140 to 110°,
the two phosphines destabilizes d orbital which expands to the opposite direction from the phosphines.
Because of the strong π-back donation, the C=C double bond takes the position trans to these two phosphines
which in turn lead to the strong overlap with the d orbital.

The presence of the empty Al 3p orbitals allow

the Rh-complexes to coordinates with DMAP very easily. This coordination increases the constraint on the
Al-N(Ph)-CH2-P chain to decrease the P1-Rh-P2 angle. As a result, the PiPr moieties move more downward
from the molecular plane and thereby the C=C double bond moves more upward. Therefore, in 1c the C=C
double bond occupies almost perpendicular position to the Rh-Al bond. In 1c, two CO molecules coordinate
with the Rh probably because of smaller steric repulsion by CO. This complex has a typical trigonal
bipyramidal structure (Figure 1). The Rh-C1 at the position trans to the PAIP is moderately longer than the
Rh-C2 by 0.03 Å but this does not indicate weak trans-influence of PAIP, because the equatorial CO cannot
interact with a good acceptor orbital. The trans-influence of PAlP is estimated in camparison with CH3 group(see 1d in Figure 5). In the presence of -CH3 group the Rh-C1 distance is moderately longer in 1c than in 1d.
This indicates that the trans-influence of aluminum ligand is similar or moderately stronger than that of CH3.
(see Figure 5). From these features, it is concluded that this new PAlP ligand has unique natures and its Rh(I)complex 1a is reactive for the heterolytic σ-bond activation because the empty 3p of Al can interact anucleophilic moiety of reactant and the doubly occupied 4d of Rh can interact with an electrophilic moiety.

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Figure 5.

Optimized geometry of 1c and Rh(CH3)(PMe3)2(CO)2 (1d).

2. Original papers
1. Teruhiko Saito, Nishamol Kuriakose, Shigeyoshi Sakaki,* Yoshiaki Nakao* Synthesis of neutral
and anionic Aluminum containing Rhodium complexes and their reactivity toward cleavage ofsrong σ–bonds, (communicated).
3. Others (Presentation at symposium)(1) Nishamol Kuriakose, Teruhiko Saito, Yoshiaki Nakao, Shigeyoshi Sakaki“Sigma-Bond Activation by New Nickel(0) Complex with Z-type Aluminum Ligand:
Theoretical Study” The 13th symposium of Fukui Institute for Fundamental Chemistry,
Kyoto, Feb. 5, 2016.

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６．共同研究員

C. Sameera
W. M.W.
C. M.
Sameera
JSPS Postdoctoral Fellow, Fukui Kenichi Memorial Research Group 1
JSPS Postdoctoral Fellow, Fukui Kenichi Memorial Research Group 1
1. Summary of the research
Palladium catalyzed regioselective ring opening and borylation of 2-arylaziridines withbis(pinacolato)diboron
Aziridines are versatile building blocks in modern organic synthesis. Regioselective ring opening ofan aziridine is a useful strategy for the synthesis of biologically important compounds. We havedeveloped a palladium catalyzed regioselective borylative ring opening reaction of 2-arylaziridines,
giving rise to give β-amino-barylethylborates (Figure 1). This is the first example of ring opening
borylation of non-vinylic aziridines and direct borylative C(sp3)–N bond cleavage of neutral organic
substrates. This work was performed in collaboration with Prof. Takeda (Osaka University).

Figure 1. Palladium catalyzed regioselective ring opening borylation of 2-arylaziridines withbis(pinacolato)diboron.
Based on our NMR studies and density functional theory (DFT) calculations, we have concluded
that the active intermediate for the reaction is a PdL2 complex [L = P(t-Bu) 2Me]. Then, themulti-component artificial force induced reaction method (MC-AFIR) was used to find transition
states for the regioselectivity-determining aziridine ring opening step that proceeds in an SN2
fashion. Based on a Boltzmann distribution of 20 calculated TSs, the regioselectivity of the reaction
was calculated (89:11), and explained the experimental regioselectivity. Figure 2 shows themechanism of the full catalytic cycle that consists of a selectivity-determining aziridine ring
opening (i.e. oxidative addition), a proton transfer process, phosphine ligand dissociation from thecatalyst, rate determining boron–boron bond cleavage, phosphine ligand coordination, and reductive
elimination. The calculated overall mechanism and selectivity are consistent with the experimental
results. This study was published in Chem. Sci. DOI: 10.1039/C6SC01120A－ 135 －

－1－

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Figure 2. Mechanism of the full catalytic cycle from experimental and computational studies.
A biomimetic [Ni-Fe] cluster
Hydrogenases (H2ases) catalyzes the reversible oxidation of H2. Three main families have been
identified for H2ases, and are labeled according to the metal stoichiometry of their active sites;[NiFe]-, [FeFe]-, and [Fe]-H2ases. Hydrogen is a widely used reagent and a vector for energy
storage and a fuel for fuel cells. Because of the many potential uses of H2, much interest has
focused on replicating the catalytic properties of hydrogenase enzymes using molecular models of
their active sites. We aim to understand the reaction between a Ni-Fe cluster and its proton reactions.
This work was performed in collaboration with Prof. Tatsumi (Nagoya University).

－2－
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$ $
2-

S S

OC
Fe

NC
NC

PPh 3
Ni
CO

Yellow&brown*(A)$

1 equiv.
H+(HCl/Et 2O soln.)
THF-40 0C?*

Colour*gets*lighter*

½*H2*
e&*

Experimental,group,proposed,these,two,structures,,*

Figure 3. Protonation of the Ni-Fe cluster.

Among the calculated spin states of the Ni-Fe cluster, closed-shell singlet state is the most stableelectronic state. Optimized structure of the singlet state and the X-ray structures are in very good
agreement (Figure 4). In the triplet state, spin density of Fe (2.08) indicated that the two unpaired
electrons are localized on Fe. Triplet state is 14.7 kcal/mol higher than the closed-shell singlet,and the calculated <S2> value of the triplet state, 2.05, is similar to the ideal values of 2.00. The
quintet state is 13.0 kcal/mol higher than the singlet state, where spin densities are mainly locatedon Fe (3.57), while some spin densities are delocalised over Ni (0.21) and S (0.16). We havechecked the performance of several other density functions, namely BLYP-D3, BHandH, M06,
and TPSSTPSS-D3. Among the tested density functionals, B3LYP-D3 functional works well forthis system. Therefore, we continue our discussion with the B3LYP-D3 functional. Based on ourelectronic structure analysis, we concluded that the ground state of the Ni-Fe cluster is a
closed-shell singlet, and the oxidation states of the metals are Fe(II) and Ni(0). Then, theprotonation would start from the singlet ground state of the cluster.

－ 137 －

－3－

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Ⅳ 研究業績 (2015)

2.39*
2.31*
2.37* 2.18*
2.31*
1.72*
2.47*
1.92* 1.92*
1.72*

2.31*
2.27*
2.17*
2.26* 2.31*

1.71*
2.46*
1.90* 1.92*

1.73*
Good$$
agreement$

S*=*0*(calculated)*

X&ray*structure*

1.96*

2.44*
2.38*
2.18*
2.41*
2.33*

2.73*
1.99* 1.96*

2.57*

2.36*

2.57*
2.54*
2.12* 2.14*

2.04*

1.72*

2.37*
2.23*
1.72*

S*=*2*(calculated)*

S*=*1*(calculated)**

Figure 4. X-ray structure and the optimised structures of the possible electronic states of the
Ni-Fe cluster.
We have used MC-AFIR method to search possible reaction paths for the protonation process. 38
reaction paths were determined by a fully-automatic MC-AFIR search. Depending on the
protonation position, we have categorized the products in to 5 groups (Figure 5). Among them,
most of the reaction paths showed protonation of the S (19 paths) and CN (12 paths). Relatively
small number of paths was found for the protonation of Ni (5 paths), and only one path showed
the protonation of CO. A bridging H complex was also formed through 1 path.
$
H+

