年
報
年 報

2010
2017

京都大学
福井謙一記念研究センター

の発展に多大な貢献をしたとして、文は じ め に化功労者の顕彰を受けられました。ま2017 年度の京都大学福井謙一記念研た、2015 年 か ら は FIFC リ サ ー チ フ ェ究センターの活動をまとめた年報をおローとして研究ならびに若手人材育成

届けします。本センターは、京都大学にご尽力頂き、逝去されるほぼ 3 週間

本部構内の北、約 1 キロの高野川沿い

前まで、活発な研究活動を展開してこの静かな住宅街に独立して位置しておられました。諸熊先生は理論化学・計ります。専任教員は理論研究部門と総算化学の領域で多くの学術的業績を挙合研究部門に 1 名ずつを持っているにげられるとともに、我が国の量子化学過ぎませんが、センター長のほか副セの分野を牽引され、多数の研究者を育ンター長とスーパーバイザーとして工成されました。謹んでご冥福をお祈り

学研究科、理学研究科、化学研究所所

申し上げます。

属の 12 名の教員にご協力頂いており、本センターでは、上記の諸熊奎治先

このメンバーが運営委員会を構成して生の招聘ののち、2009 年度に福井謙一

います。そして優れた博士研究員に研記念研究部第二を設置し、名古屋大学

究活動の機会を与える制度を持ってお名誉教授（前副学長）の大峯巖先生をり、若手研究者が国際的な雰囲気の中リサーチリーダーとして招聘し、研究

で日夜研究にいそしんでいます。福井

体制を拡大しました。なお、大峯先生

センターフェローと呼ばれる博士研究は 2010 年 4 月に分子科学研究所長に転員はセンターの雇用で、自分自身のア出されました。その後任として、2011

イデアで一定期間、自由闊達に研究で

年 4 月に京都大学物質―細胞統合シス

きる身分を保証しています。

テム拠点（iCeMS）特任教授の榊茂好2017 年度は本センターにとりまして

先生を研究部第二のリサーチリーダー

大きな出来事がありました。2017 年 11として招聘しました。榊先生は、遷移

月 27 日、FIFC リサーチフェローとして金属化合物や類縁化合物に関する研究

ご活躍であった諸熊奎治先生（分子科で顕著な業績を挙げておられ、現在は学研究所名誉教授）が、83 年間の研究

d 電子複合系の理論化学に関する研究を者人生を全うされました。本センター

推進しておられます。

では、2006 年 9 月に福井謙一記念研究2012 年にはシニアリサーチフェロー

部第一のリサーチリーダーとして諸熊として永瀬茂先生（分子科学研究所名奎治先生を米国エモリー大学から招聘

誉 教 授 ） を 招 聘 し ま し た。 永 瀬 先 生

しました。諸熊先生は、2012 年にシニ

は、望む構造、物性、機能を持つ分子

アリサーチフェローに就任され、このを自在に組み立てて思うように反応さ年の 11 月には、複雑分子系の理論研究

せる理論と計算およびコンピューター－i－シミュレーションの開発において顕著

際に、センターの博士研究員であったな業績を挙げられました。2015 年から

多くの方々が、現在、国内外の大学、は FIFC リサーチフェローとして高周期研究機関で活躍しておられます。2016

典型元素と遷移金属元素化学種の理論

年には、化学の将来の発展のために若化学に関する研究を進めておられます。

手研究者の育成の大切さを説いておら同じ年に、シニアリサーチフェローとれた福井博士の遺志を汲み、基礎化学・して田中一義先生（京都大学名誉教授）

理論化学の分野で顕著な研究業績を挙を招聘しました。田中一義先生は導電

げた若手研究者を顕彰する「福井謙一

性や磁性を有する有機化合物など量子奨励賞」を創設しました。2017 年は、機能材料に関する物理化学的研究にお

第 2 回福井謙一奨励賞が、「第一原理波いて優れた多くの業績を挙げておられ、動関数理論の固体への展開 : 量子化学

現在は元素ブロックを有する分子・高と固体電子論の融合」に関する成果が分子の理論化学に関する研究を展開さ評価された大阪大学大学院理学研究科

れています。さらに、2016 年には、化の越智正之博士に授与されました。

学反応電子動力学の基礎理論研究にお当センターの歴史を簡単にご紹介しいて著名な高塚和夫先生（東京大学名ます。ご承知のように故福井謙一京都

誉教授）をリサーチリーダーとして招大学名誉教授はフロンティア軌道理論

聘しました。センターでは非断熱電子を提案したご功績により、1981 年にわ

動力学理論による化学反応の解析に関が国で最初のノーベル化学賞を受賞さする研究を推進しておられます。

れました。福井先生が京都大学ご退官2018 年 2 月には理論研究部門の専任

後に研究を続けられるため、京都市と教授として、佐藤徹先生が着任されま

産業界などのご支援で 1985 年に財団法した。佐藤徹先生は振電相互作用に関人「基礎化学研究所」が設立されました。

する研究、特に動的ヤーンテラー効果

専任研究員数名の規模でしたが、研究や振電相互作用を解析・制御する振電のレベルは高く、当時の研究員は、東相互作用密度を用いた有機 EL 素子など

京大学、名古屋大学、分子科学研究所の機能性分子材料の理論設計を行っての教授になるなど、理論化学分野でトッいます。佐藤徹先生の研究室は、工学

プクラスの研究者として活躍していま

研究科分子工学専攻の協力講座（分子す。この基礎化学研究所は 1998 年の福材料科学講座電子物性化学分野）と井先生のご逝去の後、2002 年に本学にしても位置付けられ、大学院生、学部 4寄贈され、福井謙一記念研究センター

回生が配属されて、研究を進めています。

となり、現在に至っております。京都

私達は、センターが若手研究者の登大学の部局となった後、森島竜門となることを期待しています。実績、中辻 博、榊 茂好、田中 功、田中一義、－ ii －

赤木和夫の各先生にセンター長としてた。コーナーでは先生が使用された机、ご指導を頂きました。

椅子、ノーベル賞メダル・賞状（複製）、本センターは、国際活動も活発で、研究ノート・メモ、写真などを展示し、2005 年よりチェコおよびスロバキアと常設展示として一般に公開しています。

理論化学・計算化学シンポジウムを定加えて、福井謙一先生の生誕百年に期的に開催しております。2011 年にはあたる 2018 年に開催のメモリアルシン

国内外（主にドイツ、東欧、中国、韓ポジウム、記念式典、サテライトシン

国）から第一線の研究者を招き、第 1

ポジウム、京大総合博物館での記念展

回福井センター理論化学・計算化学国に向けて、2017 年には福井謙一生誕百際シンポジウムを開催しました。こう

年記念事業実施委員会を中心に準備をした国際連携活動をさらに活性化する進めました。

という観点から、2016 年 2 月に国際学本センターは、上述のように規模は術連携研究室（2016 年 12 月に国際連携大きくありませんが、研究活動は極め

インターディシプリナリー研究推進室て活発です。今後も、京都大学あるいと改組）を設置し、その運営上必要とは国内外との共同研究を積極的に進めなるコーディネーター役として、特定て行きたいと考えております。とくに

助教 1 名を配置しました。本センターは、

実験科学者との共同研究は重要であり、今後も、理論化学・計算化学分野におそのような連携研究をさらに活発化しけるわが国の研究拠点の役割を果たし、たいと考えております。

国際連携活動を展開して行きたいと考

この年報により、本センターの活動

えております。

に興味をお持ち頂ければ幸甚です。そまた、例年初冬に福井センターシン

して、それが共同研究の契機となり、時ポジウムを開催しており、国内外のトッ間をかけて大きな成果に結実していく

プクラスの研究者による特別講演、運営ことを念願しています。最後になりま委員の講演、並びに京都大学内外からしたが、本センターの順調な活動はひのポスター発表を行っております。研とえに工学研究科、理学研究科、化学

究発表のレベルは高く、特別講演に来研究所のご協力、ご援助の賜物であり、られた講師からも毎年高い評価を得てここに心から御礼申し上げる次第です。

おります。
さらに社会貢献活動の一環として、2019 年 2 月

2011 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、これを節目と京都大学福井謙一記念研究センター長

して本センター玄関ロビーに先生ゆか

田りの文物の展示コーナーを設置しまし－ iii －

中

勝

久

目

はじめに

Ⅰ

次

京都大学福井謙一記念研究センター長田中勝久�������

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

ⅡⅢ(1) センター長 �������������������������

2(2) 副センター長 ������������������������

3(3) スーパーバイザー ����������������������

5(4) 専任教員 ��������������������������

16(5) FIFC リサーチフェロー  ��������������������

18(6) シニアリサーチフェロー �������������������

19(7) リサーチリーダー ����������������������

24(8) 研究員 ���������������������������

25

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

26

２．日本学術振興会外国人特別研究員 �����������������

26

３．日本学術振興会特別研究員 ��������������������

26

４．博士研究員プロフィール ���������������������

27

５．日本学術振興会外国人特別研究員プロフィール �����������

42

６．日本学術振興会特別研究員プロフィール ��������������

43

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 ��������������

44

２．セミナー ……………………………………………………………………………

45（1）第 15 回福井センターセミナー（2）その他のセミナー
３．国際交流 ����������������������������

－ iv －

46

Ⅳ

４．社会へのアウトリーチ活動 ��������������������

47

５．福井謙一奨励賞の創設及び奨励賞の授与 ��������������

47

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

48

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

53

３．シニアリサーチフェロー ���������������������

60

４．リサーチリーダー ������������������������

73

５．博士研究員 ���������������������������

80

６．日本学術振興会外国人特別研究員 ����������������� 144
７．日本学術振興会特別研究員 �������������������� 147

Ⅴ資料
１．研究業績一覧 ……………………………………………………………………… 151
２．共同研究者受入れ状況 …………………………………………………………… 159
３．海外渡航一覧 ……………………………………………………………………… 159
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 ………… 160

ポスター・プログラム ……………………………… 167（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/AnnualReport2017.pdf）－v－

Ⅰ 専任教員 ･ スーパーバイザー (2017)Ⅰ

専任教員・スーパーバイザー

１．教員組織職

協議

平成２９年度
名

氏

センター長

田 中

勝 久

工学研究科材料化学専攻

副センター長谷 村

吉 隆

理学研究科化学専攻

副センター長佐 藤

啓 文

工学研究科分子工学専攻

副センター長（欠員中）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

名備考

工学研究科長北 村

隆 行

工学研究科機械理工学専攻

理学研究科長平 野丈 夫

理学研究科生物科学専攻

化学研究所長時 任

宣 博

化学研究所物質創製化学研究系

教

授

古 賀

毅

工学研究科高分子化学専攻

教

授

跡 見

晴 幸

工学研究科合成・生物化学専攻

教

授

佐 々

真 一

理学研究科物理学・宇宙物理学専攻

教

授

山 本

潤

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

山 本

量 一

工学研究科化学工学専攻

教

授

高 田

彰 二

理学研究科生物科学専攻

教

授

林

重 彦

理学研究科化学専攻

総合研究部門

准 教 授

（欠員中）

理論研究部門

教

授

佐 藤

徹

国際連携インターディシ
プリナリー研究推進室

特定助教

西 本

佳 央

専

諸熊グループFIFC リサーチ
フェロー

諸 熊

奎 治

研究員

永瀬グループFIFC リサーチ
フェロー

永 瀬

茂

研究員

榊グループ

シニアリサーチ
フェロー

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

高塚グループリサーチリーダー

高 塚

和 夫

研究員

榊グループ

研 究 員

北 浦

和 夫

研究員

－1－

専任：平成 30.2.1 －（工学研究科分子工学専攻協力講座）
任Ⅰ 専任教員 ･ スーパーバイザー (2017)

２. 教員プロフィール
⑴

センター長

【氏名】 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. 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（過去 5 年以内）
breaking by oxygen octahedral rotations in Ruddlesden-Popper NaRETiO4 family”,
Physical Review Letters 112 (2014) 187602-1-5.
2. 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 of cathodematerials with prolonged cycle life for lithium-ion battery”, Nature Communications
5 (2014) 4553-1-7.
3. 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, andK. Tanaka, “Room-temperature polar ferromagnet ScFeO3 transformed from a highpressure orthorhombic perovskite phase”, Journal of the American Chemical Society
136 (2014) 15291-15299.
4. 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.
5. K. Fujita, T. Kawamoto, I. Yamada, O. Hernandez, N. Hayashi, H. Akamatsu, W.
Lafargue-Dit-Hauret, X. Rocquefelte, M. Fukuzumi, P. Manuel, A. J. Studer, C. Knee,and K. Tanaka, “LiNbO3-type InFeO3: Room-temperature polar magnet without
second-order Jahn-Teller active ions”, Chemistry of Materials 28 (2016) 6644-6655.
6. Y. Nakatsuka, K. Pollok, T. Wieduwilt, F. Langenhorst, M. A. Schmidt, K. Fujita, S.
Murai, K. Tanaka, and L. Wondraczek, “Giant Faraday rotation through Fe0n states insuperparamagnetic FeO-SiO2 vitreous films”, Advanced Science (2017) 1600299-1-6.
7. T. Sawai, Y. Yamaguchi, N. Kitamura, T. Date, S. Konishi, K. Taga, and K. Tanaka,“Pulse-based electron spin transient nutation measurement of BaTiO3 fine particle:
Identification of controversial signal around g=2.00”, Applied Physics Letters 112(2018) 202902-1-4.
【学術関係の受賞など】 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）－2－

Ⅰ 専任教員 ･ スーパーバイザー (2017)⑵

副センター長【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】 化学物理理論【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、分子科学会、アメリカ化学会、アメリカ物理学会【主な著書、学術論文】 1. Y. Tanimura, Real-Time and Imaginary-Time Quantum Hierarchal Fokker-Planck（過去 5 年以内）
Equations, J. Chem, Phys 142, 144110 [20 pages](2015).
2. H. Ito and Y. Tanimura, Simulating two-dimensional infrared-Raman and Raman
spectroscopies for intermolecular and intramolecular modes of liquid water, J.
Chem. Phys. 144 074201 [16 pages] (2016). [JCP Editors’Picks]
3. A. Kato and Y. Tanimura, Quantum Heat Current under Non-perturbative and NonMarkovian Conditions: Applications to Heat Machines, J. Chem. Phys. 145, 224105(2016) [JCP Editors’Picks]
4. K. Nakamura and Y. Tanimura, Hierarchical Schrödinger Equations of Motion forOpen Quantum Dynamic, Phys. Rev. A 98, 012109 (2018)
5. Y. Iwamoto and Y. Tanimura, Linear Absorption Spectrum of a Quantum TwoDimensional Rotator Calculated using a Rotationally Invariant System-BathHamiltonian, J. Chem. Phys. 149, 084110 [8 page] (2018)【学術関係の受賞など】 2002 年
2012 年2015 年

分子科学研究奨励森野基金
フンボルト賞（ドイツ）
アメリカ物理学会フェロー－3－

Ⅰ 専任教員 ･ スーパーバイザー (2017)【氏名】 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【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−）、
副主査（2015 年−）
理論化学研究会 第三期世話人（2009 年− 2018 年）
分子科学会 幹事（2012 年− 2013 年）、運営委員（2012 年− 2016 年，2018 年−）
溶液化学研究会 運営委員（2015 年−）【主な著書、学術論文】 1. Yoshihiro Matsumura, Satoru Iuchi, Shuichi Hiraoka, and Hirofumi Sato,“Chiral（過去 5 年以内）
effects on the final step of an octahedron-shaped coordination capsule selfassembly”Phys. Chem. Chem. Phys., 20, 7383-7386 (2018).
2. Hisashi Okumura, Masahiro Higashi, Yuichiro Yoshida, Hirofumi Sato, and
Ryo Akiyama,“Theoretical approaches for dynamical ordering of biomolecularsystems”BBA General Subject, 1862, 212-228 (2018).
3. Maxim Shishkin, Shinichi Kumakura, Syuhei Sato, Kei Kubota, Shinichi Komaba,and Hirofumi Sato,“Unraveling the Role of Doping in Selective Stabilization of
NaMnO2 Polymorphs: Combined Theoretical and Experimental Study”Chem.
Materials, 30, 1257 (2018).
4. Kento Kasahara and Hirofumi Sato,“Dynamics theory for molecular liquids basedon an interaction site model”Phys. Chem. Chem. Phys. 19, 27917-27929 (2017).
5. Hirofumi Sato,“A modern solvation theory: quantum chemistry and statisticalchemistry”Phys. Chem. Chem. Phys. 15(20), 7450-7465 (2013).
【学術関係の受賞など】 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）－4－

Ⅰ 専任教員 ･ スーパーバイザー (2017)⑶

スーパーバイザー【氏名】 古賀

毅 （こが

つよし）

【職名】 教授【所属】 工学研究科【研究室】 桂キャンパス

高分子化学専攻
A3 棟 115 号室【直通電話】 075-383-2705【FAX】 075-383-2706【電子メールアドレス】 tkoga@phys.polym.kyoto-u.ac.jp【ホームページ】 http://www.phys.polym.kyoto-u.ac.jp【研究分野】 高分子系の統計力学・計算科学【現在の研究課題】 高分子系の構造形成とダイナミクス【研究内容キーワード】 高分子・ゲル・レオロジー【学歴】 1993 年 3 月九州大学大学院理学研究科物理学専攻博士後期課程修了【学位】 1993 年 3 月九州大学博士（理学）【略歴】 1993 年 4 月日本学術振興会特別研究員，1994 年 4 月新技術事業団 ERATO
橋本相分離構造プロジェクト研究員，1998 年 5 月京都大学工学研究科助手，
2009 年 4 月京都大学工学研究科准教授，2012 年 8 月京都大学工学研究科教授【所属学会】 高分子学会，日本レオロジー学会，The American Chemical Society【学会活動】 2016.6-2018.5: 高分子学会理事
2014.5- 現在 : 高分子学会関西支部常任幹事【主な著書、学術論文】 1. Theoretical study of inclusion complex formation of cyclodextrin and single（過去 5 年以内）
polymer chain, T. Furuya, T. Koga, POLYMER, 131, 193-201 (2017)
2. Physical gelation of supramolecular hydrogels cross-linked by metal-ligand
interactions: Dynamic light scattering and microrheological studies, H. Ozaki, T.
Indei, T. Koga, T. Narita, POLYMER, 128, 363-372 (2017)
3. Network Formation and Mechanical Properties of Telechelic Associating Polymers
with Fixed Junction Multiplicity, H. Ozaki, T. Koga, MACROMOLECULAR
THEORY AND SIMULATIONS, 26, 1600076 (2017)
4. Statistical Thermodynamic Theory of Heat-Induced Gelation of Aqueous
Methylated Polyrotaxane Solutions, H. Kojima, T. Koga, MACROMOLECULES,
49, 7015-7024 (2016)
5. Theoretical Study of Network Formation and Mechanical Properties of PhysicalGels with a Well-Defined Junction Structure, H. Ozaki, T. Koga, JOURNAL OF
PHYSICAL CHEMISTRY B, 120, 7745-7753 (2016)－5－

Ⅰ 専任教員 ･ スーパーバイザー (2017)【氏名】 跡見晴幸 （あとみはるゆき）【職名】 教授【所属】 工学研究科

合成・生物化学専攻【研究室】 桂キャンパス A4 棟 217 号室【直通電話】 075-383-2777【FAX】 075-383-2778【電子メールアドレス】 atomi@sbchem.kyoto-u.ac.jp【ホームページ】 http://www.sbchem.kyoto-u.ac.jp/atomi-lab/en/【研究分野】 応用微生物学・応用生物化学、基礎ゲノム科学、生体関連化学、生物・生体工学、
生物系、構造生物化学【現在の研究課題】 アーキアや極限環境微生物の代謝生理【研究内容キーワード】 微生物、微生物代謝、生合成、アーキア、極限環境微生物、ゲノム、超好熱菌、炭酸固定、遺伝子発現制御、合成生物学【最終学歴】 1992 年 3 月京都大学大学院工学研究科工業化学専攻博士課程単位認定退学【学位】 1992 年 3 月工学博士（京都大学）【略歴】 1992 年 4 月京都大学工学部工業化学科助手、1997 年 5 月京都大学大学院工学研究科合成・生物化学専攻助教授、2009 年 3 月京都大学大学院工学研究科合成・生物化学専攻教授【在外研究歴】 1994 年 4 月 ~1995 年 9 月ドイツ Stuttgart 大学

博士研究員【所属学会】 生物工学会、日本化学会、農芸化学会、ゲノム微生物学会、環境バイオテク
ノロジー学会、極限環境生物学会、生化学会、酵素工学研究会、バイオイ
ンダストリー協会、分子生物学会、マリンバイオテクノロジー学会、日本
ア ー キ ア 研 究 会、International Society for Extremophiles、American Society for
Microbiology【学会活動】 酵素工学研究会 会長、日本化学会バイオテクノロジー部会 部会長、
日本生物工学会 理事、ゲノム微生物学会 評議員、環境バイオテクノロジー学会 理事、日本アーキア研究会 幹事、極限環境生物学会 幹事
International Society for Extremophiles Vice-president【主な著書、学術論文】 1. Nagata R, Fujihashi M, Sato T, Atomi H, Miki K. “Identification of a
（過去 5 年以内）
pyrophosphate-dependent kinase and its donor selectivity determinants”, Nature
Commun. 9, 1765, (2018).
2. Nunoura T, Chikaraishi Y, Izaki R, Suwa T, Sato T, Harada T, Mori K, Kato Y,
Miyazaki M, Shimamura S, Yanagawa K, Shuto A, Ohkouchi N, Fujita N, Takaki
Y, Atomi H, Takai K. “A primordial and reversible TCA cycle in a facultatively
chemolithoautotrophic thermophile”, Science 359, 559-563, (2018).
3. Zheng RC, Hachisuka SI, Tomita H, Imanaka T, Zheng YG, Nishiyama M, Atomi H.
“An ornithine ω-aminotransferase required for growth in the absence of exogenous
proline in the archaeon Thermococcus kodakarensis”. J. Biol. Chem. 293, 36253636, (2018).
4. Makino Y, Sato T, Kawamura H, Hachisuka SI, Takeno R, Imanaka T, Atomi H. “Anarchaeal ADP-dependent serine kinase involved in cysteine biosynthesis and serine
metabolism”, Nature Commun. 7, 13446, (2016).
5. Aono R, Sato T, Imanaka T, Atomi H. “A pentose bisphosphate pathway for
nucleoside degradation in Archaea”, Nature Chem. Biol. 11(5):355-360, 2015.
6. Watanabe S, Kawashima T, Nishitani Y, Kanai T, Wada T, Inaba K, Atomi
H, Imanaka T, Miki K. “Structural basis of a Ni acquisition cycle for [NiFe]
hydrogenase by Ni-metallochaperone HypA and its enhancer”. Proc. Natl. Acad.
Sci. USA 112(25), 7701-7706, (2015).
7. Tominaga T, Watanabe S, Matsumi R, Atomi H, Imanaka T, Miki K. “Crystal
structures of the carbamoylated and cyanated forms of HypE for [NiFe]
hydrogenase maturation”. Proc. Natl. Acad. Sci. USA. 110, 20485-20490, (2013).
【学術関係の受賞など】 極限環境微生物学会

研究奨励賞（2004年）－6－

Ⅰ 専任教員 ･ スーパーバイザー (2017)【氏名】 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【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】 2017.4-2018.3 日本物理学会領域 11 代表【主な著書、学術論文】 1. Liquid-gas transitions in steady heat conduction, Naoko Nakagawa, Shin-ichi Sasa,
Phys. Rev. Lett. 119, 260602/1-6(2017)（過去 5 年以内）
2. Thermodynamic entropy as a Noether invariant, S.-I. Sasa, Yuki Yokokura, Phys.
Rev. Lett 116 140601/1-140601/6（2016）
3. Replica symmetry breaking in trajectories of a driven Brownian particle, Masahiko
Ueda, S.-I. Sasa, Phys. Rev. Lett 115 080605/1-080605/5（2015）
4. Derivation of Hydrodynamics from the Hamiltonian Description of Particle
Systems, S.-I. Sasa, Phys. Rev. Lett 112 100602/1-100602/5（2014）
5. 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）－7－

Ⅰ 専任教員 ･ スーパーバイザー (2017)【氏名】 山本

潤 （やまもとじゅん）【職名】 教授【所属】 大学院理学研究科

物理学・宇宙物理学専攻【研究室】 理学研究科 5 号館 218 号室【直通電話】 075-753-3788【FAX】 075-753-3788【電子メールアドレス】 junyama@scphys.kyoto-u.ac.jp【ホームページ】 http://softmatter.scphys.kyoto-u.ac.jp/【研究分野】 ソフトマター物理学【現在の研究課題】 超界面とソフトマター【研究内容キーワード】 ダイナミクス、揺らぎ、粘弾性【学歴】 1987 年 7 月東京大学大学院工学系研究科物理工学専攻博士課程中退【学位】 1990 年 6 月工学博士（東京大学）【略歴】 1987 年 8 月東京大学工学部物理工学科助手、1991 年 6 月東京大学生産技術研
究所助手、1999 年 10 月 ERATO 横山液晶微界面プロジェクト GL、2005 年 8月京都大学大学院理学研究科教授【所属学会】 日本物理学会、日本液晶学会【学会活動】 2015 年日本物理学会京都支部長、2014~2016 年日本液晶学会財務理事【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. K. Hata, Y. Takanishi, I. Nishiyama and J. Yamamoto, Softening of twist elasticity（過去 5 年以内）
in the swollen smectic C liquid crystal, Euro. Phys. Lett. 120, 56001(5P) (2017).
2. S. Bono, Y. Takanishi and J. Yamamoto, Effects of layer order on the mobility ofmesogenic molecules in SmA liquid-crystalline emulsions, Europhys. Lett., 113,
56004 (5P) (2016).
3. E. Gorecka, N. Vaupoticˇ, A. Zep, D. Pociecha, J. Yoshioka, J. Yamamoto, and H.
Takezoe, A Twist-Bend Nematic (NTB)Phase of Chiral Materials, Angew. Chem.
127, (2015) 10293 –10297.
4. Y. Kimoto, A. Nishizawa, Y. Takanishi, A. Yoshizawa and J. Yamamoto, Layer
modulated smectic-C phase in liquid crystals with a terminal hydroxyl group, Phys.
Rev. E, 89, 042503 (2014).
5. Y. Uchida, Y. Takanishi and J. Yamamoto, Controlled Fabrication and Photonic
Structure of Cholesteric Liquid Crystalline Shells, Adv. Mat., 25 (2013) 3234-3237.
【学術関係の受賞など】 2015 年日本液晶学会業績賞－8－Ⅰ 専任教員 ･ スーパーバイザー (2017)【氏名】 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. K. I. S. Mongcopa, M. Tyagi, J. P. Mailoa, G. Samsonidze, B. Kozinsky, S. A.
（過去 5 年以内）
Mullin, D. A. Gribble, H. Watanabe and N. P. Balsara, "Relationship between
Segmental Dynamics Measured by Quasi-Elastic Neutron Scattering andConductivity in Polymer Electrolytes", ACS Macro Lett., 7, 504-508 (2018).
2. H. Watanabe, Y. Matsumiya, and Y. Kwon, "Dynamics of Rouse Chains undergoing
Head-to-Head Association and Dissociation: Difference between Dielectric andViscoelastic Relaxation", J. Rheol., 61, 1151-1170 (2017).
3. Y. Doi, A. Matsumoto, T. Inoue, T. Iwamoto, A. Takano, Y. Matsushita, Y.
Takahashi, and H. Watanabe, "Re-examination of terminal relaxation behavior ofhigh-molecular-weight ring polystyrene melts", Rheol. Acta, 56, 567-581 (2017).
4. O. M. Kwon, H. Watanabe, K. H. Ahn, and S. J. Lee, "Interplay between structure
and property of graphene nanoplatelet networks formed by an electric field in apoly(lactic acid) matrix", J. Rheol., 61, 291-303 (2017)－9－Ⅰ 専任教員 ･ スーパーバイザー (2017)

5. Y. Matsumiya, H. Watanabe, O. Urakawa, and T. Inoue, "Experimental Test for
Viscoelastic Relaxation of Polyisoprene Undergoing Monofunctional Head-toHead Association and Dissociation", Macromolecules, 49, 7088-7095 (2016).
6. S. Ankiewicz, H. Orbey, H. Watanabe, H. Lentzakis, and J. Dealy, On the use ofcontinuous relaxation spectra to characterize model polymers", J. Rheol., 60, 11151120 (2016)
7. Y. Matsumiya and H. Watanabe, "Nonlinear Stress Relaxation of Miscible
Polyisoprene/Poly(p-tert-butyl Styrene) Blends in Pseudo-monodisperse State",
Macromolecules, 49, 4544-4556 (2016).
8. 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).
9. 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).
10. 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).
11. 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).
12. 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
13. 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).
14. 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",
Macromolecules, 47, 7637-7652 (2014).
15. 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).
16. 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).
17. 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).
【学術関係の受賞など】 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).

－ 10 －

Ⅰ 専任教員 ･ スーパーバイザー (2017)【氏名】 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 A. Seko, H. Hayashi, H. Kashima & I. Tanaka. Matrix- and tensor-based
recommender systems for the discovery of currently unknown inorganic（過去 5 年以内）
compounds. Physical Review Materials 2, 013805, (2018).
2 Y. Ikeda, R. Körmann, B. Dutta, A. Carreras. A. Seko, J. Neugebauer & I. Tanaka.
Temperature-dependent phonon spectra of magnetic random solid solutions. npj
Computational Materials 4, 7, (2018).
3 K. Shitara, T. Moriasa, A. Sumitani, A. Seko, H. Hayashi, Y. Koyama, R. Huang,
D. L. Han, H. Moriwake & I. Tanaka. First-Principles Selection of Solute Elements
for Er-Stabilized Bi2O3 Oxide-Ion Conductor with Improved Long-Term Stability atModerate Temperatures. Chemistry of Materials 29, 3763 (2017).
4 H. Hayashi, S. Katayama, T. Komura, Y. Hinuma, T. Yokoyama, K. Mibu, F. Oba& I. Tanaka. Discovery of a Novel Sn(II)-Based Oxide beta-SnMoO4 for DaylightDriven Photocatalysis. Advanced Science 4, 1600246 (2017).
5 Y. Hinuma, T. Hatakeyama, Y. Kumagai, Lee A. Burton, H. Sato, Y. Muraba, S.
Iimura, H. Hiramatsu, I. Tanaka, H. Hosono & F. Oba. Discovery of earth-abundantnitride semiconductors by computational screening and high-pressure synthesis.
Nature Communications 7, 11962, (2016)【学術関係の受賞など】 本多フロンティア賞（2018 年）
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）
米国ｾﾗﾐｯｸｽ学会 ﾘﾁｬｰﾄﾞ・ﾌﾙﾗｰｽ賞（2004 年）－ 11 －

Ⅰ 専任教員 ･ スーパーバイザー (2017)【氏名】 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，英国王立化学会【主な著書、学術論文】 1. Dynamic Behavior of Rh Species in Rh/Al2O3 Model Catalyst during Three-Way（過去 5 年以内）
Catalytic Reaction: An Operando X ray Absorption Spectroscopy Study, H.Asakura,
S. Hosokawa, T. Tanaka et al., J. Am. Chem. Soc., 2018, 140, 176-184.
2. Efficient Photocatalytic Carbon Monoxide Production from Ammonia and Carbon
Dioxide by the Aid of Artificial Photosynthesis, Z. Huang, K. Teramura, H.
Asakura, S. Hosokawa, T. Tanaka, Chemical Science, 2017, 8, 5797-5801.
3. Strong Metal-Support Interaction between Pt and SiO2 Following High-Temperature
Reduction: A Catalytic Interface for Propane Dehydrogenation, L. Deng, H. Miura,
T. Shishido, S. Hosokawa, K. Teramura, T. Tanaka, Chemical Communications,2017, 53, 6937-6940.
4. Thermally Stable Single Atom Pt/m-Al2O3 for the Selective Hydrogenation and CO
Oxidation, Z. Zhang, Y. Zhu, H. Asakura, B. Zhang, J. Zhang, M. Zhou, Y. Han, T.
Tanaka, A.-Q. Wang, T. Zhang, N. Yan, Nature Communications, 2017, 8:16100.
5. Which is an Intermediate Species for Photocatalytic Conversion of CO2 by H2O
as the Electron Donor: CO2 Molecule, Carbonic Acid, Bicarbonate, or Carbonate
Ions?, K. Teramura, K. Hori, Y. Terao, Z. Huan, S. Iguchi, Z. Wang, H. Asakura, S.
Hosokawa, T. Tanaka, J. Phys. Chem. C, 2017, 121, 8711-8721.
6. Visible Light-Induced Water Splitting in an Aqueous Suspension of a Plasmonic
Au/TiO 2 Photocatalyst with Metal Co-Catalysts, A. Tanaka, K. Teramura, S.
Hosokawa, H.Kominami, T. Tanaka, Chemical Science, 2017, 8, 2574-2580.
7. Promoter Effect of Pd Species on Mn Oxide Catalysts Supported on Rare-EarthIron Mixed Oxide, S. Hosokawa, R. Tada, T. Shibano, S. Matsumoto, K. Teramura, T.
Tanaka, Catalysis Science & Technology, 2016, 6, 7868-7874.
8. Investigation on Electrochemical and Photoelectrochemical Properties of Ni-Al
LDH Photocatalyst, S. Iguchi, S. Kikkawa, K. Teramura, S. Hosokawa, T. Tanaka,
Phys. Chem. Chem. Phys., 2016, 18, 13811-13819.
9. Popping of Graphene Oxide: Application in Preparing Metal Nanoparticle
Catalysts, Y. Gao, Xi Chen, J. Zhang, H. Asakura, T. Tanaka, K. Teramura, D. Ma, N.
Yan, Advanced Materials, 2015, 27, 4688-4694.
－ 12 －

Ⅰ 専任教員 ･ スーパーバイザー (2017)【氏名】 山本

量一 （やまもと

りょういち）【職名】 教授【所属】 工学研究科

化学工学専攻A 棟 118 号室【研究室】 桂キャンパス【直通電話】 075-383-2661【FAX】 075-383-2651【電子メールアドレス】 ryoichi@cheme.kyoto-u.ac.jp【ホームページ】 http://www-tph.cheme.kyoto-u.ac.jp/【研究分野】 ソフトマター／アクティブマターの計算科学【現在の研究課題】 生体組織の物理モデリング／自己泳動する微生物のシミュレーション【研究内容キーワード】 ソフトマター、アクティブマター、シミュレーション、移動現象【最終学歴】 1992 年 3 月 神戸大学大学院 工学研究科修士課程化学工学専攻修了【学位】 1996 年 3 月 博士（工学）京都大学【略歴】 1994 年 9 月 神戸大学大学院自然科学研究科物質科学専攻助手、1996 年 3 月
京都大学大学院理学研究科物理学・宇宙物理学専攻助手、2000 年 1 月 同講師、2004 年 10 月 京都大学大学院工学研究科化学工学専攻助教授、2007 年 4 月 同准教授、2008 年 10 月 同教授【在外研究歴】 2000 年 9 月 -2001 年 8 月 英国ケンブリッジ大学化学教室（J-P. Hansen 教授）（文部省在外研究員（若手））【所属学会】 日本物理学会、化学工学会、分子シミュレーション研究会【学会活動】 化学工学会理事【主な著書、学術論文】 1. C. Shih, J.J. Molina, and R. Yamamoto, Inter-particle force between two colloidal（過去 5 年以内）
particles in an oscillating electric field, Soft Matter, in print.

2. N. Oyama, K. Teshigawara, J. J. Molina, R. Yamamoto, and T. Taniguchi,
Hydrodynamic synchronization of externally driven colloids, Phys. Rev. E 97,
032611 (2018).
3. S. K. Schnyder, J. J. Molina, Y. Tanaka, and R. Yamamoto, Collective motion ofcells crawling on a substrate: roles of cell shape and contact inhibition, Sci. Rep. 7,5163 (2017).
4. 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).
5. N. Oyama, J. J. Molina, and R. Yamamoto, Purely hydrodynamic origin forswarming of swimming particles, Phys. Rev. E 93, 043114 (2016).
6. 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).
7. H. Mizuno and R. Yamamoto, General constitutive model for supercooled liquids:
Anomalous transverse wave propagation, Phys. Rev. Lett. 110, 095901 (2013).
8. J. J. Molina, Y. Nakayama, and R. Yamamoto, Hydrodynamic interactions of selfpropelled swimmers, Soft Matter 9, 4923-4936 (2013).