Fragm.1*

Low&level*

Gamma*=*200*

S S

OC
Fe

NC

PPh 3
Ni

NC

*

Low&level**
CO

Fragm.2*

*

* *

*

*

*

*

*

*

*

*

*

Figure 5. Fermentation of the molecular system for MC-AFIR calculations, and partition of themolecular system for the ONIOM calculations.
**
*

*

*

*

*

*

Among the protonated products, thermodynamically most stable complex (i) showed protonation*of a S group. Among the other possible products, (ii) (2.2 kcal/mol, protonationof Ni), (iii) (3.2,
*
*
*
* * *
*
*
*
－4－
－ 138* －
*
*
*
*
*
*
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Ⅳ 研究業績 (2015)

protonation of CN), and (iv) (2.3 kcal/mol) are only few kcal/mo higher in energy, and therefore
they may be formed under the reaction conditions. Work in progress for isolating the productcomplexes, and manuscript is in preparation.
** *

*

$

*

-

OC

HS

S

Fe

NC

NC

PPh 3

Ni

0.0/0.0

CO (i)

S S

OC
NC

-

H

Ni
CO

NC
2.2/2.2

S S
Fe

NC

PPh 3

H
4.7/2.3

(iv)

S S

OC
HCN

CO

OC

Fe
NC

CN

Fe

Ni

PPh 3

C
O

18.0/17.0

CO

PPh 3

H
NC

NC

S S
Fe

Ni
CO

24.2/21.3

-

Ni

PPh 3

14.7/14.5

-

PPh 3

(iii)

SH

S

C
CN O

8.2/6.4

O
C

CN
Fe

CO

NC

SH
Ni

4.1/3.2

OC

PPh 3

Ni

NC

(ii)

-

S

Fe

-

Ni

NC

S S

HNC

-

OC

-

OC

PPh 3

Fe

$

S S

HOC
NC
NC

-

Fe

Ni

CO
49.8/50.3

PPh 3

*

Figure 6. Possible product complexes and their relative energies (ΔE/ΔG).

*

*

*

*

*

*

2. List of original papers
1. BOOK CHAPTER: R. Ramozzi, W. M. C. Sameera, K. Morokuma, "Predicting reaction
pathways from reactants", Applied Theoretical Chemistry, World scientific publishing.
(Submitted)
2. REVIEW: W. M. C. Sameera, A. K. Sharma, S. Maeda, K. Morokuma, "Artificial force
induced reaction method for systematic determination of complex reaction
mechanisms", Chem. Rec. (Accepted)
3. S. Sasaki, S. Suzuki, W. M. C. Sameera, K. Igawa, K. Morokuma, G. Konishi, "Highly
twisted N,N-dialkylamines as a design strategy to tune simple aromatic hydrocarbons assteric environment-sensitive fluorophores". J. Am. Chem. Soc. (In press) DOI:
http://dx.doi.org/10.1021/jacs.6b03749
4. Y. Takeda, A. Kuroda, W. M. C. Sameera, K. Morokuma, S. Minakata, "Palladium-catalyzed regioselective ring-opening borylation of 2-arylaziridines withbis(pinacolato)diboron: experimental and computational studies", Chem. Sci. (In press) DOI:
10.1039/C6SC01120A
5. REVIEW: W. M. C. Sameera, S. Maeda, K. Morokuma, "Computational catalysis using theartificial force induced reaction (AFIR) method", Acc. Chem. Res. 2016, 49, 763-773.
－5－－ 139 －*
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6.

7.

8.

9.

1.

2.

3.

4.

5.

6.
7.

8.
9.

I. Funes-Ardoiz, W. M. C. Sameera, R. M. Romero, C. Martínez, J. A. Souto, D.
Sampedro, K. Muñiz, F. Maseras, "DFT rationalization of the diverse outcomes of theiodine(III)-mediated oxidative amination of alkenes", Chem. Eur. J. 2016, 22, 1-10.
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.
2015, 137, 11085-11094.
REVIEW: 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.
REVIEW: M. Besora, A. A. C. Braga, W. M. C. Sameera, J. Urbano, M. R. Fructos, P. J.
Perez, F. Maseras, "A computational view on the reactions of hydrocarbons with coinage
metal complexes", J. Organomet. Chem. 2015, 784, 2-12.
3. List of presentations at meetings.
W. M. C. Sameera, Keiji Morokuma, “Theoretical studies of control and design of catalytic
reactions using stimuli-responsive chemical species, stimuli-responsive chemical species forthe creation of functional molecules”, Hiroshima University, Japan. (Poster)W. M. C. Sameera, Keiji Morokuma, “International symposium on new development ofphysical organic chemistry: construction of chemical principles determining structures,reactions, and properties”, Fukuoka, Japan. (Poster)W. M. C. Sameera, Yasuhiro Ohki, Kazuyuki Tatsumi, Keiji Morokuma, “Biomimetic model
complexes for [NiFe] hydrogenase: density functional theory and artificial force-induced
reaction study”, The 13th FIFC symposium, Kyoto University, Japan. (Poster)W. M. C. Sameera, Keiji Morokuma, “Artificial force induced reaction method formechanistic and selectivity studies of transition metal complexes and clusters, the seventh
asia-acific conference of theoretical and computational chemistry (APCTCC 7)”, Kaohsiung,Taiwan. (Invited talk)
W. M. C. Sameera, Keiji Morokuma, “Artificial force induced reaction method forcomputational studies of transition metal complexes and clusters”, Department of Chemistry
and Molecular biology, University of Gothenburg, Sweden. (Invited talk)
W. M. C. Sameera, “The quantum mechanics of chemical reactions”, JSPS science dialogue
program, Tokyo, Japan (2015). (Invited talk)
W. M. C. Sameera, Keiji Morokuma, “Artificial force induced reaction method formechanisms involving transition metal complexes and clusters”, The 13th Fukui Centre
Seminar, Kyoto University, Japan (2015). (Invited talk)
W. M. C. Sameera, Keiji Morokuma, “Carbon-carbon bond formation reactions: DFT and
AFIR studies”the 15th ICQC meeting, Beijing, China. (Poster)W. M. C. Sameera, Bethmini Senevirathne, Muhsen Al-lbadi, Stefan Andersson, Gunnar
Nyman, “Interstellar radical species binding on ices: a hybrid QM/MM approach”, Tokyo
Institute and Technology, Japan. (Invited talk)－6－－ 140 －

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Ⅳ 研究業績 (2015)

Yanying Zhao
Yanying Zhao
Visiting Scholar
Visiting Scholar
1. Summary of the research of the year
Theoretical Study of Excited State Proton Transfer in 5-substituted-1,3,4-thiodizole-2-thione
molecules by GRRM
The photophysics and photochemistry of thiocarbonyls were reviewed by Maciejewski and Steer.
Previous studies revealed that the thione forms of small thioamides were much more stable than the thioltautomers in the ground electronic state. The calculated energy difference between the thione and thiol formsof thioacetamide was 39.1 kJ mol, which precluded thermal population of the thiol form of thioacetamide in
the ground electronic state due to a large transition energy barrier. The UV-induced HN–C=S → N=C–SH
excited state proton transfer (ESPT) reaction leading to the conversion of thione to thiol was observed for anumber of matrix-isolated thioamides. The ESPT reaction is fundamentally different from the classic excitedstate intramolecular proton transfer (ESIPT) process. ESIPT refers in particular to the proton transfer
reaction within an intramolecular hydrogen bond (−C=O···H–NC−). This is fulfilled neither for theheterocyclic compounds nor for thioacetamide.
Here,

we

theoreticallyinvestigatedtheexcited

state

decay

mechanismof

5-substituted-1,3,4-thiadizole-2-thione molecules (Scheme 1) by GRRM method. We carried out geometry
optimization using the TD-DFT method. The excited state minima S1, S2 and T1, minimum energy conicalintersection and seam crossing points are explored using SC-AFIR method. The results from theoretical
calculation are able to interpret our resonance Raman spectroscopic results. The excited state reaction
mechanism is tentatively proposed as S0→S2→S2/S1 or S2/Tn→S1/S0 or T1/S0→ S0'.
S

S

2
3

N

1

5
4

R

S

HS

N

N

H

R
N

Scheme 1－ 141 －

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Ⅳ 研究業績 (2015)

Figure 1. Geometry of local minima S1 of 5-amino-1,3,4-thiadizole-2-thione at
TD/B3LYP/6-311++G** level.

Figure 2. Geometry of local minimum S2 of 5-amino-1,3,4-thiadizole-2-thione at
TD/B3LYP/6-311++G** level.

－ 142 －

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Ⅳ 研究業績 (2015)

2. Original papers(1) Chen Xiao, Zhao Yanying*, Zhang Haibo, Xue jiadan, Zheng Xuming* Excitedstate proton transfer dynamics of thioacetamide in S2(π-π*) state: resonance Raman
spectroscopic and quantum mechanical calculations study. J. Phys. Chem. A 119,
832-842(2015)(2) Zhao Yanying, Xu Qiang* Chapter 15, Metal-organic frameworks as platforms forhydrogen generation from chemical hydrides in Organometallics and Related
Molecules for Energy Conversion, Green Chemistry and Sustainable Technology.
Springer-Verlag Berlin Heidelberg 421-467(2015). W.-Y. Wong (ed.), DOI 10.1007/
978-3-662-46054-2_15.
(3) Li Dan, Zhao Yanying*, Xue Jia-Dan, Zheng Xuming Structural dynamics of
4-formaldehyde imidazole and imidazole in light absorbing S2(π-π*) state Journalof Raman Sepctroscopy 46(3), 293-301(2015).
(4) Zhao Yanying * , Zhang Yuchen, Liu Xin, Zheng Xuming Formation,
characterization, structure and bonding analysis of the metal-carbon bond
OM-(ŋ6-C6H6) (M = Sc, Ti) complexes in solid matrix: Infrared spectroscopic andtheoretical study. J. Orgmet. Chem. 777, 25-30(2015)
3. Presentation at academic conferences
4. Others－ 143 －

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Ⅳ 研究業績 (2015)

Ming-Chung Yang
Ming-Chung Yang
Foreign Joint Researcher
Foreign joint researcher
1. A DFT Study of Addition Reactions between L4M(M=Rh, Ir), L2M(M=Pd, Pt) Fragments
and Endohedral Fullerene (Li+@C60)
Five synthetic routes have been proposed for the addition reactions of metal fragments with
C60. Denpending on to the bonding sites, the resulting complexes are denoted as η1-coordination,
η2[6,6]-coordination ([6,6] indicates the midpoint of two six-membered rings junction),η2[6,5]-coordination ([6,5] indicates the midpoint of a six and a five-membered ring junction),η5-coordination, and η6-coordination. It is known that the reactions of empty C60 with electron-richfragments such as IrCl(CO)(PPh3)2 and Pt(PPh3)2 give rise to the iridium fullerene complex(η2-C60)IrCl(CO)(PPh3)2 and iridium fullerene complex [(η2-C60)Pt(PPh3)2]. Recently, Tobita et al.
have reported the structures of iridium and platinum complexes of lithium cation encapsulated
fullerene (i.e., [{η2-(Li+@C60)}IrCl(CO)(PPh3)2](PF6-) and [{η2-(Li+@C60)}Pt (dppf)])(PF6-),
dppf=1,1′-bis(diphenylphosphino)ferrocene). These encapsulated complexes can be identified asη2[6,6]-coordination, and the most importantly, no other types of coordination was found. It was also
observed that the reaction of [IrCl(CO)(PPh3)2] with empty C60 is reversible, whereas the reactionof [IrCl(CO)(PPh3)2] with Li+@C60 is irreversible. In other words, the encapsulated iridium
fullerene complex become more stable once the Li+ is encapsulated into an empty C60. Theseexperimental evidencies raised our interests because it was reported that the encapsulated metal
cation can affect the reactivity of the C60 in the Diels-Alder reaction. However, to best of ourknowledge, no theoretical studies are reported to show the effect of a Li+ ion on the formation of
iridium and platinum complexes, and to study their selectivity.
In this work, we use AFIR method to investigate the addition reaction of L4M (M=Ir,
L4=Cl(CO)(PPh3)2) and L2M (M=Pt, L2=(PPh3)2) with E@C60 (E=0 and Li+). AFIR method isuseful to obtain approximate reaction paths systematically, and to locate approximate transition
state (TSs) and local minima (LMs) on the reaction path. Approximate stationary points can be
refined by using the standard computational methods. In the presence of precise reaction
mechanism for iridium and platinum complexes in hand, we have extended our stratergy to theelements in the third row, thus, M=Rh and Ir for L4M fragment and M= Pd and Pt for L2M fragment.
In addition, we would like to understand the role of a Li+ ion on the on the formation of metal
complexes. The following reactions were studied;
IrCl(CO)(PPh3)2 + C60→[{η2-C60)}IrCl(CO)(PPh3)2]
IrCl(CO)(PPh3)2 + Li+@C60→[{η2-(Li+@C60)}IrCl(CO)(PPh3)2]

(1a)
(1b)

－ 144 －

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Ⅳ 研究業績 (2015)

RhCl(CO)(PPh3)2 + C60→[{η2-C60)}RhCl(CO)(PPh3)2]
RhCl(CO)(PPh3)2 + Li+@C60→[{η2-(Li+@C60)}RhCl(CO)(PPh3)2]
Pt(PPh3)2 + C60→[{η2-C60)}Pt(PPh3)2]
Pt(PPh3)2 + Li+@C60→[{η2-(Li+@C60)}Pt(PPh3)2]
Pd(PPh3)2 + C60→[{η2-C60)}Pt(PPh3)2]
Pd(PPh3)2 + Li+@C60→[{η2-(Li+@C60)}Pt(PPh3)2]

(2a)
(2b)
(3a)
(3b)
(4a)
(4b)

Figure 1. Free energy profile (kcal/mol) of the reactants (L4Ir + E@C60), L4Ir----E@C60 complex,
intermediate, transition states, and final product, based on the M06/SDD/6-31G(d,p) calculations.
The red lines indicate the case in the occurrence of Li+ ion. The abbreviations OP, 66, and 65 standfor one-point attack, [6,6]-attack, and [6,5]-attack, respectively.

－ 145 －

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Ⅳ 研究業績 (2015)

Figure 2. Free energy profile (kcal/mol) of the reactants (L2Pt + E@C60), L2Pt----E@C60 complex,
intermediate, transition states, and final product, based on the M06/SDD/6-31G(d,p) calculations.
The red lines indicate the case in the occurrence of Li+ ion. The abbreviations OP, 66, and 65 standfor one-point attack, [6,6]-attack, and [6,5]-attack, respectively.
It is concluded that the multicomponent artificial force-induced reaction (MC-AFIR) searchsuggested that the [6,6] attacked is the most favorable reaction, which is consistent with theexperimental observations.
2. Original papers(1) Ming-Chung Yang, Akhilesh K. Sharma, W.M.C Sameera, Keiji Morokuma and Ming-Der Su,
A DFT Study of Addition Reactions between L4M(M=Rh, Ir), L2M(M=Pd, Pt) Fragments andEndohedral Fullerene (Li+@C60)(in preparation)－ 146 －

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Ⅴ 資料 (2015)

Ⅴ資料

１．研究業績一覧（平成 27 年度）
Volume (Number),first page tolast pageyear

Proc. Natl. Acad.
Sci. USA112, 6914

2015

Reply to Chakrabarty et al.: Particles
move even in ideal glasses

Proc. Natl. Acad.
Sci. USA112, E4821

2015

Atsushi Ikeda, Ludovic
Berthier

Thermal fluctuations, mechanicalresponse, and hyperuniformity in jammed
solidsPhys. Rev. E

92, 012309

2015

Harukuni Ikeda, Atsushi
Ikeda

One-dimensional Kac model of dense
amorphous hard spheres

EPL

111, 40007

2015

Journal of the
Mechanics andPhysics of Solids

78, 333-351

2015

№

Authors

Title

Journal1

Misaki Ozawa, Walter Kob,
Atsushi Ikeda, Kunimasa
MiyazakiEquilibrium phase diagram of a randomly
pinned glass-former