【学術関係の受賞など】 2007 年 1 月 ホソカワ研究奨励賞、2002 年 12 月 分子シミュレーション研究会
学術賞－ 13 －

Ⅰ 専任教員 ･ スーパーバイザー (2017)【氏名】 高田彰二 （たかだ

しょうじ）【職名】 教授【所属】 理学研究科

生物科学専攻生物物理学教室【研究室】 理学部 1 号館 205 号室【直通電話】 075-753-4220【FAX】 075-753-4222【電子メールアドレス】 takada@biophys.kyoto-u.ac.jp【ホームページ】 http://theory.biophys.kyoto-u.ac.jp【研究分野】 理論生物物理学【現在の研究課題】 生体分子の構造機能についての理論およびコンピュータシミュレーション研
究【研究内容キーワード】 タンパク質フォールディング、分子モーター、遺伝子動態、生体分子モデリ
ング【最終学歴】 1991 年 9 月 総合研究大学院大学数物科学研究科機能分子科学専攻博士後期課
程退学【学位】 1994 年 3 月 理学博士（総合研究大学院大学）【略歴】 1991 年～ 1995 年 岡崎国立共同研究機構技官（分子科学研究所）、1995 年～
1998 年 日本学術振興会研究員（イリノイ大学化学科）、1998 年～ 2001 年 神戸大学理学部化学科講師、2001 年～ 2007 年 同助教授、2007 年～ 2013 年 京都大学理学研究科生物科学専攻生物物理教室准教授、2013 年 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】 日本生物物理学会副会長【主な著書、学術論文】 1. M. Shimizu, Y. Noguchi, Y. Sakiyama, H. Kawakami, T. Katayama*, S. Takada*,（過去 5 年以内）
Near-atomic structural model for bacterial DNA replication initiation complex andits functional insights, Proc. Nat. Acad. Sci. USA, 113: E8021-E8030, 2016
2. C. Tan, T. Terakawa, S. Takada*, Dynamic Coupling among Protein Binding,
Sliding, and DNA Bending Revealed by Molecular Dynamics, JACS., 138: 85128522, 2016
3. S. Takada*, R. Kanada, C. Tan, T. Terakawa, W. Li, H. Kenzaki, Modeling
Structural Dynamics of Biomolecular Complexes by Coarse-Grained Molecular
Simulations, Acc. Chem. Res., 48: 3026-3035, 2015
4. W. Li, W. Wang, and S. Takada, Energy landscape views for interplays amongfolding, binding, and allostery of calmodulin domain, Proc. Nat. Acad. Sci. USA,111: 10550-10555, 2014.
5. 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.
6. 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.
7. 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.
－ 14 －

Ⅰ 専任教員 ･ スーパーバイザー (2017)【氏名】 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. Atomistic modeling of alternating access of a mitochondrial ADP/ATP membrane（過去 5 年以内）
transporter with molecular simulations. Koichi Tamura and Shigehiko Hayashi*,
PLOS ONE, 12, e0181489 (2017).
2. Photoactivation intermediates of a G-protein coupled receptor rhodopsin
investigated by a hybrid molecular simulation. Motoshi Kamiya and ShigehikoHayashi*, J. Phys. Chem. B, 121, 3842-3852 (2017).
3. Molecular mechanism of wide photoabsorption spectral shifts of color variants ofhuman cellular retinol binding protein II. Cheng Cheng, Motoshi Kamiya, Yoshihiro
Uchida, Shigehiko Hayashi*, J. Am. Chem. Soc., 137, 13362-13370 (2015)
4. 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)
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 state inan α -amylase catalysis. Kosugi Takahiro and Shigehiko Hayashi*. J. Am. Chem.
Soc., 134, 7045-7055 (2012)－ 15 －

Ⅰ 専任教員 ･ スーパーバイザー (2017)⑷

専任教員【氏名】 佐藤徹 （さとうとおる）【職名】 教授【所属】 理論研究部門【研究室】 210
【直通電話】 075-711-7849【電子メールアドレス】 tsato@fukui.kyoto-u.ac.jp【ホームページ】 準備中【研究分野】 理論化学
【現在の研究課題】 振電相互作用理論、機能性分子の理論設計【研究内容キーワード】 振電相互作用，有機 EL，Jahn-Teller 効果【学歴】 平成 9 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】 博士（工学）【略歴】 平成 9 年 4 月 日本学術振興会特別研究員（PD）（財団法人基礎化学研究所）
平成 10 年 1 月 京都大学大学院工学研究科分子工学専攻助手
平成 15 年 10 月 文部科学省在外研究員（若手）（ルーヴァンカトリック大学）
平成 16 年 3 月 京都大学福井謙一記念研究センター理論研究部門助教授
平成 23 年 1 月 京都大学大学院工学研究科分子工学専攻准教授
平成 30 年 2 月 京都大学福井謙一記念研究センター理論研究部門教授
現在に至る【所属学会】 日本コンピュータ化学会，日本化学会，フラーレン・ナノチューブ・グラフェ
ン学会 , 日本物理学会，応用物理学会，有機 EL 討論会【学会活動】 Jahn-Teller Steering Committee (2009-)【主な著書、学術論文】 1. “Fluorescence via Reverse Intersystem Crossing from Higher Triplet States in a
Bisanthracene Derivative”, Tohru Sato*, Rika Hayashi, Naoki Haruta, Yong-Jin Pu,（過去 5 年以内）
Sci. Rep. 7 4820 1-9 (2017).
2. “Thermodynamical vibronic coupling constant and density: Chemical potential andvibronic coupling in reactions”, Tohru Sato*, Naoki Haruta, and Kazuyoshi Tanaka,
Chem. Phys. Lett. 652, 157-161 (2016).
3. “A Light-Emitting Mechanism for Organic Light-Emitting Diodes: Molecular
Design for Inverted Singlet-Triplet Structure and Symmetry-Controlled Thermally
Activated Delayed Fluorescence”, Tohru Sato*, Motoyuki Uejima, Kazuyoshi
Tanaka, Hironori Kaji, and Chihaya Adachi, J. Mater. Chem. C 3, 870-878 (2015).
4. “Quantum Yield in Blue-Emitting Anthracene Derivatives: Vibronic Coupling
Density and Transition Dipole Moment Density”, Motoyuki Uejima, Tohru Sato*,
Daisuke Yokoyama, Kazuyoshi Tanaka, and Jong-Wook Park, Phys. Chem. Chem.
Phys. 16, 14244-14256 (2014) .
5. "Jahn-Teller Instability of Icosahedral [W@Au12]—", Tohru Sato*, Erwin Lijnen,
Arnout Ceulemans, J. Chem. Theo. Comput. 10, 613-622 (2014).
【学術関係の受賞など】 2016 年度日本コンピュータ化学会学会賞
平成 23 年 3 月 欧州委員会 Erasumus Mundus Scholar－ 16 －

Ⅰ 専任教員 ･ スーパーバイザー (2017)【氏名】 西本佳央 （にしもと

よしお）【職名】 特定助教【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

名古屋大学大学院理学研究科博士課程（後期課程）
物質理学専攻修了【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
2016 年 12 月 京都大学福井謙一記念研究センター・特定助教【所属学会】 日本化学会・理論化学研究会・分子科学会【主な著書、学術論文】 1. Nishimoto, Y.; Fedorov, D. G. “Adaptive frozen orbital treatment for the fragment
molecular orbital method combined with density-functional tight-binding”, J.
（過去 5 年以内）
Chem. Phys. 2018, 148, 064115.
2. Kitoh-Nishioka, H.; Welke, K.; Nishimoto, Y.; Fedorov, D. G.; Irle, S. “Multi-Scale
Simulations on Charge Transport in Covalent Organic Frameworks: Including
Dynamics of Transfer Integrals from FMO-DFTB/LCMO”, J. Phys. Chem. C 2017,
121, 17712–17726.
3. Nishimoto, Y.; Kondo, H.; Yamaguchi, K.; Yokogawa, D.; Yamaguchi, J.; Itami, K.;
Irle, S. “Theoretical Elucidation of Potential Enantioselectivity in a Pd-Catalyzed
Aromatic C–H Coupling Reaction”, J. Org. Chem. 2017, 82, 4900–4906.
4. Nishimoto, Y. “Analytic Hyperpolarizability and Polarizability Derivative with
Fractional Occupation Numbers for Large Extended Systems”, J. Chem. Phys.
2017, 146. 084101.
5. Nishimoto, Y.; Fedorov, D. G. “Three-body expansion of the fragment molecularorbital method combined with density-functional tight-binding”, J. Comput. Chem.
2017, 38, 406–418.
【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－ 17 －

Ⅰ 専任教員 ･ スーパーバイザー (2017)⑸

FIFC リサーチフェロー【氏名】 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開発の理論と計算【研究内容キーワード】 高周期典型元素、遷移金属、ナノカーボン、機能性分子【最終学歴】 1975 年 3 月 大阪大学大学院基礎工学研究科博士課修了【学位】 1975 年 3 月 工学博士（大阪大学）【略歴】 ロチェスター大学博士研究員、オハイオ州立大学博士研究員、分子科学研究所技官を経て、1980 年 4 月 横浜国立大学助教授、1991 年 4 月 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、総合研究大学
院大学教授、20012 年 3 月 同名誉教授、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 FIFC 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. X. Lu, L. Feng, T. Akasaka, and S. Nagase, Current Statues and Future（過去 5 年以内）
Developments of Endohedral Metallofullerenes, Chem. Soc. Rev., 41, 7723-7760(2012).
2. S. Nagase, Multiple Bonds between Lead Atoms and Short Bonds between
Transition Metals, Pure Appl. Chem., 85, 649-659 (2013).
3. X. Lu, T. Akasaka, and S. Nagase, Carbide Cluster Metallofullerenes: Structure,
Properties, and Possible Origin, Acc. Chem. Res., 46, 1627-1635 (2013).
4. M. Yamada, T. Akasaka, and S. Nagase, Carbene Additions to Fullerenes, Chem.
Rev., 113, 7209-7264 (2013).
5. 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).
6. 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).
7. 赤阪健，山田道夫，前田優，永瀬茂，化学の要点シリーズ 17「フラーレンの化学」（日本化学会編），共立出版 (2016).
【学術関係の受賞など】 2012 年 文部科学大臣表彰科学技術賞（研究部門）、2012 年 福井メダル (AsiaPacific Association of Theoretical & Computational Chemists) 、2013 年 日本化学会賞

－ 18 －

Ⅰ 専任教員 ･ スーパーバイザー (2017)⑹

シニアリサーチフェロー【氏名】 榊茂好 （さかきしげよし）【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・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. Theoretical Study of One-Electron Oxidized Mn(III)– and Ni(II)–Salen（過去 5 年以内）
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).
2. 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).
3. 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).
4. 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).
5. Theoretical Study of Hydrogenation Catalysis of Phosphorus Compound andPrediction of Catalyst with High Activity and Wide Application Scope, G. Zeng, S.
Maeda, T. Taketsugu, S. Sakaki, ACS Cat., 6, 4859-4870 (2016).
6. Catalytic Hydrogenation of Carbon Dioxide with Ammonia-Borane by PincerType Phosphorus Compounds: Theoretical Prediction, GX. Zeng, S. Maeda, T.
Taketsugu, S. Sakaki, J. Am. Chem. Soc., 138, 13481-13484 (2016).
7. Mo − Mo Quintuple Bond is Highly Reactive in H-H, C-H, and O-H σ-Bond
Cleavages Be-cause of the Polarized Electronic Structure in Transition State, Y.
Chen, S. Sakaki, Inorg. Chem., 56, 4011-4020 (2017).
8. Theoretical study of one-electron-oxidized salen complexes of group 7 (Mn(III),
Tc(III), and Re( III)) and group 10 metals (Ni(II), Pd(II), and Pt(II)) with the
3D-RISM-GMC-QDPT method: localized vs. delocalized ground and excitedstates in solution, S. Aono, M. Nakagaki, S. Sakaki, Phys. Chem. Chem. Phys., 19,16831-16849 (2017).
9. How to Control Inversion vs. Retention Transmetallation between PdII-Phenyl
and CuI-Alkyl Complexes: Theoretical Insight, H. Zheng, K. Semba, Y. Nakao, S.
Sakaki, J. Am. Chem. Soc., 139, 14065-14076 (2017).
【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）－ 19 －

Ⅰ 専任教員 ･ スーパーバイザー (2017)【氏名】 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】 福井謙一記念研究センター 206【直通電話】 075-711-7867【FAX】 075-781-4757【電子メールアドレス】 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【学位】 1978 年 3 月

京都大学工学研究科石油化学専攻博士課程修了
工学博士（京都大学）【略歴】 1979 年 6 月 米国エナージー・コンバージョン・デバイシズ社リサーチケミスト、
1981 年 12 月 京都大学工学部助手、1988 年 12 月 同 助教授、1996 年 11 月
京都大学大学院工学研究科教授、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. 統計力学入門 化学者の視点から（単著，化学同人，2014）（過去 5 年以内） 2. Carbon Nanotubes and Graphene（共編著，Elsevier Science，2014）
3. 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）
4. ボール物理化学 第 2 版（上）（監訳ならびに共訳，化学同人，2015）
5. 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. 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).
2. 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).
3. 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).
4. 元素ブロックの機能発現・電子化物を与える無機元素ブロック（共著） セラミックス，51, No. 11, 739-742 (2016).
5. 2016 年ノーベル賞を読み解く 物理学賞 さまざまな可能性を秘めたエキ
ゾチックな状態とは？（単著） 化学，71, No. 12, 24-27 (2016).
6. 化学つれづれ草 第一回 理屈っぽい化学？
（単著）
化学 72, No. 5, 55 (2017).
7. 化学つれづれ草 第二回 福井研究室の日常（単著）
化学 72, No. 6, 31 (2017).
8. 化学つれづれ草 第三回 博士課程 考（単著）化学 72, No. 7, 29 (2017).
9. 化学つれづれ草 第四回 米国のベンチャー企業（単著）化学 72, No. 8, 27(2017).
10. 化学つれづれ草 第五回 米国の研究資金事情（単著）化学 72, No. 9, 18(2017).
11. 化学つれづれ草 第六回 日本の大学と研究資金（単著）化学 72, No. 10,
29 (2017).
12. 化学つれづれ草 第七回 妄想と基礎研究資金（単著）化学 72, No. 11, 46(2017).
13. 化学つれづれ草 第八回 企業と大学の研究（単著）化学 72, No. 12, 28(2017).
14. 化学つれづれ草 第九回 オリジナルな研究（単著）化学 73, No. 1, 59(2018).
－ 20 －

Ⅰ 専任教員 ･ スーパーバイザー (2017)15. 化学つれづれ草 第十回 理論化学と計算化学（単著）化学 73, No. 2, 29(2018).
16. 化学つれづれ草 第十一回 分割統治と化学（単著）化学 73, No. 3, 24(2018).
（以上和文総説）
1. 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).
2. 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).
3. 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).
4. 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).
5. 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).
6. 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).
7. Vibronic Couplings in C60 Derivatives for Organic Photovoltaics (N. Iwahara, T.
Sato, K. Tanaka, and H. Kaji) Chem. Phys. Lett., 590, 169-174 (2013).
8. 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).
9. 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).
10. 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).
11. 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).
12. 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).
13. 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).
14. 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).
15. 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).
16. 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).
－ 21 －

Ⅰ 専任教員 ･ スーパーバイザー (2017)17. 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).
18. 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).
19. 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).
20. 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).
21. 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).
22. 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).
23. 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).
24. 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).
25. 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).
26. Multiscale Simulation of Charge Transport in a Host Material, N, N’-Dicarbazole-3,5-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).
27. 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).
28. 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).
29. 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).
30. 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).
31. 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).
32. 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).
－ 22 －

Ⅰ 専任教員 ･ スーパーバイザー (2017)33. 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).
34. (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).
35. 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).
36. 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).
37. Synthesis and Magnetic Properties of Linear Two-coordinate Monomeric
Diaryliron(II) Complexes Bearing Fused-ring Bulky“Rind”Groups (S. Goda, M.
Nikai, M. Ito, D. Hashizume, K. Tamao, A. Okazawa, N. Kojima, H. Fueno, K.
Tanaka, Y. Kobayahsi, and T. Matsuo) Chem. Lett., 45, 634-636 (2016).
38. Thermodynamical Vibronic Coupling Constant and Density: Chemical Potential
and Vibronic Coupling in Reactions (T. Sato, N. Haruta, and K. Tanaka) Chem.
Phys. Lett., 652, 157-161 (2016).
39. C o l o r Tu n i n g o f A l t e r n a t i n g C o n j u g a t e d P o l y m e r s C o m p o s e d o fPentaazaphenanthrene by Modulating Their Unique Electronic Structures
Involving Isolated-LUMOs (H. Watanabe, M. Hirose, K. Tanaka, K. Tanaka, and Y.
Chujo) Polym. Chem., 7, 3674-3680 (2016).
40. Arsole-Containing π-Conjugated Polymer by the Post-Element-Transformation
Technique (Y. Matsumura, M. Ishidoshiro, Y. Irie, H. Imoto, K. Naka, K. Tanaka, S.
Inagi, and I. Tomita) Angew. Chem. Int. Ed., 55, 15040-15043 (2016).
41. Radical Cation of an Oligoarylamine Having a Nitroxide Radical Substituent:
A Coexistent Molecular System of Localized and Delocalized Spins (A. Ito, R.
Kurata, Y. Noma, Y. Hirao, and K. Tanaka) J. Org. Chem., 81, 11416-11420 (2016).
42. Borophosphonate Cages as Element-blocks: Ab Initio Calculation of the Electronic
Structure of a Simple Borophosphonate, [HPO3BH]4, and Synthesis of Two Novel
Borophosphonate Cages with Polymerizable Groups (J. Zapico, M. Shirai, R.
Sugiura, N. Idota, H. Fueno, K. Tanaka, and Y. Sugahara) Chem. Lett., 46, 181-184(2017).
43. Stereoisomerization of 1,4-Dihydroarsinetetracarboxylic Acid Diimides under
Non-acidic Condition from cis- to trans-Forms (K. Naka, T. Kato, K. Abe, M.
Ishidoshiro, S. Nishiyama, S. Tanaka, H. Imoto, S. Watase, K. Matsukawa, H.
Fueno, and K. Tanaka) Heterocycles, 94, 923-937 (2017).
44. Studies of Spherically Distributed LUMO and Electron-Accepting Properties ofCaged Hexakis(germasesquioxanes) (J. Ohshita, T. Tsuchida, K. Komaguchi, K.
Yamamoto, Y. Adachi, Y. Ooyama, Y. Harima, and K. Tanaka) Organometallics,
36, 2536-2540 (2017).
45. Induced-Dipole-Directed, Cooperative Self-Assembly of a Benzotrithiophene (T.
Ikeda, H. Adachi, H. Fueno, K. Tanaka, and T. Haino) J. Org. Chem., 82, 1006210069 (2017).
46. A Stable Free Tetragermacyclobutadiene Incorporating Fused-ring Bulky
EMind Groups (K. Suzuki, Y. Numata, N. Fujita, N. Hayakawa, T. Tanikawa, D.
Hashizume, K. Tamao, H. Fueno, K. Tanaka, and T. Matsuo) Chem. Commun., 54,
2200-2203 (2018).
（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－ 23 －