2

Misaki Ozawa, Walter Kob,
Atsushi Ikeda, Kunimasa
Miyazaki

3

4

池田

水野

昌司

英如

5

A. Nicolas, F. Puosi, H.
Mizuno, and J.-L. Barrat

Elastic consequences of a single plastic
event: Towards a realistic account ofstructural disorder and shear wave
propagation in models of flowing
amorphous solids

6

H. Mizuno, S. Mossa, andJ.-L. Barrat

Beating the amorphous limit in thermal
conductivity by superlattices design

Scientific
Reports

5, 14116(15pages)

2015

永瀬

茂

7

J.-D. Guo, S. Nagase, and
P. P. Power

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

Organometallics

34, 2028-2033

2015

8

T. Yang, S. Nagase,
T. Akasaka, J. M. Poblet,
K. N. Houk, M. Ehara, and
X. Zhao(2+2) Cycloaddition of Benzyne toEndohedral Metallofullerenes M3N@C80(M = Sc, Y): A Rotating-Intermediate
Mechanism

J. Am. Chem.
Soc.

137, 6820-6828

2015

9

T. Sasamori, T. Sugahara,
T. Agou, J.-D. Guo,
S. Nagase, R. Streubel, andN. Tokitoh

Synthesis and Characterization of a
1,2-Digermabenzene

Organometallics

34, 2106-2109

2015

10

T. Agou, T. Wasano,
T. Sasamori, J.-D. Guo,
S. Nagase, and N. Tokitoh

Ring Expansion to 1-Bromo-1alumacyclonona-2,4,6,8-tetraene by
Insertion of Two Alkyne Molecules into
the Al-C Bonds

Angew. Chem.
Int. Ed.

54, 9568-9571

2015

11

Y.-J. Guo, H. Zheng, T. Yang,
S. Nagase, and X. Zhao

Theoretical Insight into the Ambiguous
Endohedral Metallofullerene Er3C74:
Covalent Interactions among Three
Lanthanide Atoms

Inorg. Chem.

54, 8066-8076

2015－ 147 －

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Ⅴ 資料 (2015)№

Authors

Title

JournalVolume (Number),first page tolast page

year

12

T. Sasamori, T. Sugahara,
T. Agou, K. Sugamata, J.D. Guo, S. Nagase, and N.
TokitohReaction of a Diaryldigermyne with
Ethylene

Chem. Sci.

6, 5526-5530

2015

13

P. Zhao, H. Lei, C. Ni,
J.-D. Guo, S. Kamali,
J. C. Fettinger, F. Grandjean,
G. J. Long, S. Nagase, and
P. P. Power

Quasi-Three-Coordinate Iron and
Cobalt Terphenoxide Complexes{Ar iPr8OM(ì-O)}2 (Ar iPr8 = C6H-2,6-(C6H22,4,6-iPr3)2-3,5-iPr2; M = Fe or Co) with
M(III)2(ì-O)2 Core Structures and thePeroxide Dimer of 2-Oxepinoxyl Relevant
to Benzene Oxidation

Inorg. Chem.

54, 8914-8922

2015

14

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

Synthesis, Structure, and Reactivities of
Iminosulfane- and Phosphane-Stabilized
Carbones Exhibiting Four-Electron Donor
Ability

Chem. Eur. J.

21,15405-15411

2015

15

J.-D. Guo, D. J. Liptrot,
S. Nagase, and P. P. Power

The Multiple Bonding in Heavier
Group 14 Element Alkene Analogues is
Stabilized Mainly by Dispersion Force
Effects

Chem. Sci.

6, 6235-6244

2015

16

M. Kako, K. Miyabe, K. Sato,
M. Suzuki, N. Mizorogi,
W.-W. Wang, M. Yamada,Y. Maeda, M. M. Olmstead,
A. L. Balch, S. Nagase, andT. Akasaka

Preparation, Structural Determination,
and Characterization of Electronic
Properties of Bis-Silylated and BisGermylated Lu3N@I h-C80

Chem. Eur. J.

21, 16411-16420

2015

17

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

Diverse Coordination Modes in Tin
Analogues of a Cyclopentadienyl Anion
Depending on the Substituents on the Tin
AtomDalton Trans.

44,
16266-16271

2015

18

Y. Maeda, T. Tsuchiya,
T. Kikuchi, H. Nikawa,T. Yang, X. Zhao, Z. Slanina,
M. Suzuki, M. Yamada,
Y. Lian, S. Nagase, X. Lu,
and T. Akasaka

Effective Derivatization and Extractionof Insoluble Missing Lanthanum
Metallofullerenes La@C2n (n = 36-38)
with Iodobenzene

Carbon98, 67-73

2016

19

Z. Slanina, F. Uhlík, X. Lu,
T. Akasaka, K. H. Lemke,
T. M. Seward, S. Nagase, and
L. Adamowicz

Calculations of the Water-Dimer
Encapsulated into C84

Fullerenes,
Nanotubes,
CarbonNanostruct.

24, 1-7

2016

20

R. Zhao, Y. Guo, P. Zhao,
M. Ehara, S. Nagase, and
X. ZhaoWarning to Theoretical Structure
Elucidation of Endohedral
Metallofullerenes

J. Phys. Chem. C

120, 1275-1283

2016

21

T. Sasamori, J. M. V. Franco,
J.-D. Guo, K. Sugamata,
S. Nagase, R. Streubel, andN. Tokitoh

Selenium-Substituted Phosphaalkenes
Obtained through 1, 2-Eliminationof Chlorosilanes from
Selenenylchlorophines

Eur. J. Inorg.
Chem.

678-684

2016

22

J.-D. Guo, T. Sasamori,Y. Yamamoto, H. Matsubara,
S. Nagase, and H. Yorimitsu

Computational Picture of Silyl Transferfrom Silylsilatranes to Arylpalladium
Chloride

Bull. Chem. Soc.
Jpn.

89, 192-194

2016－ 148 －

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Ⅴ 資料 (2015)№

Authors

Volume (Number),first page tolast pageyear

Bull. Chem. Soc.
Jpn.

89, 361-368

2016

Title

JournalCrystal Structure of
4-methybenzenecarbothioic Acidand Computational Investigationsof Benzenecarbochlcogenoic Acids(C6H5COEH and C6H5CEOH, E = S, Se,
Te)

23

S. Kato, O. Niyomura,
K. Tani, M. Ebihara,
J.-D. Guo, and S. Nagase

榊

茂好

24

Wei Guan, Shigeyoshi
Sakaki, Takuya Kurahashi,and Seijiro Matsubara

Reasons Two Nonstrained C-C σ-Bonds
Can Be Easily Cleaved in Decyanative[4+2] Cycloaddition Catalyzed by
Nickel(0)/Lewis Acid Systems.
Theoretical InsightACS Catalytsis

5, 1-10

2015

25

Noriaki Ochi, Tsuyoshi
Matsumoto, Takuya Dei,
Yoshiaki Nakao, Hirofumi
Sato, Kazuyuki Tatsumi,
Shigeyoshi Sakaki

Heterolytic Activation of Dihydrogen
Molecule by Hydroxo-/Sulfido-Bridged
Rutheni um–Germanium Dinuclear
Complex. Theoretical Insights

Inorg. Chem.