Ⅰ 専任教員 ･ スーパーバイザー (2017)⑺

リサーチリーダー【氏名】 高塚

和夫 （たかつかかずお）【職名】 リサーチリーダー【所属】 福井謙一記念研究センター【研究室】 209

【直通電話】 075-711-7902【FAX】 075-711-7902【電子メールアドレス】 kaztak@fukui.kyoto-u.ac.jp【ホームページ】 http://mns2.fukui.kyoto-u.ac.jp【研究分野】 理論化学，分子科学基礎論【現在の研究課題】 非断熱電子動力学による化学反応論，超高速励起状態化学，化学動力学理論，
多体量子動力学理論【研究内容キーワード】 化学動力学・電子波束動力学・非断熱現象の科学・レーザー化学【学歴】 1978 年 3 月

大阪大学大学院基礎工学研究科化学系専攻学位取得卒業【学位】 工学博士【略歴】 1978 年 8 月
1979 年 9 月
1982 年 1 月
1987 年 4 月

ノースダコタ州立大学 博士研究員
カルフォルニア工科大学博士研究員
岡崎国立共同研究機構分子科学研究所理論研究系助手
名古屋大学教養部助教授（名古屋大学大学院工学研究科および理学研究科を担当）
1992 年 4 月 名古屋大学大学院人間情報学研究科教授
1997 年 10 月－ 2016 年 3 月 東京大学大学院総合文化研究科教授
1998 年 4 月－ 2016 年 3 月 東京大学教授 理学系研究科化学専攻（兼担）2001 年 4 月－ 2016 年 3 月 自然科学研究機構分子科学研究所教授（兼任）【所属学会】 日本化学会，日本物理学会，アメリカ化学会，分子科学会，理論化学会【学会活動】 計算分子科学研究拠点長（2016 年 3 月まで）
．各種評価委員会委員（非公開），
Chem. Phys. 誌等編集委員【主な著書、学術論文】 論文（過去 5 年以内） 1. T. Yonehara, K. Hanasaki, K. Takatsuka.“Fundamental approaches tononadiabaticity: Towards a chemical theory beyond the Born-Oppenheimer
paradigm” Chemical Reviews, 112, 499-542 (2012)
2. K. Takatsuka, S. Takahashi “Towards many-dimensional real-time quantum theory
for heavy particle dynamics. II. Beyond semiclassics by quantum smoothing of
singularity in quantum-classical correspondence” Phys. Rev. A 89, 012109 (12pages) (2014).
3. Kentaro Yamamoto and Kazuo Takatsuka “On photocatalytic cycle of water
splitting with small manganese oxides and the roles of water cluster as a direct
resource of oxygen molecules.” PCCP, 20, 6708-6725 (2018)
4. Kazuo Takatsuka “Lorentz-like force emerging from kinematic interactions
between electrons and nuclei in molecules. A quantum mechanical origin ofsymmetry breaking that can trigger molecular chirality.” J. Chem. Phys. 146,
084312 (10 pages) (2017).
5. Kazuo Takatsuka “Theory of molecular nonadiabatic electron dynamics incondensed phases.” J. Chem. Phys. 147, 174102 (13 pages) (2017).
単行本
1. Kazuo Takatsuka, Takehiro Yonehara, Kota Hanasaki, and Yasuki Arasaki“Chemical Theory beyond the Born-Oppenheimer Paradigm: Nonadiabatic
Electronic and Nuclear Dynamics in Chemical Reactions”，(World Scientific,
Singapore, 2014)
2. 高塚和夫，田中秀樹「分子熱統計力学」（東京大学出版会，2014）【学術関係の受賞など】 分子科学会賞（2013 年），日本化学会賞（2014 年），
Mizushima-Raman Lectureship Award（2016 年）－ 24 －

Ⅰ 専任教員 ･ スーパーバイザー (2017)⑻

研究員【氏名】 北浦和夫 （きたうらかずお）【職名】 研究員【所属】 福井謙一記念研究センター

榊グループ【電子メールアドレス】 kazuo.kitaura@riken.jp【研究分野】 計算化学
【現在の研究課題】 巨大分子系の電子状態計算法【研究内容キーワード】 巨大分子・タンパク質・電子状態【学歴】 1976 年 3 月 大阪市立大学理学研究科化学専攻博士課程修了【学位】 1976 年 3 月 理学博士（大阪市立大学）【略歴】 1979 年 8 月 分子科学研究所理論研究系助手、1981 年 9 月 大阪市立大学理学部助手、1989 年 7 月 岡崎国立共同研究機構分子科学研究所助教授（電子計算機センター）、1993 年 4 月 大阪府立大学総合科学部教授、2001 年 7 月 産業技術総合研究所計算科学研究部門グループ長、2007 年 4 月 京都大学薬学研究科

教授、2011 年 12 月 神戸大学システム情報学研究科特命教授、2016 年 4 月 京
都大学福井謙一記念研究センター研究員【所属学会】 日本化学会、日本薬学会【主な著書、学術論文】 1. Hiroya Nakata, Takeshi Nagata, Dmitri G. Fedorov, Satoshi Yokojima, Kazuo（過去 5 年以内）
Kitaura, Shinichiro Nakamura, "Analytic second derivatives of the energy in the
fragment molecular orbital method", J. Chem. Phys. 138, 164103 (2013).

2. Nakanishi, Isao; Murata, Katsumi; Nagata, Naoya; Masakuni Kurono, Takayoshi
Kinoshita, Misato Yasue, Takako Miyazaki, Yoshinori Takei, Shinya Nakamura,

Atsushi Sakurai, Nobuko Iwamoto, Keiji Nishiwaki, Tetsuko Nakaniwa,Y usuke

Sekiguchi, Akira Hirasawa, Gozoh Tsujimoto Kazuo Kitaura, "Identification ofprotein kinase CK2 inhibitors using solvent dipole ordering virtual screening", Eur.
J. Med. Chem. 96, 396-404 (2015).

3. Fedorov, Dmitri G.; Kitaura Kazuo, "ubsystem Analysis for the Fragment
Molecular Orbital Method and Its Application to Protein-Ligand Binding in
Solution", J. Phys. Chem. A, 120, 2218-2231 (2016).

－ 25 －

Ⅱ 博士研究員 (2017)

Ⅱ

博士研究員等１．博士研究員組織職

平成２９年度名氏

名多羅間 充 輔
福井センターフェロー

伊丹

將人

藪中

俊介

Schnyder, Simon Kaspar
福井センターフェロー
諸熊グループ研究フェロー
福井センターフェロー

伊勢川 美 穂鈴木聡

Sharma, Akhilesh Kumar
Puripat, Maneeporn
青野

信治

中垣

雅之

Zheng, Hong

榊グループ

研究フェローLu, Jing
Zhong, Ronglin
Julong. Jiang
松岡

高塚グループ研究フェロー貴英

山 本 憲太郎
長谷川 太 祐
新崎

康樹

氏

名

２．日本学術振興会外国人特別研究員
職
榊グループ

名
外国人特別研究員

Ren, Xuefeng

３．日本学術振興会特別研究員
職
高塚グループ

名

氏

特別研究員

－ 26 －

松崎名黎Ⅱ 博士研究員 (2017)

４. 博士研究員プロフィール【氏名】 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。
アクティブマター研究会 2017（2017 年 1 月 20-21 日）の世話人をしました。
アクティブマター研究会 2018（2018 年 1 月 19-20 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).
6. M. Tarama, “Swinging motion of active deformable particles in Poiseuille flow”,
Phys. Rev. E 96, 022602 (2017).
7. M. Tarama, “Dynamics of Deformable Active Particles under External Flow Field”,
J. Phys. Soc. Jpn. 86, 101011 (2017).
8. M. Tarama and R. Yamamoto, “Mechanics of cell crawling by means of force-freecyclic motion”, J. Phys. Soc. Jpn. 87, 044803 (2018).
【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)－ 27 －

Ⅱ 博士研究員 (2017)【氏名】 伊丹將人 （いたみ

まさと）【職名】 福井センターフェロー【所属】 福井謙一記念研究センター【研究室】 212 号室【直通電話】 075-711-7894【電子メールアドレス】 itami@fukui.kyoto-u.ac.jp【研究分野】 統計物理学【現在の研究課題】 表面での時空間平均応力ゆらぎの特異性・熱流に誘起された非平衡力【研究内容キーワード】 ゆらぐ流体力学・大偏差理論・線形応答理論【学歴】 2016 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博士課程修了【学位】 2016 年 3 月

博士（理学）（京都大学）【略歴】 2016 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】 日本物理学会【主な著書、学術論文】 1. Masato Itami and Shin-ichi Sasa, "Universal Form of Stochastic Evolution for Slow
Variables in Equilibrium Systems" J. Stat. Phys. 167, 46-63 (2017).
（過去 5 年以内）
2. Masato Itami and Shin-ichi Sasa, "Derivation of Stokes' Law from Kirkwood's
Formula and the Green-Kubo Formula via Large Deviation Theory" J. Stat. Phys.
161, 532-552 (2015).
3. Masato Itami and Shin-ichi Sasa, "Nonequilibrium Statistical Mechanics for
Adiabatic Piston Problem" J. Stat. Phys. 158, 37-56 (2015).
4. Masato Itami and Shin-ichi Sasa, "Macroscopically measurable force induced bytemperature discontinuities at solid-gas interfaces" Phys. Rev. E 89, 052106 (2014).

－ 28 －

Ⅱ 博士研究員 (2017)【氏名】 藪中

俊介（やぶなかしゅんすけ）【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【直通電話】 075-711【FAX】 075-781-4757【電子メールアドレス】 yabunaka@fukui.kyoto-u.ac.jp【ホームページ】 http://statphys.scphys.kyoto-u.ac.jp/~yabunaka/yabunaka/Welcome.html【研究分野】 ソフトマター物理【現在の研究課題】 選択的溶媒和効果を取り入れた電気二重層のダイナミクスの研究、アクティ
ブ流体力学【研究内容キーワード】 選択的溶媒和効果、電気二重層、アクティブマター
【学歴】 2014 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博士後期課程
修了【学位】 2014 年 3 月

理学博士（京都大学）【略歴】 2012 年 4 月 JSPS Research Fellow (DC)2014 年 4 月 JSPS Research Fellow (PD)2016 年 12 月 京都大学福井謙一記念研究センターフェロー【所属学会】 日本物理学会【主な著書、学術論文】 1. “Collision between chemically-driven self-propelled drops”, Shunsuke Yabunaka
and Natsuhiko Yoshinaga, Journal of Fluid Mechanics, November 2016, Pages（過去 5 年以内）
205-233
2. “Structure formation due to antagonistic salts”, Akira Onuki, Shunsuke Yabunaka,
Takeaki Araki and Ryuichi Okamoto Current Opinion in Colloid & Interface
Science Volume 22, April 2016, Pages 59–64
3. “Functional renormalization group approach to noncollinear magnets”, B.
Delamotte, M. Dudka, D. Mouhanna, and S. Yabunaka, Phys. Rev. B 93, 064405
4. “Electric double layer composed of an antagonistic salt in an aqueous mixture:
Local charge separation and surface phase transition”, Shunsuke Yabunaka,and
Akira Onuki, Physical review letters 119, 118001, (2017)
5. “Surprises in O (N) Models: Nonperturbative Fixed Points, Large N Limits, andMulticriticality”, Shunsuke Yabunaka and Bertrand Delamotte, Physical review
letters 119, 191602 (2017)【学術関係の受賞など】 JSPS Research Fellowships for Young Scientists(DC) 2012-2014
JSPS Research Fellowships for Young Scientists(PD) 2014-2017
Journal of Chemical Physics Editors’choice 2015

－ 29 －

Ⅱ 博士研究員 (2017)【氏名】 Simon Kaspar Schnyder【職名】 FIFC Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 208【直通電話】 075-711-7863【電子メールアドレス】 schnyder@fukui.kyoto-u.ac.jp【研究分野】 Soft matter physics, Biophysics, Computational physics【現在の研究課題】 Structure and dynamics of cellular tissues, anomalous transport in heterogeneous
media【研究内容キーワード】 Cell migration, Epithelial tissues, Lorentz model, Porous media, Percolation,
Anomalous diffusion【学歴】 January 2010, Diploma in Physics, University of Konstanz, Konstanz, Germany
May 2014, Doctor of Science , University of Düsseldorf, Düsseldorf, Germany【学位】 Doctor of Science from University of Düsseldorf【略歴】 June 2014 - November 2014, Postdoctoral Fellow, University of Düsseldorf
December 2014 - December 2016, Postdoctoral Fellow, Department of Chemical
Engineering, Kyoto University
January 2017 - now, FIFC Fellow, Fukui Institute for Fundamental Chemistry, Kyoto
University【所属学会】 German Physical Society (DPG)【主な著書、学術論文】 1. S. K. Schnyder, & J. Horbach, “Crowding of interacting fluid particles inporous media through molecular dynamics: breakdown of universality for soft
（過去 5 年以内）
interactions”, Physical Review Letters, 120(7), 78001 (2018).
2. J. Horbach, N. H. Siboni, & S. K. Schnyder, “Anomalous transport in heterogeneous
media“, The European Physical Journal Special Topics, 226(14), 3113–3128 (2017).
3. S. K. Schnyder, J. J. Molina, Y. Tanaka, R. Yamamoto, “Collective motion ofcells crawling on a substrate: roles of cell shape and contact inhibition“, Scientific
Reports 7, 5163 (2017).
4. S. K. Schnyder, T. O. E. Skinner, A. Thorneywork, D. G. A. L. Aarts, J. Horbach,R. P. A. Dullens, “Dynamic heterogeneities and non-Gaussian behaviour in 2D
randomly confined colloidal fluids”, Physical Review E (2017).
5. M. Heinen, S. K. Schnyder, J. F. Brady, H. Löwen, “Classical liquids in fractal
dimension”, Physical Review Letters 115, 097801 (2015).
6. S. K. Schnyder, M. Spanner, F. Höfling, T. Franosch, J. Horbach, “Rounding of thelocalization transition in model porous media”, Soft Matter 11, 701 (2015).

－ 30 －

Ⅱ 博士研究員 (2017)【氏名】 伊勢川

美穂 （いせがわみほ）【職名】 助教【所属】 カーボンニュートラル・エネルギー国際研究所（I2CNER），九州大学【研究室】 I2CNER, NEXT-FC【直通電話】 092-802-6741【電子メールアドレス】 isegawa.miho.169@m.kyushu-u.ac.jp【研究分野】 計算化学
【現在の研究課題】 Reaction process for electrochemical and photochemical conversion of carbon dioxide【研究内容キーワード】 触媒、分子変換機構、スペクトロスコピー、化学エネルギー変換【学歴】 2009 年 9 月 京都大学大学院理学研究科化学専攻博士課程修了【学位】 2009 年 9 月 京都大学理学博士【略歴】 2010 年 1 月 米国ミネソタ大学博士研究員
2013 年 3 月 京都大学福井謙一記念研究センター研究員
2014 年 6 月 ドイツ 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 年 1 月 京都大学福井謙一記念研究センター研究員
2018 年 2 月 九州大学、I2CNER 助教【主な著書、学術論文】 1. DFT Study on Fe(IV)-Peroxo Formation and H Atom Triggered O 2 activation（過去 5 年以内）
by NiFe Hydrogenase, M. Isegawa, A. K. Sharma, S. Ogo, K. Morokuma.,
Organomettalics, 37, 1534 (2018).
2. Copper-catalyzed Enantioselective Boron Conjugate Addition: DFT and AFIR
Study on Different Selectivities of Cu(I) and Cu(II) Catalysts, M. Isegawa, W.
M. C. Sameera, A. K. Sharma, T. Kitanosono, Masako Kato, S. Kobayashi, K.
Morokuma., ACS Catalysis, 7, 5370 (2017).
3. Ionization Energies and Aqueous Redox Potentials of Organic Molecules:
Comparison of DFT, Correlated ab Initio Theory and Pair Natural Orbital
Approaches, M. Isegawa, F. Neese, D. A. Pantazis, J.Chem. Theory Comput. 12,2272 (2016).
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. 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).
6. Predicting pathways for terpene from first principles-routes to known and newsesquiterpenes, M. Isegawa, S. Maeda, D. J. Tantillo, and K. Morokuma Chemical
Science, 5, 1555 (2014).