54, 576-585

2015

26

Hisako Hashimoto, Yuto
Odagiri, Yasuhiro Yamada,
Nozomi Takagi, Shigeyoshi
Sakaki, and Hiromi Tobita

Isolation of a Hydrogen-BridgedBis(silylene) Tungsten Complex: A
Snapshot of a Transi-tion State for
1,3-Hydrogen Migration

J. Am. Chem.
Soc.

137, 158-161

2015

27

Naokazu Yoshikawa,
Shinichi Yamabe, Shigeyoshi
Sakaki, Nobuko Kanehisa,
Tsuyoshi Inoue,and Hiroshi
TakashimaTransition States of the 3MLCT to3MC Conversion in Ru(bpy)2(phenderivative)2+ Complexes

J. Mol. Struct.

1094, 98-108

2015

28

Hajime Kameo, Tatsuya
Kawamoto, Didier Bourissou,
Shigeyoshi Sakaki, andHiroshi Nakazawa

Evaluation of the sigma-Donation fromGroup 11 Metals (Cu, Ag, Au) to Silane,
Ger-mane, and Stannane Based on theExperimental/Theoretical Systematic
Approach

Organometallics

34, 1440-1448

2015

29

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

2015

30

Nozomi Takagi, Kazuya
Ishimura, Masafuyu Matsui,
Ryoichi Fukuda, Toru Matsui,
Takahito Nakajima, Masahiro
Ehara, and Shigeyoshi Sakaki

How Can We Understand Au8 Cores andEntangled Ligands of Selenolate- andThio-late-Protected Gold Nanoclusters
Au24(ER)20 and Au20(ER)16 (E = Se, S;
R = Ph, Me)? A Theoretical Study

J. Am. Chem.
Soc.

137, 8593-8602

2015

31

K. Kido, K. Kasahara,
H. Sato, S. Sakaki

A molecular level study of selective cation
capture by a host-guest mechanism for 25,
26, 27, 28-tetramethoxycalix[4]arene in
MClO4 solution (M=Na, K)

Mol. Simu.SI

41, 881-891

2015

32

Masafuyu Matsui, Masato
Machida, Shigeyoshi Sakaki

Characterization of AlPO4(110) Surface
in Adsorption of Rh Dimer and Its
Comparison with gamma-Al2O3(100)Surface: A Theoretical Study

J. Phys. Chem. C

119,19752-19762

2015

33

Hajime Kameo, Shigeyoshi
Sakaki

Activation of Strong Boron-Fluorineand Silicon-Fluorine sigma-Bonds:
Theoretical Un-derstanding andPrediction

Chem. Eur. J.

21,13588-13597

2015－ 149 －

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Ⅴ 資料 (2015)

Volume (Number),first page tolast pageyear

Chem. Eur. J.

22, 1076-1087

2015

Masayuki Nakagaki and
Shigeyoshi Sakaki

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

Phys. Chem.
Chem. Phys.

17,16294-16305

2015

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

2015

Shigeyoshi Sakaki

Theoretical and Computational Study of aComplex System Consisting of Transition
Metal Element(s): How to Understand andPredict Its Geometry, Bonding Nature,
Molec-ular Property, and Reaction
Behavior

Bull. Chem. Soc.
Jpn.

88, 889-938

2015

Naoki Haruta, Tohru Sato,and Kazuyoshi Tanaka

Reactivity Index for Diels-Alder
Cycloadditions to Large Polycyclic
Aromatic Hydrocarbons Using Vibronic
Coupling Density

TetrahedronLett.

56, 590-594

2015

39

Takuya Matsumoto, Kazuo
Tanaka, Kazuyoshi Tanaka,
and Yoshiki Chujo

Synthesis and Characterization of
Heterofluorenes Containing Fourcoordinated Group 13 Elements:
Theoretical and Experimental Analyses
and Comparison of Structures, Optical
Properties and Electronic States

Dalton Trans.

44, 8697-8707

2015

40

Yuichi Hirai, Takayuki
Nakanishi, Yuichi Kitagawa,
Koji Fushimi, Tomohiro
Seki, Hajime Ito, Hiroyuki
Fueno, Kazuyoshi Tanaka,Toshifumi Satoh, andYasuchika Hasegawa

Luminescent Coordination Glass:Remarkable Morphological Strategy for
Assembled Eu (III) Complexes

Inorg. Chem.

54, 4364-4370

2015

41

Furitsu Suzuki, Katsuyuki
Shizu, Hisafumi Kawaguchi,
Shinya Furukawa, Tohru
Sato, Kazuyoshi Tanaka, andHironori KajiMultiscale Simulation of Charge
Transport in a Host Material, N, N’Dicarbazole-3,5-benzene (mCP), for
Organic Light-Emitting Diodes

J. Mater. Chem.
C3, 5549-5555

2015

42

Daisuke Sakamaki, Soichiro
Yano, Toshiyuki Kobashi
Shu Seki, Takuya Kurahashi,
Seijiro Matsubara, Akihiro
Ito, and Kazuyoshi Tanaka

A Triphenylamine with Two Phenoxy
Radicals Having Unusual Bonding Pattersand a Closed-Shell Electronic State

Angew. Chem.
Int. Ed.

54, 8267-8270

2015

43

Shintaro Iwamoto, Yuu
Inatomi, Daisuke Ogi,
Satoshi Shibayama, Yukiko
Murakami, Minami Kato,
Kazuyuki Takahashi,
Kazuyoshi Tanaka, Nobuhiko
Hojo, and Yohji Misaki

New Tris- and Pentakis-Fused Donors
Containing Extended Tetrathiafulvalenes:
New Positive Electrode Materials for
Reachargeable Batteries

Beilstein J. Org.
Chem.

11, 1136-1147

2015

№

Authors

Title

34

Yue Chen, Yusuke Sunada,
Hideo Nagashima,
Shigeyoshi Sakaki,

Theoretical Study of Pd11Si6 Nanosheet
Compounds Including Seven-Coordinated
Si Spe-cies and Its Ge Analogues

35

36

37

Journal

田中 一義

38－ 150 －

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Ⅴ 資料 (2015)

Volume (Number),first page tolast pageyear

Chem. Phys.
Lett.

633, 190-194

2015

Highly Efficient Blue
Electroluminescence Using DelayedFluorescence Emitters with Large
Overlap Density between Luminescentand Ground States

J. Phys. Chem. C

119,26283-26289

2015

46

Takayuki Maegawa,Yasuyuki Irie, Hiroaki Imoto,
Hiroyuki Fueno, Kazuyoshi
Tanaka, and Kensuke Naka

para-Bisvinylhexaisobutyl-Substituted
T8 Caged Monomer: Synthesis andHydrosilylation Polymerization

Polym. Chem.

6, 7500-7504

2015

47

Liangchun Li, Tsukasa
Matsuo, Daisuke Hashizume,
Hiroyuki Fueno, Kazuyoshi
Tanaka, and Kohei Tamao

Coplanar Oligo(p-phenylenedisilenylene)s as Si=Si Analogues of Oligo(pphenylenevinylene)s: Evidence forExtended π-Conjugation through the
Carbon-Silicon π-Frameworks

J. Am. Chem.
Soc.

137,
15026-15035

2015

48

Ryohei Kurata, Kazuyoshi
Tanaka, and Akihiro Ito

Isolation and Characterization of
Persistent Radical Cation and Dication of
2,7-Bis(dianisylamino)pyrene

J. Org. Chem.

81, 137-145

2016

49

Megumi Kobayashi, Naoki
Hayakawa, Tsukasa Matsuo,
Baolin Li, Takeo Fukunaga,
Daisuke Hashizume,
Hiroyuki Fueno, Kazuyoshi
Tanaka, and Kohei Tamao(Z)-1,2-Di(1-pyrenyl)disilene: Synthesis,
Structure, and Intramolecular ChargeTransfer Emission

J. Am. Chem.
Soc.

138, 758-761

2016

50

Akihiro Ito, Masashi Uebe,
Kazuki Takahashi, Hiroshi
Ishikawa, Daisuke Sakamaki,
Hiroyasu Sato, Takashi
Matsumoto, and Kazuyoshi
TanakaSynthesis and Characterization of
6,13-Diamino-Substituted Pentacenes

Chem. Eur. J.

22, 2165-2170

2016

51

Hirotaka Uji, Kazuyoshi
Tanaka, and Shunsaku
KimuraO2-Triggered Directional Switchingof Photocurrent in Self-Assembled
Monolayer Composed of Porphyrin- andFullerene-Terminated Helical Peptides on
Gold

J. Phys. Chem. C

120, 3684-3689

2016

Driven anomalous diffusion: An example
from polymer stretching

Phys. Rev. E

92, 012601

2015

Reciprocating motion of active
deformable particles

Europhys. Lett.

114, 30002

2016

Third-order density-functional tightbinding combined with the fragment
molecular orbital method

Chem. Phys.
Lett.

636, 90-96

2015

№

Authors

Title

44

Masashi Uebe, Akihiro Ito,
Yuichiro Kameoka, Tohru
Sato, and Kazuyoshi Tanaka

Fluorescence Enhancement of NonFluorescent Triphenylamine: A Recipe to
Utilize Carborane Cluster Substituents

45

Katsuyuki Shizu, Hiroki
Noda, Hiroyuki Tanaka,
Masatsugu Taneda, Motoyuki
Uejima, Tohru Sato,
Kazuyoshi Tanaka, Hironori
Kaji, and Chihaya Adachi

齋藤
52

拓也
Takuya Saito, and Takahiro
Sakaue

多羅間
53

西本
54

Journal充輔

M. Tarama and T. Ohta

佳央
Yoshio Nishimoto, Dmitri G.
Fedorov, and Stephan Irle

－ 151 －

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Ⅴ 資料 (2015)

Title

JournalVolume (Number),first page tolast pageyear

Yoshio Nishimoto

Time-dependent density-functional tightbinding method with the third-order
expansion of electron density

J. Chem. Phys.

143(9), 094108

2015

56

Yoshio Nishimoto, Hiroya
Nakata, Dmitri G. Fedorov,and Stephan Irle

Large-Scale Quantum-MechanicalMolecular Dynamics Simulations Using
Density-Functional Tight-Binding
Combined with the Fragment MolecularOrbital Method

J. Phys. Chem.
Lett.

6(24),
5034-5039

2015

57

Yoshio Nishimoto

DFTB/PCM Applied to Ground andExcited State Potential Energy Surfaces

J. Phys. Chem. A

120(5), 771-784

2016

Ionization Energies and Aqueous Redox
Potentials of Small Organic Molecules:
Capabilities and Limitations of Modern
Methods

J. Chem. Theory
Comput.

12, 2272-2284

2016

Exploration of Quenching Pathwaysof Multiluminescent Acenes Using the
GRRM Method with the SF-TDDFT
MethodJ. Phys. Chem. A

119 (47),
11479-11487

2015

Artificial Force Induced Reaction Method
for Systematic Determination of Complex
Reaction Mechanisms

Chem. Rec.

DOI: 10.1002/
ter.201600052

2016

3D-RISM-MP2 Approach to Hydration
Structure of Pt(II) and Pd(II) Complexes:
Unusual H‑Ahead Mode vs Usual
O‑Ahead One

J. Chem. Theory
Comput.

12 (3),
1189-1206

2016

62

S. Sasaki, S. Suzuki,
W. M. C. Sameera, K. Igawa,K. Morokuma, G. Konishi

Highly twisted N,N-dialkylamines as adesign strategy to tune simple aromatichydrocarbons as steric environmentsensitive fluorophores

J. Am. Chem. Soc

138, 8194-8206

2016

63

Y. Takeda, A. Kuroda,
W. M. C. Sameera,
K. Morokuma, S. Minakata

Palladium-catalyzed regioselective ringopening borylation of 2-arylaziridines
with bis(pinacolato)diboron: experimental
and computational studies

Chem. Sci.

7, 6141-6152

2016

64

W. M. C. Sameera, S. Maeda,
K. Morokuma

Computational catalysis using theartificial force induced reaction (AFIR)
methodAcc. Chem. Res.

49, 763-773.

2016

65

I. Funes-Ardoiz, W. M. C.
Sameera, R. M. Romero,
C. Martínez, J. A. Souto,
D. Sampedro, K. Muñiz,
F. Maseras

DFT rationalization of the diverse
outcomes of the iodine(III)-mediatedoxidative amination of alkenes

Chem. Eur. J. ​22, 1-10.

2016№

Authors

55

伊勢川

58

鈴木

59

美穂

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

聡
S.Suzuki, S. Maeda,
K. Morokuma

Akhilesh Kumar Sharma
60

青野

61

W. M. C. Sameera, Akhilesh
Kumar Sharma, Satoshi
Maeda, Keiji Morokuma

信治
Shinji Aono, Toshifumi Mori,and Shigeyoshi Sakaki

W. M. C. Sameera－ 152 －

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Ⅴ 資料 (2015)

Volume (Number),first page tolast pageyear

J. Am. Chem. Soc

137,11085-11094

2016

The ONIOM Method and its Applications

Chem. Rev.

115, 5678-5796.

2015

A computational view on the reactionsof hydrocarbons with coinage metal
complexes

J. Organomet.
Chem.

784, 2-12.

2015

№

Authors

Title

Journal

66

W. M. C. Sameera,
M. Hatanaka, T. Kitanosono,
S. Kobayashi, K. Morokuma

The Mechanism of Iron(II)-catalyzed
Asymmetric Mukaiyama Aldol Reaction
in Aqueous Media: Density Functional
Theory and Artificial Force-Induced
Reaction Study

67

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

68

J. Llaveria, Á. Beltrán,W. M. C. Sameera, A. Locati,
M. M. Díaz-Requejo,
M. I. Matheu, S. Castillón,
F. Maseras, P. J. Pérez－ 153 －

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Ⅴ 資料 (2015)

２．共同研究者受入れ状況（平成 27 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

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・計算化学諸熊 奎治

W.M.C.
SAMEERA

外国人
共同研究者

平成 26 年 9 月 16 日 ~平成 28 年 7 月 31 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

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

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

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

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

University of South
Carolina（アメリカ）・
教授

複雑分子系の理論化
学

諸熊 奎治

NGUYEN Hoa My

招へい
外国人学者

平成 27 年 6 月 6 日 ~平成 27 年 8 月 28 日

ベトナム大学（ベトナム）･ 講師

メチシリン耐性黄色ブドウ球菌(MRSA)のベータラクタム抗生物質抵抗性の計算化学的方法による研究

諸熊 奎治

YANG MingChung

外国人
共同研究者

平成 27 年 8 月 10 日 ~平成 28 年 8 月 9 日

National Chiayi
University（台湾）・博士研究員

複雑分子系の計算化学的研究

YUAN Kun

外国人
共同研究者

平成 27 年 10 月 10 日 ~平成 28 年 1 月 10 日

Xi'an Jiaotong
University（中国）・
PhD 学生ナノカーボンの分子間相互作用の量子化
学計算

諸熊 奎治

EISENSTEIN
Odile

招へい
外国人学者

平成 27 年 10 月 23 日 ~平成 27 年 11 月 21 日

University ofMontpellier 2（フランス）・名誉教授

有機金属化学と均一系触媒反応の理論化
学・計算化学的研究

諸熊 奎治

ZHAO Yanying

招へい
外国人学者

平成 27 年 12 月 1 日 ~平成 28 年 11 月 30 日

Zhejiang Sci-Tech
University（中国）・准教授

複雑分子系の理論と計算研究

榊

KWAN HUNG,
Enrique

外国人
共同研究者

平成 28 年 2 月 1 日 ~平成 29 年 1 月 31 日

中央大学（日本）・
博士研究員

アルカンの触媒的脱水素化反応の計算化
学研究

永瀬

茂

茂好

－ 154 －

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Ⅴ 資料 (2015)