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Ⅱ 博士研究員 (2017)【氏名】 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. S.Suzuki, S. Maeda, K. Morokuma, Exploration of Quenching Pathways ofMultiluminescent Acenes Using the GRRM Method with the SF-TDDFT Method, J.
（過去 5 年以内）
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. Phys.,138, 8194-8206 (2016)
3. S.Sasaki, S.Suzuki, K. Igawa, K. Morokuma, G. Konishi, The K-Region in
Pyrenes as a Key Position to Activate Aggregation-Induced Emission: Effects ofIntroducing Highly Twisted N,N-Dimethylamines, J. Org. Chem., 82, 6865-6873(2017)【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－ 32 －

Ⅱ 博士研究員 (2017)【氏名】 Akhilesh Kumar Sharma【職名】 Postdoctoral Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room No. 207【直通電話】 075-711-7893【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 organometalic reactions【研究内容キーワード】 DFT, AFIR, Reaction Mechanism, Stereoselectivity【学歴】 Master of Science, Himachal Pradesh University, Shimla, India (2006)【学位】 Ph.D., Indian Institute of Technology (IIT), Bombay, Mumbai, India (2014)【略歴】 Research Associate, Indian Institute of Technology (IIT), Bombay, Mumbai, India(2014-2015)【主な著書、学術論文】 1. W. M. C. Sameera, Akhilesh K. Sharma, Satoshi Maeda, Keiji Morokuma, “Artificial
Force Induced Reaction Method for Systematic Determination of Complex（過去 5 年以内）
Reaction Mechanisms” Chemical Record, 16 (5), 2349-2363 (2016).
2. Ming-Chung Yang, Akhilesh K. Sharma, W. M. C. Sameera, Keiji Morokuma, andMing-Der Su, “Theoretical Study of Addition Reactions of L4M(M = Rh, Ir) andL2M(M = Pd, Pt) to Li+@C60” J. Phys. Chem. A, 121 (13), 2665-2673 (2017).
3. Miho Isegawa, W. M. C. Sameera, Akhilesh K. Sharma, Taku Kitanosono, Masako
Kato, Shu Kobayashi, and Keiji Morokuma, "Copper-catalyzed Enantioselective
Boron Conjugate Addition: DFT and AFIR Study on Different Selectivities of Cu(I)and Cu(II) Catalysts" ACS Catal., 7 (8), 5370–5380 (2017).
4. Akhilesh K. Sharma, W. M. C. Sameera, Masayoshi Jin, Laksmikanta Adak,
Chiemi Okuzono, Takahiro Iwamoto, Masako Kato, Masaharu Nakamura, andKeiji Morokuma “DFT and AFIR Study on the Mechanism and the Origin of
Enantioselectivity in Iron-Catalyzed Cross-Coupling Reactions” J. Am. Chem. Soc.,
139 (45), 16117-16125 (2017).
5. Miho Isegawa, Akhilesh K. Sharma, Seiji Ogo, and Keiji Morokuma, “DFT Studyon Fe(IV)-Peroxo Formation and H Atom Transfer Triggered O2 Activation by NiFe
Complex” Organometallics, 37(10), 1534-1545 (2018).
【学術関係の受賞など】 “2014 Eli Lilly and Company Asia Outstanding Thesis Award” for Best Thesis
Fellowship from council for Scientific and Industrial Research (CSIR), India to Pursue
PhD.

－ 33 －

Ⅱ 博士研究員 (2017)【氏名】 Maneeporn Puripat【職名】 Research Fellow【所属】 Nara Institute of Science and Technology
Institute for Research Initiatives
Graduate School of Materials Science【研究室】 8916-5 Takayama-cho, Ikoma, Nara 630-0192, JAPAN【直通電話】 0743-72-6026【電子メールアドレス】 puripat@ms.naist.jp【ホームページ】 http://www.naist.jp/en/【研究分野】 Theoretical Chemistry【現在の研究課題】 Theoretical/Computational Chemistry for Complex Molecular Systems【研究内容キーワード】 Transition state, Catalysis, Catalytic reaction, Reaction mechanism【学歴】 Ph.D. (Nanoscience Technology), Chulalongkorn University, Thailand (2016)
B.Sc. (Physics, 2nd class Hon.), Chulalongkorn University, Thailand (2011)【学位】 Doctor of Philosophy from Chulalongkorn University, Thailand【略歴】 1. Special Lecturer, Rajamangala University of Technology Phra Nakhon (RMUTP),
Bangkok, Thailand (2012-2016)
2. Research Fellow, Fukui Institute for Fundamental Chemistry (FIFC), Kyoto
University, Kyoto, Japan (2016-2017)
3. Lecturer, Rajamangala University of Technology Thanyaburi (RMUTT), Pathum
Thani, Thailand (2017-2018)
4. Research Fellow, Nara Institute of Science and Technology, Nara (NAIST), Japan(2018-present)【主な著書、学術論文】 1. Maneeporn Puripat, Romain Ramozzi, Miho Hatanaka, Waraporn Parasuk,
Vudhichai Parasuk, and Keiji Morokuma, “The Biginelli reaction is a ureacatalyzed（過去 5 年以内）
organocatalytic multicomponent reaction” J. Org. Chem. 80 (14), 6959-6967 (2015).
2. Arifin, Maneeporn Puripat, Daisuke Yokogawa, Vudhichai Parasuk, and Stephan
Irle, “Glucose transformation to 5-hydroxymethylfurfural in acidic ionic liquid: A
quantum mechanical study” J. Comput. Chem. 37 (3), 327-335 (2016).
3. Tomoharu Oku, Masaki Okada, Maneeporn Puripat, Miho Hatanaka,
Keiji Morokuma, and Jun-Chul Choi “Promotional effect of CH3I onhydroxycarbonylation of cycloalkene using homogeneous rhodium catalysts with
PPh3 ligand” J. Co2. Util. 25, 1-5(2018).
【学術関係の受賞など】 1. The Development and Promotion of Science and Technology Talents Project (DPST)(Royal Government of Thailand scholarship) of Thailand (2004-2016)
2. The New Energy and Industrial Technology Development Organization (NEDO).
(2016-present)－ 34 －

Ⅱ 博士研究員 (2017)【氏名】 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、
周期的分子結晶解析【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】 分子科学会、理論化学会、錯体化学会【主な著書、学術論文】 1. Aono S., Hosoya T., and Sakaki S., “A 3D-RISM-SCF method with dual solvent
boxes for a highly polarized system: application to 1,6-anhydrosugar formation（過去 5 年以内）
reaction of phenyl alpha- and beta-D-glucosides under basic conditions” Phys.
Chem. Chem. Phys. 17, 6368, (2013)
2. Aono S., 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. 10,1062, (2014).
3. 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.
Chem. Theory Comput. 12, 1189-1206, (2016).
4. Aono S, Nakagaki M., and Sakaki S. “Theoretical Study of One-Electron Oxidized
Salen Complexes of Group 7 (Mn(III), Tc(III), and Re(III)) and Group 10 Metals(Ni(II), Pd(II), and Pt(II)) with 3D-RISM-GMC-QDPT Method: Localized vs.
Delocalized Ground and Excited States in Solution” Phys. Chem. Chem. Phys. 19,
16831-16849, (2017).

－ 35 －

Ⅱ 博士研究員 (2017)【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 ““Hetero-dinuclear complexes of 3d
metals with a bridging dinitrogen ligand: theoretical prediction of the characteristic（過去 5 年以内）
features of geometry and spin multiplicity” Phys. Chem. Chem. Phys., 18, 2636526375 (2016).
2. Takako Muraoka, Haruhiko Kimura, Gama Trigagema, Masayuki Nakagaki,
Shigeyoshi Sakaki, and Keiji Ueno “Reactions of Silanone(silyl)tungsten
and -molybdenum Complexes with MesCNO, (Me 2SiO) 3, MeOH, and H2O:
Experimental and Theoretical Studies” Organometallics, 36, 1009-1018(2017).
3. 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)
4. 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)
5. 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)－ 36 －

Ⅱ 博士研究員 (2017)【氏名】 Jing Lu【職名】 Research 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】 jing@fukui.kyoto-u.ac.jp【研究分野】 Computational Chemistry【現在の研究課題】 Theoretical study of bimetallic alloyed nanoclusters/particles【研究内容キーワード】 Bimetallic alloyed nanoclusters/particles, core-shell structure, oxygen reduction
reaction【学歴】 June 2016, Doctor of Sci., Faculty of Chemistry, Northeast Normal University, P.R.
China【学位】 Doctor of Science from Northeast Normal University【略歴】 Aug. 2016, Postdoctoral Fellow, FIFC, Kyoto University【主な著書、学術論文】 1. Lu, J.; Ishimura, K.; Sakaki, S., Theoretical Insight into Core–Shell Preference for
Bimetallic Pt-M (M = Ru, Rh, Os, and Ir) Cluster and Its Electronic Structure. J.
（過去 5 年以内）
Phys. Chem. C 122, 9081-9090 (2018).
2. Lu, J.; Zheng, Y.; Zhang, J., Computational design of benzo [1,2-b:4,5-b']
dithiophene based thermally activated delayed fluorescent materials. Dyes andPigments 127, 189-196 (2016).
3. Lu, J.; Zheng, Y.; Zhang, J., Rational design of phenoxazine-based donor-acceptordonor thermally activated delayed fluorescent molecules with high performance.
Phys. Chem. Chem. Phys. 17, 20014-20020 (2015).
4. Lu, J.; Yao, Y.; Shenai, P. M.; Chen, L.; Zhao, Y., Elucidating the enhancement in
optical properties of low band gap polymers by tuning the structure of alkyl side
chains. Phys. Chem. Chem. Phys. 17, 9541-9551 (2015).
5. Lu, J.; Zheng, Y.; Zhang, J., Tuning the color of thermally activated delayed
fluorescent properties for spiro-acridine derivatives by structural modification of theacceptor fragment: a DFT study. RSC Adv. 5, 18588-18592 (2015).

－ 37 －

Ⅱ 博士研究員 (2017)【氏名】 Rong-Lin Zhong【職名】 Research Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 303【直通電話】 075-711-7907【FAX】 075-711-7907【電子メールアドレス】 zhongrl@fukui.kyoto-u.ac.jp【ホームページ】 http://tcclab.jlu.edu.cn/info/1045/1082.htm【研究分野】 Computational Chemistry【現在の研究課題】 Theoretical Study of Complex Systems Including d-electrons【研究内容キーワード】 Palladium catalysis, oxidative addition, reaction mechanism【学歴】 June 2010, bachelor of Chemistry Education, Faculty of Chemistry, Northeast Normal
University
June 2015, Doctor of Physical Chemistry, Institute of Functional Material Chemistry,
Faculty of Chemistry, Northeast Normal University【学位】 Doctor of Physical Chemistry from Northeast Normal University【略歴】 Otc. 2016, Lecturer, Jilin University【主な著書、学術論文】 1. Yadav, R. M.; Nagaoka, M.; Kashihara, M.; Zhong, R.-L.; Miyazaki, T.; Sakaki, S.;
Nakao, Y. J. Am. Chem. Soc., 2017, 139, 9423-9426.
（過去 5 年以内）
2. R.-L. Zhong, H.-L. Xu,* Z.-R. Li* and Z.-M. Su*. Role of Excess Electrons in
Nonlinear Optical Response. J. Phys. Chem. Lett. 2015, 6, 612-619
3. R.-L. Zhong, H.-L. Xu,* S.-L. Sun, Y.-Q. Qiu, and Z.-M. Su*. The Excess Electron
in a Boron Nitride Nanotube: Pyramidal NBO Charge Distribution and RemarkableFirst Hyperpolarizability. Chem. Eur. J. 2012, 18, 11350 – 11355.
4. R.-L. Zhong, H.-L. Xu,* S. Muhammad, J. Zhang and Z.-M. Su*. The stability andnonlinear optical properties: Encapsulation of an excess electron compound LiCN/
Li within boron nitride nanotubes. J. Mater. Chem., 2012, 22, 2196–2202.
5. R.-L. Zhong, S.-L. Sun, H.-L. Xu,* Y.-Q. Qiu, and Z.-M. Su*. BN Segment Doped
Effect on the First Hyperpolarizibility of Heteronanotubes: Focused on an Effective
Connecting Pattern. J. Phys. Chem. C 2013, 117, 10039-10044.
【学術関係の受賞など】 1. 2012, National scholarship for PhD candidate.
2. 2013, Excellent graduate student of Northeast Normal University.

－ 38 －

Ⅱ 博士研究員 (2017)【氏名】 松岡

貴英 （まつおかたかひで）【職名】 特別研究員【所属】 理化学研究所

計算科学センター【研究室】 501
【直通電話】 078-940-5678【FAX】 078-304-4975【電子メールアドレス】 matsuoka@fukui.kyoto-u.ac.jp【研究分野】 計算分子科学【学歴】 2011 年 3 月 慶應義塾大学大学院理工学研究科前期博士課程修了
2014 年 3 月 慶應義塾大学大学院理工学研究科後期博士課程修了【学位】 2014 年 3 月

博士（理学）（慶應義塾大学）【略歴】 2014 年 4 月
2016 年 4 月

慶應義塾大学准訪問研究員、2015 年 7 月
京大福井センター研究フェロー

東京大学特定研究員、【所属学会】 日本化学会，分子科学会【主な著書、学術論文】 1. Takahide Matsuoka, Sayo Oonishi, Satoshi Yabushita, “Theoretical study on
angular momentum polarization parameters, branching ratios, and anisotropy（過去 5 年以内）
parameters of chlorine atoms from Photodissociation of Iodine Monochloride”, Int.
J. Quantum Chem. 113(3), 375—381 (2013).
2. Takahide Matsuoka, Satoshi Yabushita, “Theoretical study on the photofragment
branching ratios and anisotropy parameters of ICl in the second absorption band”,
Chem. Phys. Lett. 592, 75—79 (2014).
3. Takahide Matsuoka, Satoshi Yabushita, “Quantum Interference Effects
Theoretically Found in the Photodissociation Processes of the Second Absorption
Bands of ICl and IBr Molecules”, J. Phys. Chem. A 119(37), 9609—9620 (2015).
4. Takahide Matsuoka, Kazuo Takatsuka, “Dynamics of photoionization frommolecular electronic wavepacket states in intense pulse laser fields: A nonadiabatic
electron wavepacket study”, J. Chem. Phys. 146(13), 134114 (2017).
5. Takahide Matsuoka, Kazuo Takatsuka, “Nonadiabatic electron wavepacket
dynamics behind molecular autoionization”, J. Chem. Phys. 148(1), 014106 (2018).

－ 39 －

Ⅱ 博士研究員 (2017)【氏名】 山本憲太郎 （やまもと

けんたろう）【職名】 研究フェロー【所属】 福井謙一記念研究センター

高塚グループ305【研究室】 福井謙一記念研究センター【電子メールアドレス】 kyamamoto@fukui.kyoto-u.ac.jp【研究分野】 理論化学
【現在の研究課題】 非断熱電子動力学理論による化学反応の研究【研究内容キーワード】 非断熱遷移，電荷分離【学歴】 2015 年 3 月

東京大学大学院理学系研究科化学専攻博士過程修了【学位】 2015 年 3 月

理学博士（東京大学）【略歴】 2014 年

東京大学技術補佐員，2015 年

東京大学特任研究員【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. K. Yamamoto and K. Takatsuka, "Electronic quantum effects mapped onto nonBorn-Oppenheimer nuclear paths: Nonclassical surmounting over potential barriers（過去 5 年以内）
and trapping above the transition states due to nonadiabatic path-branching", J.
Chem. Phys. 140, 124111 (2014).
2. K. Yamamoto and K. Takatsuka, "An Electron Dynamics Mechanism of Charge
Separation in the Initial-Stage Dynamics of Photoinduced Water Splitting in X–
Mn–Water (X=OH, OCaH) and Electron–Proton Acceptors", ChemPhysChem 16,2534 (2015).
3. K. Yamamoto and K. Takatsuka, "Dynamical mechanism of charge separation byphotoexcited generation of proton–electron pairs in organic molecular systems. A
nonadiabatic electron wavepacket dynamics study", Chem. Phys. 475, 39 (2016).
4. K. Yamamoto and K. Takatsuka, "Photoinduced Charge Separation Catalyzed by
Manganese Oxides onto a Y-Shaped Branching Acceptor Efficiently Preventing
Charge Recombination", ChemPhysChem 18, 537 (2017).
5. K. Yamamoto and K. Takatsuka, "On the photocatalytic cycle of water splittingwith small manganese oxides and the roles of water clusters as direct sources ofoxygen molecules", Phys. Chem. Chem. Phys. 20, 6708 (2018).

－ 40 －

Ⅱ 博士研究員 (2017)【氏名】 新崎康樹 （あらさき

やすき）【職名】 研究フェロー【所属】 福井謙一記念研究センター

高塚グループ【研究室】 東京大学駒場キャンパス 16 号館 408【研究分野】 理論化学

【現在の研究課題】 非断熱動力学理論による化学反応【研究内容キーワード】 非断熱相互作用、クラスター、励起状態動力学【学歴】 2000 年 9 月

東京大学大学院総合文化研究科博士課程修了【学位】 2000 年 9 月

博士（学術）（東京大学）【略歴】 2000 年 10 月 東京大学インテリジェント・モデリング・ラボラトリー研究員
2002 年 10 月 東京大学大学院総合文化研究科 研究員【所属学会】 分子科学会【主な著書、学術論文】 1. Y. Arasaki and K. Takatsuka, Pulse-train photoelectron spectroscopy of electronic
and nuclear dynamics in molecules, ChemPhysChem 14, 1387-1396 (2013).
（過去 5 年以内）
2. Y. Arasaki, Y. Mizuno, S. Scheit, and K. Takatsuka, Induced photoemission fromdriven nonadiabatic dynamics in an avoided crossing system, J. Chem. Phys. 141,234301 (2014, 14 pages).
3. Y. Arasaki, Y. Mizuno, S. Scheit, and K. Takatsuka, Stark-assisted quantum
confinement of wavepackets. A coupling of nonadiabatic interaction and CW-laser, J.
Chem. Phys. 144, 044107 (2016, 10 pages).
4. Y. Arasaki and K. Takatsuka, Time-resolved photoelectron signals from bifurcating
electron wavepackets propagated across conical intersection in path-branching
dynamics, Chem. Phys. 493, 42-48 (2017).
5. K. Takatsuka, T. Yonehara, K. Hanasaki, and Y. Arasaki, Chemical Theory Beyond
the Born-Oppenheimer Paradigm: Nonadiabatic Electronic and Nuclear Dynamics
in Chemical Reactions (World Scientific, Singapore, 2014).

－ 41 －

Ⅱ 博士研究員 (2017)

５. 日本学術振興会外国人特別研究員プロフィール【氏名】 Xue-Feng Ren【職名】 Postdoctoral Fellow【所属】 Morokuma Group, Fukui Institute of Fundamental Chemistry【研究室】 Room No.212【直通電話】 075-711-7647【FAX】 075-781-4757【電子メールアドレス】 renxf@cumt.edu.cn【研究分野】 Computational Chemistry【現在の研究課題】 excited state emission decay【研究内容キーワード】 DFT, AFIR, PES【学歴】 Ph.D. Physical Chemistry, Jilin University, Changchun【学位】 Ph.D. Physical Chemistry, Jilin University, Changchun【略歴】 Nanjing University, 2010-2012, Ph.D fellow
China University of Mining and Technology, Xuzhou, associate professor【主な著書、学術論文】 1. Xue‑Feng Ren, Guo‑Jun Kang, Qiong‑Qiong He, and et. al, Theor Chem Acc 2016,
135, 24（過去 5 年以内）
2. Xue Feng Ren, Guo Jun Kang, Shou Feng Zhang, and et. Al, J. Photochem.
Photobio. A: Chemistry, 2015, 311, 85
3. Guo Jun Kang, Xue Feng Ren,* Si Yu Bai, J Organomet. Chem. 2015, 785, 44【学術関係の受賞など】 JSPS Research Fellowships－ 42 －

Ⅱ 博士研究員 (2017)

６. 日本学術振興会特別研究員プロフィール【氏名】 松崎黎 （まつざきれい）【職名】 FIFC フェロー【所属】 高塚グループ【研究室】 福井記念研究センター 303【直通電話】 711-7907【FAX】 711-7907【電子メールアドレス】 matsuzaki@fukui.kyoto-u.ac.jp【ホームページ】 http://mns2.fukui.kyoto-u.ac.jp/【研究分野】 計算化学
【現在の研究課題】 非断熱電子動力学における核の量子性【研究内容キーワード】 非断熱系、核の量子性【学歴】 2017年3月

慶應義塾大学大学院基礎理工学専攻博士課程修了【学位】 2017年3月

博士（理学）【略歴】 2015年4月 慶應義塾大学助教（有期・研究奨励）、2016年4月 日本学術振興会特別研究員DC2、2017年4月 日本学術振興会特別研究員PD、2018年4月
福井謙一記念研究センター フェロー
【所属学会】 日本化学会、分子科学会【主な著書、学術論文】 1. R.Matsuzaki, S.Asai, C.W.McCurdy, S.Yabushita, “Construction of complex STONG basis sets by the method of least squares and their applications”, Theoretical（過去 5 年以内）
Chemistry Accounts, 133, 1521 (2014)
2. R.Matsuzaki, S.Yabushita, “Optimization of complex slater-type functions withanalytic derivative methods for describing photoionization differential crosssections”, J.Comput.Chem. 38, 910 (2017)
3. R. Matsuzaki, S.Yabushita, “Calculation of photoionization differential crosssections using the complex Gauss-type orbitals”, J.Comput.Chem. 38, 2030 (2017)【学術関係の受賞など】 Journal of Physics B Atomic, Molecular and Optical Physics Best Poster Award 2013

－ 43 －

Ⅲ 研究広報活動 (2017)

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 15 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2018 年 2 月 2 日（金） 10:00 – 19:00

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

10:15 – 11:15
佐々真一 （京都大学 大学院理学研究科）「気液転移と熱伝導が出会うとき：19 世紀科学から 21 世紀科学への展開」
11:30 – 12:30
北浦

和夫 （京都大学 福井謙一記念研究センター）「The Group Molecular Orbital Method For Large Molecular Systems」
―

休

憩

―

13:50 – 14:50
幾原

雄一 （東京大学 大学院工学研究科）「原子直視 STEM 法の新展開と材料科学への応用」
15:00 − 15:30

福井謙一奨励賞表彰式

15:30 − 17:20

ポスターセッション

17:30 − 19:00

懇親会（１F 多目的ルーム）－ 44 －

Ⅲ 研究広報活動 (2017)

２．セミナー（1）第 15 回 福井センターセミナー
日時2017 年（平成 29 年）5 月 25 日（木） 15:00 – 17:20

場

所

京都大学 福井謙一記念研究センター（１階 106 室）
15:00 – 15:40
Yoshio Nishimoto (Kyoto Univ.)“Analytic Derivatives with Fractional Occupation Number”
15:40 – 16:20
Mitsusuke Tarama (Kyoto Univ.)“Nonlinear Dynamics of Active Deformable Particles : From Liquid
Droplets to Biological Cells”― Break ―16:30 – 17:20
Dmitri G.Fedorov (Advanced Industrial Science and Technology)“Large Scale Quantum-Mechanical Calculations with the Fragment
Molecular Orbital Method”（2）その他のセミナー
Contact

Kazuo
Takatsuka

Speaker

Mikiya
Fujii

Title

Affiliation

Date

Change separation
pathways in P3HT/PCBM
photovoltaic blends,
and their crystalline
dependencies.

The
University ofTokyo

June 9(Fri),
2017－ 45 －

Ⅲ 研究広報活動 (2017)

Contact

Speaker

Title

Affiliation

Date

Alena
Kremleva

Quantum chemical modelingof electrochemistry of
Mn substituted Kegginpolyoxoanions. Effects ofelectrolyte environment

Technische
Universität
MünchenNovember
1 (Wed),2017

VladimirG. Malkin

Relativistic calculations of
EPR parameters And theirinterpretation

SlovakAcademy Of
Sciences

Olga L.
Malkina

Contact betweek hydrogenatoms observed by through-space indirect NMR coupling

SlovakAcademy Of
Sciences

Marek J.
WójcikTheoretical Modeling ofVibrational Spectra of
Hydrogen-Bonded Systems,
Ice and Aqueous Ionic
Solutions

Jagiellonian
University

January
24 (Wed),2018

Shigeyoshi
Sakaki

Hirotaka
Ihara

Self-organization-based
Supramolecular Gel:
Molecular Design andApplications

Kumamoto
University

February
5 (Mon),2018

Shigeyoshi
SakakiWeston T.
BordenWhy Are N2 and O2
Unreactive?

University ofNorth Taxas

March
27 (Tue),
2018

Shigeyoshi
Sakaki

Shigeyoshi
Sakaki

Shigeyoshi
Sakaki

December
11 (Mon),2017

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）－ 46 －

Ⅲ 研究広報活動 (2017)

4．社会へのアウトリーチ活動＜研究紹介＞
2017年（平成29年）9月30日（１）京都大学アカデミックデイへ参加

高塚 和夫 リサーチリーダー他が「ポスターを使っての対話」コーナーへ参加
ポスタータイトル：分子科学の超高速実験と動的電子描像

榊 茂好 リサーチリーダー他が「ちゃぶ台で対話」コーナーへ参加話

題：フロンテイア軌道理論；役に立つの？

場

所：京都大学百周年時計台記念館＜学術講演＞
2017年（平成29年）11月2日（２）田中 一義 シニアリサーチフェロー
演

題：計算化学はどのように役立つか

行事名：京都グリーンケミカル・ネットワーク人材育成事業
場

所：京都市成長産業創造センター

5．福井謙一奨励賞の創設及び奨励賞の授与
福井謙一博士の生誕百年を控え、日頃から、化学の将来の発展のためには若手研究者の育成の大切さを説いておられた福井博士の意志を汲み、基礎化学、理論化学の分野で顕著な研究業績を挙げた若手研究者を顕彰する福井謙一奨励賞を創設した。
平成 29 年秋に公募し、応募のあった中から委員会で選考の結果、次のとおり選考された。
表彰式は、平成 30 年 2 月 2 日（金）に開催の福井謙一記念研究センターシンポジウムの中で行い受賞者に表彰状と記念楯が授与され、続いて受賞題目に関した講演が行われた。

受賞者：越知 正之（大阪大学

大学院理学研究科

助教）

受賞題目：第一原理波動関数理論の固体への展開：量子化学と固体電子論の融合－ 47 －

Ⅳ 研究業績 (2017)

Ⅳ

研究業績
Yoshio Nishimoto

１．専任教員Program-Specific Assistant Professor
1. Summary of the research of the year
Development of FMO-DFTB/AFO
Recent progress in linear-scaling quantum
mechanical methods enables large-scalecalculations for more than one million
atoms. The fragment molecular orbital(FMO) method is one of the linear-scaling
methods, and a combination with thedensity-functionaltight-binding(DFTB)

method is potentially applicable to evenlarger systems. I have been developing the
combination, FMO-DFTB method [1], inthese years.
In this fiscal year, I combined
FMO-DFTB with the adaptive frozen
orbital (AFO) treatment [2]. The wholealgorithm is shown in Fig. 1. In FMO, one
has to divide a large system into fragments.
Although this sounds straightforward when
the system consists of isolated molecules orcluster, such as water, a special care has tobe paid when we try to divide it acrosscovalent bonds. The conventional procedure
is referred to as the hybrid orbital projection(HOP) approach. Users usually have toprepare sp3 hybrid orbitals in prior to
calculations, and orbitals in fragments areprojected out from the variational space to
avoid duplication in the actual calculation.
The AFO approach is conceptually similar,
but it employs localized orbitals generated
in model systems on the fly. Model systems
are constructed from a subspace of theFig. 1 Algorithm for computing FMO/AFO gradients. Eachcircle represents solving Z-vector equations. Arrows represent
the flow of Lagrangian, localization, auxiliary density, andderivative contributions－ 48 －

Ⅳ 研究業績 (2017)

whole system. In spite of the similarity, derivations and implementations of the analytic derivative of thetotal energy with the AFO approach is not straightforward, and they have not been realized.
Eventually, first-order derivatives can be analytically computed as in Fig. 1. The algorithm implies
that four types of response (Z-vector) equations have to be solved in FMO-DFTB/AFO, while theconventional FMO-DFTB/HOP required only the second Z-vector equation, called the self-consistent
Z-vector equation. The first type of the Z-vector equations arises from freezing occupied and projecting out
virtual orbitals in fragments. The third and fourth do from response contributions in model systems, because
the geometry of the model system is dependent on coordinates of the real system. It is apparent that the latter
contributions do not exist in the conventional FMO/HOP method, since hybrid orbitals to be projected out
are generated for fixed structures. Because of the complexity, FMO/AFO is 1.6–2.3 times expensive than
FMO/HOP. The extra cost is mostly relevant to matrix algebra, in particular matrix multiplications. The
deviations of the implemented gradient from numerical gradients is on the order of 10-5 hartree/bohr, and theresidual error should be attributed to the limited accuracy of numerical gradients. As a demonstrative
example, FMO2-DFTB2/HOP had a large error for a zeolite system (+32.84 kcal/mol), but it decreased toonly -0.60 kcal/mol with FMO2-DFTB2/AFO.
It is now possible to apply FMO-DFTB/AFO to molecular dynamics (MD) simulations. As ademonstration, we prepared a large boron-nitride nano-ring consisting of 1,180,800 atoms with 65,550
fragments and 131,100 detached bonds. It took 181 hours for 500 MD steps on a computer node with 24
CPU cores, so a single step took only 22 minutes on average. It thus shows that calculations for one million
atom systems on a laboratory-scale computer resource are not challenging any more. Developers of FMO areplanning that recent developments, including some improvements for previous implementations, are released
in 2018, as a part of GAMESS-US.

Mechanism of a Pd-Catalyzed Aromatic C–H Coupling Reaction
C–H functionalization is a rapidly growing field in organic chemistry because of its potential applications inthe synthesis of pharmaceuticals, natural products, agrochemicals, and organic materials. The utility of C–H
functionalization is particularly pronounced when structural isomers and/or stereoisomers can be
distinguished. As one of the most fundamental reactions, the C–H coupling of heteroarenes with arylboron
compounds has been extensively studied both experimentally and theoretically. However, this type ofreaction usually requires a stoichiometric amount of co-oxidants such as 1,4-benzoquinone, Cu(II) halides,and Ag(I) salts, which results in chemical waste except in some rare cases. Moreover, these catalysts
generally exhibit low reactivity when sterically demanding substrates are employed.
Recently, Itami, Yamaguchi, and co-workers discovered an aromatic C–H coupling reaction ofheteroarenes and sterically hindered arylboronic acids utilizing a Pd/Fe dual catalyst that could overcome theabove-mentioned drawbacks [3]. The dual catalyst consists of Pd(II)-sulfoxide-oxazoline (sox) andiron-phthalocyanine (FePc), where FePc is considered to oxidize Pd(0) to Pd(II) with oxygen in the air as theterminal oxidant. Despite the aforementioned attractive features, the highest enantiomeric excess (ee) value
was 61%, and understanding of the reaction mechanism, which would aid in developing a catalyst which－ 49 －

Ⅳ 研究業績 (2017)delivers a higher ee, has been limited. We
reported an experimental substituent effectstudy of a model reaction as well as atheoretical investigation to clarify thereaction mechanism of the representative
reaction shown in Fig. 2 [4].
All the structures were optimized
using density functional theory (DFT) as
implemented in Gaussian 09. We selected
B3PW91 exchange–correlation functionalwith 6-31G(d) and LANL2DZ basis set for

Fig. 2 Aromatic C–H coupling reaction of a thiophene

typicalderivative and a hindered arylboronic acid, assisted by a Pd/Fe

and

Pd

atoms,

respectively(abbreviated as BSI). Energy refinement fordual catalyst.

optimized structures was performed as DF-SCS-MP2/(aug-)cc-pVTZ as implemented in MOLPRO 2012. We
added augmented functions for N, O, and S atoms and pseudopotential (ECP28MDF) for Pd (BSII). Solvent
effect was implicitly added by performing reference Hartree–Fock calculation with COSMO solvation modelwith nonelectrostatic energies of the SMD solvation model.
The reaction profile (Fig. 3) showed that the (S)-product should be dominant because the highest
activation energy of the transition state (TS) leading to the (S)-product (TS4-5S) is 3.0 kcal/mol lower than the
TS leading to the (R)-product (TS4-5R). This finding is consistent with the experimental conditions at 70°C.
Other important TSs are the C–C bond formation step (TS8-9S and TS8-9R) and the abstraction of a proton to

Fig. 3 Proposed reaction profile as the COSMO-DF-SCS-MP2/BSII//B3PW91/BSI level of theory. Blue andred lines (blue lines come lower except at 10 and TS10-11) represent free energies of reaction coordinates leading
to (S)- and (R)-stereoisomers, respectively.
－ 50 －

Ⅳ 研究業績 (2017)

form a double bond on the thiophene ring (TS11-12S and TS11-12R). Activation energies of these steps are lower
than that of the C–B bond transmetalation. The HOAc species generated in the catalytic cycle may be
converted to OAc- and water in the oxidation step. The water may then hydrolyze AcO–B(OH)2 resulting inregeneration of 2oac.
The main question is why the energy difference of 3.0 kcal/mol emerges at this enantioselective
step. To address this, we calculated the interaction energy between the aryl group on the Pd center and thetolyl group of the sox ligand. The interaction energies at the DF-SCS-MP2/BSII level of theory was 1.9 and1.8 kcal/mol for TS4-5S and TS4-5R, respectively, so the difference of 0.2 kcal/mol only represents ~5% of thetotal energy difference of 3.0 kcal/mol, implying that steric repulsion alone cannot reasonably explain theenantioselectivity of the catalytic reaction.
We next focused on the electronic structure effect of the rotation of the tolyl group. We adopted thenatural bond orbital (NBO) analysis at the B3PW91/BSI level of theory. Our analysis revealed that TS4-5S
and hypothetical TS4-5S with the dihedral angle between O–S–C–C atoms equivalent to that of TS4-5R arestabilized by 5.9 and 3.3 kcal/mol, respectively, by the interaction between the donor (occupied C–Cπ-orbital on the tolyl group) and the acceptor (unoccupied S–O σ*-orbital on the sox ligand) NBOs. Theinteraction corresponds to the hyperconjugation between these orbitals. The difference of the interactionenergies is 2.6 kcal/mol, which is close to the difference of the activation energies at TS4-5S and TS4-5R,
namely 3.0 kcal/mol. Although we suggested some substitutions which are expected to yield a better eebased on the analysis of stabilization energies of different substitutions of the sox ligand, these are difficult torealize experimentally.
In summary, our study indicates that the rate-determining and stereoselective step of the reaction is
the C–B translmetalation of the arylboronic acid. NBO analysis reveals that the difference between theactivation energy of two TSs leading to (S)- and (R)-products (TS4-5S and TS4-5R) is attributed to thehyperconjugation between π-orbitals on the tolyl and the S–O σ*-bonding orbitals on the sox ligand. Ourinvestigations of the substituent effect of the sox ligand imply that the design of a highly selective catalyst ischallenging.
References[1] Nishimoto, Y.; Fedorov, D. G.; Irle, S. J. Chem. Theory Comput. 2014, 10, 4801–4812.
[2] Nishimoto, Y.; Fedorov, D. G. J. Chem. Phys. 2018, 148, 064115.
[3] Yamaguchi, K.; Kondo, H.; Yamaguchi, J.; Itami, K. Chem. Sci. 2013, 4, 3753–3757.
[4] Nishimoto, Y.; Kondo, H.; Yamaguchi, K.; Yokogawa, D.; Yamaguchi, J.; Itami, K.; Irle, S. J. Org. Chem.
2017, 82, 4900–4906.