３．海外渡航一覧（平成 27 年度）

職

名

氏

名

期間（自）

期間（至）

目

的

地

准

教

授

池田

昌司

2015/5/2

2015/5/9

フランス

研

究

員

諸熊

奎治

2015/6/6

2015/6/14

中国

共同研究者

W.M.C. Sameera

2015/6/6

2015/6/14

中国

共同研究者

RAMOZZI, Romain
Raurcel, Marcel

2015/6/6

2015/6/14

中国

共同研究者

JAMAL, Adeel Ashraf

2015/6/6

2015/6/14

中国

特定研究員

青野

信治

2015/6/8

2015/6/13

中国

特定研究員

中垣

雅之

2015/6/8

2015/6/13

中国

特定研究員

多羅間

充輔

2015/6/16

2015/7/3

ドイツ

研

究

員

諸熊

奎治

2015/7/12

2015/7/19

アメリカ合衆国

研

究

員

諸熊

奎治

2015/8/23

2015/8/26

中国

研

究

員

諸熊

奎治

2015/8/31

2015/9/7

ノルウェー、スウェーデン

准

教

授

池田

昌司

2015/10/13

2015/10/17

大韓民国

研

究

員

榊

茂好

2015/11/19

2015/11/30

スペイン

研

究

員

諸熊

奎治

2015/11/21

2015/11/30

スペイン

2015/12/13

2015/12/20

アメリカ合衆国

共同研究者

JAMAL, Adeel Ashraf

研

究

員

諸熊

奎治

2015/12/14

2015/12/21

アメリカ合衆国

研

究

員

榊

茂好

2015/12/15

2015/12/21

アメリカ合衆国

研

究

員

永瀬

茂

2015/12/15

2015/12/21

アメリカ合衆国

特定研究員

多羅間

充輔

2015/12/17

2015/12/20

アメリカ合衆国

研

究

員

諸熊

奎治

2016/1/24

2016/1/29

台湾

研

究

員

榊

茂好

2016/1/24

2016/1/29

台湾

研

究

員

永瀬

茂

2016/1/24

2016/1/29

台湾

2016/1/24

2016/1/29

台湾

2016/1/25

2016/1/28

台湾

共同研究者
特定研究員

W.M.C. Sameera
青野信治－ 155 －

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Ⅴ 資料 (2015)

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－ 156 －

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Ⅴ 資料 (2015)

第 13 回京都大学福井謙一記念研究センターシンポジウム
プログラム
日時

平成 28(2016)年 2 月 5 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 10:00～15:00)
 開会の辞 赤木 和夫（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
 田中 一義 (京都大学 福井謙一記念研究センター) 司会：永瀬 茂（福井センター）「発光性分子材料の理論化学的設計」             ・・・10:15-11:15－ 休憩 － 西森 秀稔 (東京工業大学 大学院理工学研究科) 司会：佐々 真一（京大院理）「量子アニーリング理論と D-Wave マシン」

    ・・・11:30-12:30－ 昼休み － 永谷 清信＊ (京都大学 大学院理学研究科) 司会：池田 昌司（福井センター）「X 線自由電子レーザーとの付き合い方」

   ・・・14:00-15:00＊

八尾誠先生のご都合により、永谷清信先生に同内容でご代講いただく事になりました。
－ 休憩 －ポスターセッション (3 階大会議室 15:30～17:20)
懇親会 (1 階多目的ルーム 17:30～19:00)－ 157 －

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Ⅴ 資料 (2015)

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.

密度行列繰込み群による鉄―硫黄クラスターの構造および電子状態に関する理論的研
究○中谷 直輝、長谷川 淳也（北大触媒研）

2.

Computational Investigation of the Structural Dependence of Switching Efficiency
of Exchange Interaction and Hyperpolarizability on Diarylethenes〇西澤 尚平[1]、Arnaud Fihey[2]、Denis Jacquemin[2]、長谷川 淳也[3]、松田 建児[1]（京大院工[1]、ナント大 CEISAM[2]、北大触セ[3]）3.

有限温度における分子運動エネルギーの同位体効果○河津 励[1,2]、立川 仁典[2]（分子研[1]、横市大院生命ナノ[2]）4.

金属－炭素結合の開殻性と三次非線形光学特性についての研究○高椋章太、永海貴識、岸亮平、北河康隆、中野雅由（阪大院基礎工）

5.

インデノフルオレン系の開殻性、芳香族性、非線形光学物性に関する理論研究○福田 幸太郎、藤吉 純也、岸 亮平、中野 雅由（阪大院基礎工）6.

一次元シリコン鎖の第二超分極率における開殻性とσ/π共役の効果○松井 啓史、福田 幸太郎、伊藤 聡一、藤吉 純也、永海 貴識、泉 志旺、岸 亮平、
中野 雅由（阪大院基礎工）

7.

開殻性を持つフェナレニルラジカル二量体の二光子吸収特性に関する理論研究◯松下 尚之、福田 幸太郎、伊藤 聡一、松井 啓史、藤吉 純也、永海 貴識、泉 志旺、
岸 亮平、中野 雅由（阪大院基礎工）－ 158 －

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Ⅴ 資料 (2015)8.

高効率シングレットフィッションを示すペロピレン分子配置の量子化学計算に基づく探索○永海貴識[1]、伊藤聡一[1]、久保孝史[2]、中野雅由[1]（阪大院基礎工[1]、阪大院理[2]）9.

無置換 boron-dipyrromethene(BODIPY)と亜鉛ジピリン錯体の光物性に関する理論的研究○浅岡瑞稀、西久保玲奈、宮城公磁、竹林拓、北河康隆、中野雅由（阪大院基礎工）

10. ニコチンアミドの酸化還元における理論研究○西久保玲奈、浅岡瑞稀、北河康隆、中野雅由（阪大院基礎工）
11. TbPc2 錯体の安定および準安定構造に関する理論研究○北河康隆、浅岡瑞稀、宮城公磁、西久保玲奈、中野雅由（阪大院基礎工）
12. カテコール−キノン会合体の開殻性と第二超分極率の相関についての理論研究○泉 志旺、永海 貴識、藤吉 純也、伊藤 聡一、岸 亮平、中野 雅由（阪大院基礎工）13. 直線状縮合多環炭化水素系の開殻性と誘導電流密度異方性の相関に関する理論研究○藤吉純也、福田幸太郎、永海貴識、岸亮平、北河康隆、中野雅由（阪大院基礎工）14. 実在コラヌレン骨格を含む開殻一重項π共役系の非線形光学効果に関する理論的研究○南田有加、福田幸太郎、松井啓史、永海貴識、藤吉 純也、岸亮平、中野雅由（阪大院基礎工）
15. ニトロベンゼンのアニリンへの還元の経路の追跡○山邊 信一、山崎 祥子（奈良先端大、奈良教育大）
16. Theoretical study of the Zn-catalyzed aqueous Aldol reaction○Miho Hatanaka[1] （Faculty of Sci. and Eng. Kindai Univ. [1]）17. β-ジケトン型配位子を持つ Eu 錯体の発光強度の温度依存性に関する理論的研究○辻 佑樹[1]、畑中 美穂[1] （近大理工[1]）18. Eu 錯体の補助配位子と発光量子収率の関係○田中 孝幸[1]、畑中 美穂[1]（近大理工[1]）－ 159 －

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Ⅴ 資料 (2015)19. 熱流に誘起された力をめぐって○伊丹將人、佐々真一（京都大学）
20. Driven Anomalous Diffusion in Polymer Stretching○Takuya Saito[1] and Takahiro Sakaue[2]（FIFC[1], Kyushu Univ.[2]）21. アモルファス固体における弾性不均一性と熱伝導率○水野 英如（京大福井セ）
22. 時間依存密度汎関数強束縛（TD-DFTB）法に関する理論開発○西本 佳央（京大福井セ）
23. Construction of basis sets of 3d transition metals (Sc-Zn) for F12 explicitly
correlated method○伊勢川 美穂[1]、Robert Izsak、Dimitrios A. Pantazis、Frank Neese（京大福井セ[1]、マックスプランク研究所・化エ変換[2]）24. Theoretical Studies of Alkali Metal-Graphite Intercalation Compounds○Wataru Ota, Maxim Shishkin and Hirofumi Sato（京大院工）25. 分子シミュレーションによる ADP/ATP 輸送体の交互アクセス機構の原子論的解明○田村 康一、林 重彦（京大院理）26. 水溶性レチナール結合タンパク質の色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）27. XFEL を用いたヨウ化ウラシルの多価イオン化と電荷ダイナミクスの実験的観測○永谷 清信[1,2]、本村 幸治[3]、和田 真一[2,4]、福澤 宏宣[2,3]、大村 訓史[5]、立花徹也[3]、伊藤 雄太[3]、Mondal Subhendu[3]、古賀 亮介[4]、松波 健司[1]、酒井 司[1]、Kukk Edwin[6]、高橋 優祐[7]、菅野 学[7]、Rudenko Artem[8]、Nicolas Christophe[9]、Liu XiaoJing[9]、Miron Catalin[9]、Zhang Yizhu[10]、Jiang Yuhai[10]、Chen Jianhui[11]、Mailam Anand[12]、Kim Don Eon[12]、登野 健介[13]、矢橋 牧名[2]、河野 裕彦[7]、八尾 誠[1]、上田 潔[2,3]（京大院理[1]、理研放射光センター[2]、東北大多元研[3]、広島大院理[4]、広島工大[5]、University of Turku[6]、東北大院理[7]、Kansas State University[8]、Synchrotron Soleil[9]、SARI CAS[10]、SINAP CAS[11]、POSTECH[12]、JASRI[13]）－ 160 －