2. Original papers(1) Nishimoto, Y.; Kondo, H.; Yamaguchi, K.; Yokogawa, D.; Yamaguchi, J.; Itami, K.; Irle, S.
“Theoretical Elucidation of Potential Enantioselectivity in a Pd-Catalyzed Aromatic C–H
Coupling Reaction”－ 51 －

Ⅳ 研究業績 (2017)

J. Org. Chem. 82(9), 4900–4906 (2017).
(2) Kitoh-Nishioka, H.; Welke, K.; Nishimoto, Y.; Fedorov, D. G.; Irle, S.
“Multi-Scale Simulations on Charge Transport in Covalent Organic Frameworks: Including
Dynamics of Transfer Integrals from FMO-DFTB/LCMO”
J. Phys. Chem. C 121(33), 17712–17726 (2017).
(3) Nishimoto, Y.; Fedorov, D. G.
“Adaptive frozen orbital treatment for the fragment molecular orbital method combinedwith density-functional tight-binding”
J. Chem. Phys. 148(6), 064115 (2018).
3. Presentation at academic conferences(1) 西本 佳央「巨大拡張系への応用に向けた少数軌道占有数を用いた解析的三次微分」
第 20 回理論化学討論会（1L07）、京都府、2017 年 5 月 16 日
(2) Yoshio Nishimoto“Analytic Hyperpolarizability and Polarizability Derivative with Fractional Occupation
Numbers for Large Extended Systems”
11th Triennial Congress of the World Association of Theoretical and Computational
Chemists (PO1-26), Munich, August 28th, 2017(3) 西本 佳央「少数軌道占有数を用いた二次の coupled-perturbed 方程式」
第 11 回分子科学討論会（1P083）、宮城県、2017 年 9 月 15 日
4. Others(1) Yoshio Nishimoto“Analytic Derivatives with Fractional Occupation Number”
15th Fukui Center Seminar, Kyoto, May 25, 2017(2) 西本 佳央「フロンティア軌道理論について」
京都大学サマーデザインスクール2017、京都府、2017年9月13日(3) 西本 佳央「福井謙一生誕百年記念事業のご紹介とフロンティア軌道に関連した展示物の準備」
第15回福井謙一記念研究センターシンポジウム、京都府、2018年2月2日－ 52 －

Ⅳ 研究業績 (2017)

２．FIFC リサーチフェロー

Shigeru Nagase
Shigeru Nagase
FIFC Research Fellow
FIFC Research Fellow
1. Summary of the Research of the Year(a) Van Der Waals Heterogeneous Layer-Layer Carbon Nonostructures Including π •••H-C-C-H•••π •••H-C-C-H Stacking Based on Graphene and Graphene Sheets
Noncovalent interactions such as π•••π stacking and CH•••π interaction are essential forsupramolecular carbon nanostructures. Graphite is the typical homogenous carbon matter based on theπ•••π stacking of graphene sheets. Even in the systems that do not contain aromatic groups, the stability of
diamondoid dimer and layer-layer graphane dimer originates from the C-H•••H-C noncovalent interactions.
Therefore, the structures and properties of novel heterogeneous layer-layer carbon-nanostructurescontaining the π•••H-C-C-H•••π stacking based on [n]-graphan, [n]-graphene and their derivatives aretheoretically investigated for n = 16–54 using the dispersion-corrected density functional theory at theB3LYP-D3 level. The Energy decomposition analyses show that the dispersion interaction is the mostimportant for the stabilization of both double- and multi-layer-layer [n]-graphane@graphene. Binding
energies between graphane and graphene sheets show distinct additive CH•••π interactions. For
comparison and simplicity, the H-H bond energy equivalent number of carbon atoms (NHEQ) is employed
to describe the strength of these noncovalent interactions. The NHEQ of graphene dimers, graphane dimers,
and double-layered graphane@graphene are 103, 143, and 110, respectively, which indicates that thestrength of the CH•••π interaction is close to that of the π•••π interaction and is much stronger than that of
the C-H•••H-C interaction in large size systems. Additionally, frontier molecular orbitals, electron density
differences, and visualized noncovalent interaction regions are discussed to understand deeply the natureof the CH•••π stacking interaction in construction of heterogeneous layer-layer graphane@graphene
structures. It is expected that the present study will be helpful in creating new functional supramolecularmaterials based on graphane and graphene carbon nanostructures.

(b) The Electron Transfer of Monotitanium-Encapsulated Fullerenes, Which Depends on
Fused Pentagon Distributions
The novel properties of monotitanium-encapsulated fullerenes are investigated using density functional
theory calculations. For encapsulation of a titanium atom inside a fullerene, it is the most interesting findingthat the properties of the fullerene are very sensitive to the distributions of fused pentagonal carbon rings in
the fullerene cage. When the titanium atom is bound on a doubly or triply fused pentagon part, the formed
endohedral fullerenes exhibit entirely different electron-transfer character, unlike the current knowledge on
mono-metallofullerenes. The titanium atom prefers to reside on the triply fused pentagon part because ofstronger interactions between titanium and cage carbons in the highly strained fused part. This finding isremarkable because the important stabilization of triply fused pentagons upon endohedral doping has been

－ 53 －

Ⅳ 研究業績 (2017)

underestimated up to now in the chemistry of endohedral metallofullerenes. It should be emphasized that
endohedral titatium doping is a feasible approach to the stabilization of highly strained triply
fused-pentagon part in the search for unconventional fullerenes for practical applications. The selective
electron-transfer character is extended to the study of the encapsulation of other neighboring metal atoms
such as calcium and scandium. Because of their different capability to accept d electrons, fullerene cageswith fused pentagon parts show selective metal encapsulation character.
(c) Epoxy and Oxidoannulene Oxidation Mechanisms of Chlorofullerenes Containing Fused

Pentagonal Carbon Rings
Recently, the oxidative functionalization of chlorofullerenes (#271C50Cl10 and #913C56Cl10) containing
doubly fused pentagons in the fullerene cage was carried out, which leads to two monoepoxides with theoxygen atom added at the ortho site of pentalene in the doubly fused pentagon. It is of great interest to
uncover how the reactivity of the chlorofullerenes violating the isolated pentagon rule upon is changed
upon oxidation. Therefore, two possible formation processes (ozone molecule and oxygen radical served asoxidation reagents) of the two oxides were systematically investigated by density functional theory
calculations. For the ozone oxidation, two possible pathways were explored, and the results indicate that the
biradical mechanism Pathos-RACDP is kinetically more favorable than Pathos-RABP, where R, A, and P
represent reactants, ozonide intermediates, and oxidation products, respectively, and B, C, and D represent
another three oxygen-containing intermediates. The products obtained by ozone oxidation ([6,6]-55-closed
epoxides P−C3−C29 for #271C50Cl10 and P−C42−C43 for #913C56Cl10 with oxygen atom added at the shortest andhighest HOMO-contribution bonds) are consistent with experimental observations. However, the oxygen
radical additions on these two chlorofullerenes favor the generation of two [5,6]-66-open oxidoannulene
adducts (P−C3−C2 and P−C42−C54). Subsequent analyses of their geometrical features and structural
stabilities suggest that these two open-ring oxidoannulene adducts are energetically unfavorable, which areconverted to more stable closed ring epoxides via a pirouette-type transition state. In these two diverse
oxidation procedures, the favorable C−C bonds for ozone attacking and C atoms for oxygen-adsorption are
rationalized in terms of their bond lengths and HOMO contributions as well as pyramidalization angles(d) Deciphering the Role of Long-Range Interactions in the Ambiguous Structures ofEndohedral Metallofullerenes
Structure elucidation is a vital step to study endohedral metallofullerene (EMF). In this context, thetheoretical investigation is very powerful in determining the structures of EMFs. Therefore, the ambiguous
structures of Sc2C70 of current interest were first investigated using four different density functional theory(DFT) methods at the wB97XD, M06-2X, B3LYP, and PBE0 levels, combined with statistical mechanics.
The calculated results show that Sc2C2@C2v(6073)-C68 is the most stable and abundant for Sc2C70 within thetemperature of EMF formation. The DFT methods without long-range corrections, such as B3LYP and
PBE0, tend to underestimate the stabilities of the Sc2C2@C68 structures, as in the Sc2C2@C72 cases.
However, the B3LYP and PBE0 methods give the relative energies of the La2C2@C94 isomers which arealmost identical to the energies obtained by the M06-2X method. It was found that long-range interactions－ 54 －

Ⅳ 研究業績 (2017)

play an important role in the interaction energies between encapsulated species clusters and carbon cages
for Sc2C2@C68, Sc2C2@C72, La2C2@C94, and La2@C96, while they play a minor role for Sc2@C70 and
Sc2@C74. This can be attributed to the structure differences. For Sc2C2@C68, Sc2C2@C72, La2C2@C94, and
La2@C96, the encapsulated species is not effectively coordinated by cage carbons because of the constraintof the shapes of encapsulated species (Sc2C2@C68, Sc2C2@C72, and La2C2@C94) or the absence of pentalenefragments in carbon cages (La2C2@C94 and La2@C96). This can be generalized to other EMFs. That is,long-range interactions play an important role for both clusterfullerenes and conventional fullerenes
satisfying the well-known isolated pentagon rule. The DFT methods without long-range corrections giveseemingly correct relative energies for some EMFs, because all the isomers are systemically overestimatedto the same degree. However, it should be emphasized that the use of the DFT methods without long-range
corrections are dangerous for the investigation of the reactivity and regioselectivity. The comparison of
Sc2@C2v(7854)-C70 and Sc2C2@C2v(6073)-C68 in the simulated UV−vis-NIR spectra also confirms that theexperimentally isolated Sc2C70 isomer is Sc2C2@C2v(6073)-C68 (not Sc2@C2v(7854)-C70).

(e) Effects of Substituents and Initial Degree of Functionalization of Alkylated
Single-Walled Carbon Nanotubes on Their Thermal Stability and Photoluminescence
Properties
Alkylated single-walled carbon nanotubes (SWNTs) have been thermally treated to determine theinfluence of substituents and the degree of functionalization on their thermal stability andphotoluminescence (PL) properties. Alkylated SWNTs were prepared by treating SWNTs with sodium
naphthalenide and alkyl bromide. The defunctionalization of the alkylated SWNTs was monitored byabsorption and Raman spectra. Selective recovery of the characteristic absorption and radial breathingmode peaks was observed during the thermal treatment, which indicates that the thermal stability of thealkylated SWNTs decreases with increases in SWNT diameter and degree of functionalization. n-Butylated
and phenethylated SWNTs showed higher thermal stability than sec-butylated and benzylated SWNTs for asimilar degree of functionalization, respectively. The diameter selectivity and effect of substituents on thethermal elimination reaction were well confirmed by density functional theory calculations at reasonablelevels. In addition, it was shown that the initial degree of functionalization of the alkylated SWNTs, withthe alkyl group and degree of functionalization being kept constant after thermal treatment, strongly affects
their PL properties such as Stokes shift and PL peak intensity.

(f) Formation of Stone-Wales Edge: Multistep Reconstruction and Growth Mechanisms of
Zigzag Nanographene
The existence of Stone–Wales (5-7) defects at the graphene edge has been clarified experimentally. In
contrast, the theoretical study on the formation mechanism is still imperfect. In particular, theregioselectivity of multistep reactions at the edge (self-reconstruction and growth with foreign carbon
feedstock) is essential to understand the kinetic behavior of reactive boundaries, though the investigations
are still lacking. Herein, by using finite sized models, multistep reconstructions and carbon dimer additionsof a bared zigzag edge are introduced using density functional theory calculations. The zigzag to 5-7－ 55 －

Ⅳ 研究業績 (2017)transformation is proved as a site-selective process to generate alternating 5-7 pairs sequentially and thefirst step with the largest barrier is suggested as the rate-determining step. Conversely, successive C2
insertions on the active edge are calculated to elucidate the formation of the 5-7 edge during graphene
growth. A metastable intermediate with a triple sequentially fused pentagon fragment is proved as the key
structure for the 5-7 edge formation. These findings are expected to be valuable to uncover the reactivity ofunsaturated graphene edge and helpful to achieve controlled synthesis of graphene with desired edge
structures for various device applications.

(g) Adamantylidene Addition to M3N@Ih-C80 (M = Sc, Lu) and Sc3N@D5h-C80:
Experimental and Theoretical Characterization of the [5,6]-Open and [6,6]-Open
Adducts
Additions of adamantylidene (Ad) to M3N@Ih-C80 (M=Sc, Lu) and Sc3N@D5h-C80 have beenaccomplished by photochemical reactions with 2-adamantyl-2,3’-[3H]-diazirine. For M3N@Ih-C80, theaddition led to rupture of the [6,6]- or [5,6]-bonds of the Ih-C80 cage, forming the [6,6]-open fulleroid as the
major isomer and the [5,6]-open fulleroid as the minor isomer. For Sc3N@D5h-C80, the addition also
proceeded regioselectively to yield three major isomeric Ad mono-adducts, despite the fact that there arenine types of C-C bonds in the D5h-C80 cage. The molecular structures of the seven Ad mono-adducts,
including the positions of the encaged trimetallic nitride clusters, have been unambiguously determinedthrough single-crystal XRD analyses. Furthermore, results have shown that stepwise addition of Ad to
Lu3N@Ih-C80 affords several Ad bis-adducts, two of which have been isolated and characterized. The
X-ray structure of one bis-adduct clearly revealed that the second Ad addition took place at a [6,6]-bondclose to an endohedral metal atom. The regioselectivity has been rationalized by performing density
functional theory calculations.

(h) Other Research Subjects(1) "Photoreactions of Endohedral Metallofullerene with Siliranes: Electronic Properties ofCarbosilylated Lu3N@Ih-C80", (2) "Fullerene C70 as a Nanoflask that Reveals the Chemical Reactivity ofAtomic Nitrogen", (3) "Temperature Dependence of Anisotropic Transient Conductivity of a
La@C2v-C82(Ad) Crystal", (4) "Preparation, Structural Determination, and Characterization of Electronic
Properties of [5,6]- and [6,6]-Carbosilylated Sc3N@Ih-C80", (5) "Synthesis, Electronic Structure, andReactivities of Two-Sulfur Stabilized Carbones Exhibiting Four-Electron Donor Ability", (6) "Eu@C72:
Computed Comparable Populations of Two Non-IPR Isomers", (7) "Functionalization of Endohedral
Metallofullerenes with Reactive Silicon and Germanium Compounds", (8) "Synthesis and Photoinduced
Electron-Transfer Reactions in a La2@Ih-C80-Phenoxazine Conjugate", (9) "Concave Binding of Cationic Li
to Quadrannulene", (10) "A Mechanistic Study on Cationic Li Prompted Diels-Alder Cycloaddition of
Cycloparaphenylene", (11) "Stability Issues in Computational Screening of Carbon Nanostructures:
Illustrations on La Endohedrals", (12) "Revisit of the Saito-Dresselhause-Dresselhaus C2 Ingestion Model:
On the Mechanism of Atomic-Carbon-Participated Fullerene Growth", (13) "Computational Comparison of－ 56 －

Ⅳ 研究業績 (2017)

the Water-Dimer Encapsulation into D2(22)-C84 and D2d(23)-C84", (14) "A Computational Characterizationof CO@C60"

2. Original Papers(1) Y. Maeda, Y. Takehana, J. –S. Dang, M. Suzuki, M. Yamada, and S. Nagase,"Effect of Substituents and Initial Degree of Functionalization of Alkylated Single-Walled Carbon
Nanotubes on Their Thermal Stability and Photoluminescence Properties"
Chem. Eur. J., 23, 1789-1794 (2017).
(2) K. Yuan, R. –S. Zhao, J. –J. Zheng, H. Zheng, S. Nagase, S. –D. Zhao, Y. –Z. Liu, and X. Zhao,
"Van

der

Waals

Heterogeneous

Layer-Layer

CarbonNanostructures

Involvingπ•••H-C-C-H•••π•••H-C-C-H Stacking Based on Graphene and Graphane Sheets"
J. Comput. Chem., 38, 730-739 (2017).
(3) M. Yamada, T. Abe, C. Saito, T. Yamazaki, S. Sato, N. Mizorogi, Z. Slanina, F. Uhlík, M. Suzuki, Y.
Maeda, Y. Lian, X. Lu, M. M. Olmstead, A. L. Balch, S. Nagase, and T. Akasaka,"Adamantylidene Addition to M3N@Ih-C80 (M = Sc, Lu) and Sc3N@D5h-C80: Synthesis andCrystallographic Characterization of the [5,6]-Open and [6,6]-Open Adducts"
Chem. Eur. J., 23, 6552-6561 (2017).
(4) M. Kako, K. Minami, T. Kuroiwa, S. Fukazawa, Y. Arikawa, M. Yamada, Y. Maeda, Q. –Z. Li, S.
Nagase, and T. Akasaka,"Photoreactions of Endohedral Metallofullerene with Siliranes: Electronic Properties ofCarbosilylated Lu3N@Ih-C80"
Molecules, 22, 850 (10 pages) (2017).
(5) Y. Morinaka, R. Zhang, S. Sato, H. Nikawa, T. Kato, K. Furukawa, M. Yamada, Y. Maeda, M.
Murata, A. Wakamiya, S. Nagase, T. Akasaka and Y. Murata,"Fullerene C70 as a Nanoflask that Reveals the Chemical Reactivity of Atomic Nitrogen"Angew. Chem. Int. Ed., 56, 6488-6491 (2017).
(6) M. Yamada, S. Sato, W. Choi, S. Seki, T. Abe, M. Suzuki, Y. Maeda, S. Nagase, and T. Akasaka,"Temperature Dependence of Anisotropic Transient Conductivity of a La@C2v-C82(Ad) Crystal"
Chem. Lett., 46, 973-975 (2017).
(7) M. Kako, T. Sugiura, K. Miyabe, M. Yasui, M. Yamada, Y. Maeda, J. –D. Guo, S, Nagase, and T.
Akasaka,"Preparation, Structural Determination, and Characterization of Electronic Properties of [5,6]- and[6,6]-Carbosilylated Sc3N@Ih-C80"
Chem. Asian. J., 12, 1391-1399 (2017).
(8) J. –S. Dang, W. –W. Wang, J. –J. Zheng, X. Zhao, and S. Nagase,"Fused-Pentagon-Configuration-Dependent Electron Transfer of Monotitanium Encapsulated
Fullerenes"
Inorg. Chem., 56, 6890-6896 (2017).
(9) T. Morosaki, R. Iijima, T. Suzuki, W. –W. Wang, S. Nagase, and T. Fujii,－ 57 －

Ⅳ 研究業績 (2017)"Synthesis, Electronic Structure, and Reactivities of Two-Sulfur Stabilized Carbones Exhibiting
Four-Electron Donor Ability"
Chem. Eur. J., 23, 8694-8702 (2017).
(10) Z. Slanina, F. Uhlík, S. Nagase, T. Akasaka, L. Adamowicz, and X. Lu,"Eu@C72: Computed Comparable Populations of Two Non-IPR Isomers"
Molecules, 22, 1053 (8 pages) (2017).
(11) Q. –Z. Li, J. –J. Zheng, X. Zhao, and S. Nagase,"Epoxy and Oxidoannulene Oxidation Mechanisms of Fused-Pentagon Chlorofullerenes: Oxides
Linked by a Pirouette-Type Transition State"
J. Org. Chem., 82, 6541-6549 (2017).
(12) M. Kako, S. Nagase, and T. Akasaka,"Functionalization of Endohedral Metallofullerenes with Reactive Silicon and Germanium
Compounds"
Molecules, 22, 1179 (17 pages) (2017).
(13) T. Akasaka, A. Nakata, M. Rudolf, W. –W. Wang, M. Yamada, M. Suzuki, Y. Maeda, R. Aoyama, T.
Tsuchiya, S. Nagase, and D. M. Guldi,"Synthesis and Photoinduced Electron-Transfer Reactions in a La2@Ih-C80-Phenoxazine Conjugate"
ChemPlusChem, 82, 1067-1072 (2017).
(14) J. –S. Dang, W. –W. Wang, X. Zhao, and S. Nagase,"Concave Binding of Cationic Li to Quadrannulene"
Phys. Chem. Chem. Phys., 19, 20773-20777 (2017).
(15) J. –S. Dang, W. –W. Wang, J. –J. Zheng, S. Nagase, and X. Zhao,"Formation of Stone-Wales Edge: Multistep Reconstruction and Growth Mechanisms of Zigzag
Nanographene"
J. Comput. Chem., 38, 2241-2247 (2017).
(16) J. –S. Dang, W. –W. Wang, X. Zhao, and S. Nagase,"A Mechanistic Study on Cationic Li Prompted Diels-Alder Cycloaddition of Cycloparaphenylene"
Org. Chem. Front., 4, 1757-1761 (2017).
(17) R. Zhao, K.Yuan, S. Zhao, M. Ehara, S. Nagase, J. M. Poblet, and X. Zhao,"Deciphering the Role of Long-Range Interaction in Endohedral Metallofullenes: A Revisit to
Sc2C70"J. Phys. Chem. C, 121, 20481-20488 (2017).
(18) Z. Slanina, F. Uhlík, L. Adamowicz, T. Akasaka, S. Nagase, and X. Lu,"Stability Issues in Computational Screening of Carbon Nanostructures: Illustrations on La
Endohedrals"
Mol. Simul., 43, 1472-1479 (2017).
(19) W. –W. Wang, J. –S. Dang, X. Zhao, and S. Nagase,"Revisit of the Saito-Dresselhause-Dresselhaus C2 Ingestion Model: On the Mechanism ofAtomic-Carbon-Participated Fullerene Growth"－ 58 －

Ⅳ 研究業績 (2017)

Nanoscale, 9, 16742-16748 (2017).
(20) Z. Slanina, F. Uhlík, S. Nagase, T. Akasaka, L. Adamowicz, and X. Lu,"Computational Comparison of the Water-Dimer Encapsulation into D2(22)-C84 and D2d(23)-C84"
ECS, J. Solid State Sci. and Tech., 6, M3113-M3115 (2017).
(21) Z. Slanina, F. Uhlík, S. Nagase, T. Akasaka, L. Adamowicz, and X. Lu,"A Computational Characterization of CO@C60"
Fullerenes, Nanotubes, Carbon Nanostruct., 25, 624-629 (2017).