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Ⅴ 資料 (2015)28. SACLA のシングルショット X 線回折による単一クラスターの形状解析○西山俊 幸 [1] 、 Bostedt Christoph[2] 、 Ferguson Kenneth R.[2] 、 Hutchison

Christopher[1]、永谷 清信[1,3]、福澤 宏宣[3,4]、本村 幸治[4]、和田 真一[3,5]、酒井 司[1]、松波 健司[1]、立花 徹也[4]、伊藤 雄太[4]、Xu Weiqing[4]、Mondal Subhendu[4]、梅本 嵩之[5]、Nicolas Christophe[6]、Miron Catalin[6,7]、亀島 敬[8]、城地 保昌[8]、登野 健介[8]、初井 宇記[3]、矢橋 牧名[3]、上田 潔[3,4]、八尾 誠[1] （京大院理[1]、SLAC
National Accelerator Laboratory[2]、理研 RSC[3]、東北大多元研[4]、広大院理[5]、Synchrotron SOLEIL[6]、ELI-NP[7]、JASRI[8]）29. ルドルスデン-ポッパー相 AgRTiO4 における酸素八面体回転による反転対称性の破れ○吉田 傑[1]、藤田 晃司[1]、久家 俊洋[1]、赤松 寛文[2]、Arnab Sen Gupta[2]、Venkatraman Gopalan[2]、田中 勝久[1] （京大院工[1], ペンシルバニア州立大学[2])30. QM/MM 法による Ru(II)-SO2 錯体の結晶内異性化反応の理論的研究○青野 信治、榊 茂好（京大福井セ）
31. Embedded cluster model を用いた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]）32. Gas Adsorption into Porous Coordination Polymers Consisting of Cu PaddleWheel Units: Theoretical Investigation of the Interaction between Gas Moleculeand Organic Ligand○ Jia-Jia Zheng[1,2], Ryotaro Matsuda[2], Susumu Kitagawa[2] and Shigeyoshi
Sakaki[1] （FIFC[1], WPI-iCeMS[2]）33. Sigma-Bond Activation by New Nickel(0) Complex with Z-type Aluminum Ligand:
Theoretical Study○Nishamol Kuriakose[1], Shigeyoshi Sakaki[1], Teruhiko Saito[2], Yoshiaki Nakao [2]（FIFC [1], Grad. School. of Eng. Kyoto Univ.[2]）34. Reaction mechanism of silylene coordinated Mo and W complexes :Productselectivity for metals and solvents○Masayuki Nakagaki[1], Takako Muraoka[2], Keiji Ueno[2] and Shigeyoshi Sakaki[1]（FIFC[1]、School of Science and Technology, Gunma Univ.[2]）－ 161 －

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35. Characteristic Features of Transmetallation of Pd(II)-Ph Complex with Cu(I)-alkyl
Complex: Theoretical Study○Hong Zheng[1], Kazuhiko Semba[2], Yoshiaki Nakao[2] and Shigeyoshi Sakaki[1]（FIFC[1], Department of Material chemistry. Kyoto Univ.[2]）36. Cu38-nMn 金属微粒子の構造、電子状態、及び吸着特性に関する理論研究(M = Ru, Rh,
Pd, Ag, Os, Ir, Pt, Au;n = 0, 1, 2, 6)○高木 望[1]、 石村和也[2]、松井正冬[1]、 福田良一[1,2]、江原正博[1,2]、 榊 茂好[1,3]（京大 ESICB[1]、分子研[2]、京大福井セ[3]）37. Reactivity of Biomimetic Model Complexes for [NiFe] Hydrogenase: Density
Functional Theory and Artificial Force-Induced Reaction Study○W. M. C. Sameera[1], Yasuhiro Ohki[2], Zilong Li, Kazuyuki Tatsumi[2], and Keiji
Morokuma[1]（FIFC[1], Grad. School. of Sci. and Research Center for Materials Science,
Nagoya Univ.[2]）38. Computational Insights on the Mechanism and the Origin of Enantioselectivity in
Fe-Catalyzed Cross-Coupling Reaction

2○A. K. Sharma [1], W. M. C. Sameera [1], M. Nakamura [2] and K. Morokuma [1]（FIFC[1], Grad. School. of Eng. Kyoto Univ. [2]）39. Computational study on the photochemistry of (Z)-4,4-difluorobut-2-enal: Norrish
type II reaction vs cis-trans isomerization○Pedro J. Castro and Keiji Morokuma（FIFC）
40. A density functional study of the Addition Reactions Between L4M(M=Rh, Ir),
L2M(M=Pd, Pt) fragments and Endohedral Fullerene (Li+@C60)○Ming-Chung Yang[1], W.M.C Sameera[2], Keiji Morokuma[2] and Ming-Der Su[1,3]（Department of Applied Chemistry, National Chiayi University[1]、FIFC[2]、Departmentof Medicinal and Applied Chemistry, Kaohsiung Medical University[3]）41. Theoretical

Insight

into

Aggregation

InducedEmissioninbis(alkylamino)anthracene○鈴木聡、諸熊奎治（京大福井センター）－ 162 －

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Ⅴ 資料 (2015)

42. Theoretical study on ring opening and closing mechanism of diarylethene
derivatives○ Kimichi Suzuki[1], Satoshi Suzuki[2], Satoshi Maeda[1], and Keiji Morokuma[2]（Hokkaido University[1], FIFC[2]）43. 共役ポリマーとキラルネマチック液晶を組み合わせた選択反射による白色円偏光
Chiral resolution affording white circularly polarized light with tuned handedness
through selective reflection○大田冬木、閻家林、赤木和夫（京大院工）
44. キラル液晶場での光架橋重合によるヘリカルネットワークポリマーの合成とキラルテンプレートへの応用
Synthesis of Helical Network Polymers by Photo-crosslink Polymerization in
Chiral Liquid Crystal Field and Their Application to Chiral Templates○稲垣拓也、朴珍旴、赤木和夫（京大院工）45. キラルおよびラセミ芳香族共役系ポリマー間でのヘリカル積層π- π相互作用に基づ
く キ ラリ ティ 転写 (Chirality Transfer through Interchain Helically π -Stacking
Interactions between Chiral and Racemic Aromatic Conjugated Polymers)○野津 賢祐、 渡辺 和誉、 赤木 和夫（京大院工）－ 163 －

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５．福井センターセミナー

ポスター・プログラム

第１３回
福井センターセミナー
The 13th Fukui Center Seminar
2015年9月29日(火) 15:00-17:20

京都大学福井謙一記念研究センター1F 多目的室 (Room: 1F 106)
http://www.fukui.kyoto-u.ac.jp/〒606-8103 京都市左京区高野西開町34-4（℡075-711-7708)(at FIFC, Kyoto Univ. on September, 29(Tue.), 2015)

15:00～15:40

W. M. C. SAMEERA (FIFC)“Artificial force induced reaction method formechanisms involving transition metal complexes
and clusters”
15:40～16:20

Takuya SAITO (FIFC)“Driven Anomalous Diffusion in Polymer Stretching”
Break (10 min.)16:30～17:20

Masayuki OHZEKI (Kyoto Univ.)“Accelerated Langevin Dynamics and its application
to machine learning”
多数の方のご来場を歓迎いたします
We welcome all of you to join.

－ 164 －

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京都大学福井謙一記念研究センター

年報

2015

2016 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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