3. Review
M. Kako, S. Nagase, and T. Akasaka,"Functionalization of Endohedral Metallofullerenes with Reactive Silicon and Germanium Compounds"
Molecules (Review), 22, 1179 (17 pages) (2017).

－ 59 －

Ⅳ 研究業績 (2017)３．シニアリサーチフェロー

Shigeyoshi Sakaki
Shigeyoshi Sakaki

Senior Research Fellow, Kenichi Fukui Memorial Research Groups II
Senior Research Fellow, Kenichi Fukui Memorial Research Group II

1. Summary of the research of 2017
The complex systems consisting of transition metal element(s), heavy main-group element(s), organicgroup(s) play important roles as metal enzymes, industrial catalysts, catalysts for fine organic synthesis,
photo-sensitizer, molecular switch, luminescence material and so on. Also, they are important research target
in the physical chemistry and molecular science, because they exhibit a variety of new geometry, newchemical bond, rich molecular property, rich reactivity, and useful catalysis. 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 multi-nuclear transition metal complexes which need the application ofmulti-reference wave-function theory in theoretical calculation. Another example is significantly large
coupling of electronic structure with surrounding atmosphere such as solvation effects, molecular crystal
effects and so on.
Our group is theoretically investigating the complex systems bearing complicated electronic structurewith electronic structure theory. In 2017, we performed various theoretical studies, as follows: (i) Reactivityof Mo−Mo Quintuple Bond for H−H, C−H, and O−H σ‑Bond Cleavages, (ii) Theoretical Study of [2 +2]-type Reaction of Metal−Metal σ‑Bond with Fullerene Forming an η1‑C60 Metal Complex: Mechanistic
Details of Formation Reaction and Prediction of a New η1‑C60 Metal Complex, (iii) Characteristic Featuresof CO2 and CO Adsorptions to Paddle-Wheel-type Porous Coordination Polymer, (iv) Core−Shell versus
Other Structures in Binary Cu38−nMn Nanoclusters (M = Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au; n = 1, 2, and
6): Theoretical Insight into Determining Factors, (v) How to Control Inversion vs Retention Transmetalation
between PdII−Phenyl and CuI−Alkyl Complexes, (vi) Theoretical Study of Nickel-Catalyzed Selective
Alkenylation of Pyridine: Reaction Mechanism and Crucial Roles of Lewis Acid and Ligands in Determining
the Selectivity, (vii) A coordination strategy to realize a sextuply-bonded complex, (viii) Theoretical study of
one-electron-oxidized salen complexes of group 7 (Mn(III), Tc(III), and Re( III)) and group 10 metals (Ni(II),
Pd(II), and Pt(II)) with the 3D-RISM-GMC-QDPT method: localized vs. delocalized ground and excitedstates in solution, (ix) Embedded Cluster Model for Al2O3 and AlPO4 Surfaces Using Point Charges andPeriodic Electrostatic Potential, and so on. We wish to report some of them, below.
(i) Reactivity of Mo−Mo Quintuple Bond for H−H, C−H, and O−H σ‑Bond Cleavages
Metal-metal multiple bond has been reported very old day by Professor Cotton. Since then, its
interesting bonding nature attracted a lot of interests in molecular science and coordination chemistry.
Roos/Gagliardi group and Out group have investigatedthe metal-metal multiple bond using multi-reference
method and elucidated the interesting bonding nature ofmetal-metal multiple bond. However, the reactivity andcatalysis of metal-metal multiple bond have not beenreported for long time. Recently, several groups reported
Scheme 1. Dinuclear Mo complex with Mo-Mo
pioneering works on organometallic reaction and quintuple bond.
catalysis. But, the details of such reactivity and catalysis－ 60 －

Ⅳ 研究業績 (2017)

have not been investigate well.
We investigated the recently reported high reactivity of the Mo−Mo quintuple bond of Mo2(N^N)2 (1){N^ N = μ-κ2-CH[N(2,6-iPr2C6H3)]2} in the H−H σ-bond cleavage. DFT calculations disclosed that the H−H
σ-bond cleavage by 1 occurs with nearly no barrier to afford the cis-dihydride species followed by cis−transisomerization to form the trans-dihydride product, which is consistent with the experimental result. The O−H
and C−H bond cleavages by 1 were computationally predicted to occur with moderate (ΔG°⧧ = 9.0 kcal/mol)and acceptable activation energies (ΔG°⧧ = 22.5 kcal/mol), respectively, suggesting that the Mo−Mo
quintuple bond can be applied to various σ-bond cleavages. In these σ-bond cleavage reactions, thecharge-transfer, CT(Mo→XH), from the Mo−Mo quintuple bond to the X−H (X = H, C, or O) bond and theCT(XH→Mo) from the X−H bond to the Mo−Mo bond play crucial roles. Though the HOMO (dδ-MO) of 1
is at lower energy and the LUMO + 2 (dδ*-MO) of 1 is at higher energy than those of RhCl(PMe3)2 (LUMO
and LUMO + 1 of 1 are not frontier MO), the H−H σ-bond cleavage by 1 more easily occurs than that by the
Rh complex. Hence, the frontier MO energies are not the reason for the high reactivity of 1. The highreactivity of 1 arises from the polarization of dδ-type MOs of the Mo−Mo quintuple bond in the transition
state. Such a polarized electronic structure enhances the bonding overlap between the dδ-MO of the Mo−Mo
bond and the σ*-antibonding MO of the X−H bond to facilitate the CT(Mo→XH) and reduce the exchange
repulsion between the Mo−Mo bond and the X−H bond. This polarized electronic structure of the transition
state is similar to that of a frustrated Lewis pair. The easy polarization of the dδ-type MOs is one of theadvantages of the metal−metal multiple bond, because such polarization is impossible in the mononuclear
metal complex.
(ii) Theoretical Study of [2 + 2]-type Reaction of Metal−Metal σ‑Bond with Fullerene Forming anη1‑C60 Metal Complex: Mechanistic Details of Formation Reaction and Prediction of a New η1‑C60
Metal Complex
Reaction of fulerene with transition metal
complex
has
been
rare.
However,
C60[CpRu(CO)2]2, only one transition-metal
fullerene complex with pure η1-coordinatedbonds, was recently synthesized through thereaction between dinuclear Ru complex[CpRu(CO)2]2 and C60. Though new properties
can be expected in the η1-coordinatedmetal-fullerene complex, its characteristicfeatures are unclear, and the [2 + 2]-typeformation reaction is very slow with a very small
yield. A density functional theory study discloses
that the η1-coordinated bond is formed by a large
overlap between the Ru dσ orbital and C pσ one
involved in the lowest unoccupied molecularorbital (LUMO) (π*) of C60 unlike the Figure 1. Gibbs energy profile of the reaction between
well-known η2- coordinated metal-fullerene C60 and [CpRu(CO)2]2
complex which has a π-type coordinate bond withmetal dπ orbital. The binding energy per one Ru−C bond is much smaller than those of η2-coordinatedPt(PMe3)2(C60) and IrH(CO)(PH3)2(C60) because the Ru d orbital exists at low energy. The formation reaction－ 61 －

Ⅳ 研究業績 (2017)

occurs via Ru−Ru bond cleavage on the C60 surface followed by a direction change of CpRu(CO)2 to afford
C60[CpRu(CO)2]2 in a stepwise manner via two asymmetrical transition states to avoid asymmetry-forbidden character. The calculated Gibbs activation energy (ΔG°‡) is very large and the Gibbs
reaction energy (ΔG°) is moderately negative, which are consistent with a very slow reaction rate and verysmall yield. The charge transfer from CpRu(CO)2 to fullerene CT(Ru → C60) is important in the reaction, but
it is small due to the presence of the Ru d orbital at low energy, which is the reason for the large ΔG°‡ andmoderately negative ΔG°. The use of Li+@C60 is theoretically predicted to accelerate the reaction andincrease the yield of Li+@C60[CpRu(CO)2]2, because the CT(Ru → C60) is enhanced by the low energy
LUMO of Li+@C60. It is also predicted that Li+@C60[Re(CO)4(PMe3)]2 is a next promising target for thesynthesis of the η1-coordinated metal-fullerene complex, but syntheses of C60[Co(CO)4]2, C60[Re(CO)5]2,
Li+@C60[Co(CO)4]2, and Li+@C60[Re(CO)5]2 are difficult.
(iii) Characteristic Features of CO2 and CO Adsorptions to Paddle-Wheel-type Porous Coordination
Polymer
Porous coordination polymers (PCPs) or metalorganic frameworks (MOFs) have attracted recent
attention as potential materials for gas storage, gas
separation, and catalysis. Because a variety of metal
ions and organic linkers are available for synthesis,
geometry and property of PCP can be well-tuned forachieving the purpose. Actually, many PCPs withexcellent adsorption ability for target gas molecule
have been designed and synthesized by tuning
geometries and properties of PCPs. However, we do
not have correct knowledge about the position andbinding energy of gas molecule in PCPs.
In this work, we theoretically investigatedadsorptions of CO, N2, NO, and CO2 in apaddle-wheel type porous coordination polymer(PCP) [Cu(aip)]n (aip = 5-azidoisophthalate) with Figure 2. Optimized geometry of CO, N2, NO, andONIOM[MP4(SDQ):ωB97XD] method using a CO2 interacting with paddle-wheel Cu(II) PCPs.
model system consisting of two [Cu2(O2CC6H4-R)4]
units (R = H and Me) and one [Cu2(O2CC6H4−R)4] unit, namely, dimer and monomer models. The
experimental CO adsorption position was reproduced well by the present calculation with the dimer model.
For adsorptions of CO, N2, NO, and CO2 in the dimer model, the position of gas molecule deviates from thenormal one that is found in the monomer model and becomes more distant from the surrounding phenylgroup(s) of the neighbor [Cu(aip)] unit. For all of these gas molecules, the calculated binding energy (BE) atthe deviating adsorption position is larger than that at the normal one against our expectation that the normal
position is the best for the gas adsorption. The deviation of gas adsorption position arises from the interaction
between the organic linker (O2CC6H4−R moiety) and gas molecule. For all cases, the exchange repulsion
with the organic linker decreases to a larger extent than the attractive electrostatic and dispersion interactions
decrease when going from the normal position to the deviating one. To enhance the binding energy of gas
molecule, the introduction of electron-donating substituent on phenyl moiety is computationally
recommended for this PCP.
－ 62 －

Ⅳ 研究業績 (2017)(iv) Core−Shell versus Other Structures in Binary Cu38−nMn Nanoclusters (M = Ru, Rh, Pd, Ag, Os,
Ir, Pt, and Au; n = 1, 2, and 6): Theoretical Insight into Determining Factors
Binary transition-metal (TM) nanoparticles consisting of two types of metal elements have attracted agreat deal of interest recently because they are goodcandidates for such functional materials as heterogeneous
catalysts, gas absorption materials, and magnetic storage
materials. One good example is Pd−Pt binary
nanodendrites, which exhibit a high activity for oxygen
reduction. Other good examples include Pd−M (M = Pt orAu) and Ag−Cu binary nanoparticles, which are useful as
dihydrogen gas absorption materials3,5,6 and catalysts
for alkaline fuel cells, respectively. To understand andeffectively use such binary TM nanoparticles, one needs Scheme 2. Stable binary metal clusters.
knowledge about their fundamental properties such as
geometry, electronic structure, and electron and spin distributions. Theoretical and computational knowledge
about such properties is indispensable for making new developments in the chemistry of binary TM
nanoparticles. DFT calculations of binary transition-metal nanoclusters Cu38−nMn (M = Ru, Rh, Pd, Ag, Os, Ir,
Pt, and Au; n = 1, 2, and 6) clearly show that a core−shell structure Cu32M6(core) with M in the core is stablefor M = Ru, Rh, Os, and Ir but unstable for M = Pd, Ag, Pt, and Au. These results are consistent with thesegregation energies evaluated for Cu37M. Electron population is more accumulated on the core M atoms in
Energygeometrychanges in the CO2
Cu38−nMn(core) (M = Ru, Rh, Os, and Ir) than onFigure
the core3.Cu
atoms andin Cu
38. Such electron accumulationhydrogenationby three-coordinatedcompounds
substantially occurs for M = Ru, Rh, Os, and Ir because
the d orbitalsof these transitionPmetals
are not fully
occupied. A linear relationship was first found between the segregation energy and the increase in thed-orbital population of the core atom, indicating that the electron accumulation at the Mn core is one of theimportant factors for the segregation energy and the stabilization of the core−shell structure; in other words,
a core−shell structure with M atom(s) in the core is stable when the d orbitals of M are not fully occupied.
For M = Pd, Pt, and Au, the fused-alloy structure is more stable than the core−shell and phase-separated
structures. For M = Ag, the fused-alloy structure is as stable as the phase-separated one but the core−shellstructure is less stable. In these metals, the d orbitals are either nearly or fully occupied, and as a result,electron accumulation at the Mn core does not occur as much. For Cu32M6(core), the deformation energy of
the Cu32 shell increases in the order Ru < Rh ≪ Pd < Ag and Os < Ir ≪ Pt < Au, because the size of theM6 core is substantially large for M = Pd, Ag, Pt, and Au. These results suggest that a large atom tends not totake the core position. The cohesive energies of Ru, Rh, Os, and Ir are larger than those of Pd, Ag, Pt, and Au,
indicating that the cohesive energy is also an important property for understanding and discussing thestructures of binary metal clusters/particles.
(v) How to Control Inversion vs Retention Transmetalation between PdII−Phenyl and CuI−Alkyl
Complexes
Transition-metal-catalyzed cross-coupling reaction is an important reaction for C−C bond formation.
Catalytic cycle of conventional cross-coupling reaction is well-known to consist of oxidative addition of aryl
halide (ArX) to palladium(0) complex, transmetalation between palladium(II) aryl complex andorganometallic reagent (R−M), and reductive elimination of product (Ar−R) from palladium(II) complex.
For better understanding of the cross-coupling reaction, a theoretical study of each elementary step is－ 63 －

Ⅳ 研究業績 (2017)

necessary. Nakao and co-workers and Buchwald and co-workers have independently reported the reductive
crosscoupling reaction between 1-arylalkenes and aryl bromides using Pd/Cu cooperative catalyst.
Transmetalation between Pd(Br)(PhA)(PCyp3)2 (Ph = phenyl, Cyp = cyclopentyl) andCu(CaHMePhB)(NHC) (NHC = 1,3-bis(2,6-diisopropylphenyl)-imidazolidin-2-ylidene) is an importantelementary step in recently reported catalytic cross-coupling reaction by Pd/Cu cooperative system. DFT
study discloses that the transmetalation occurs with inversion of the stereochemistry of the CaHMePhB group.
In its transition state, the CaHMePhB group has almost planar structure around the Ca atom. That planar
geometry is stabilized by conjugation between the π* orbital of the PhB and the 2p orbital of the Ca. Anotherimportant factor is activation entropy (ΔS°‡); retention transmetalation occurs through Br-bridging transition
state, which is less flexible than that of the inversion transmetalation because of the Br-bridging structure,
leading to a smaller activation entropy in theretention transition state than in the inversion
group,
transition
state.
For
CaHMeEt
transmetalation occurs in a retention manner. In
the planar CaHMeEt group of the inversion
transition state, the Ca 2p orbital cannot find a
conjugation partner because of the absence of
π-electron
systemin
the
CaHMeEt. Scheme 2. Inversion vs. retention transmetallation
Transmetalation of CaHMe(CH=CH2) occurs in a between PdII(Ph) and CuI(alkyl) complexes.
retention manner because the vinyl π* is lesseffective for the conjugation with the Ca 2p because of its higher orbital energy than the Ph π*. The
introduction of electronwithdrawing substituent on the PhB is favorable for inversion transmetalation. These
results suggest that the stereochemistry of the Ca atom in transmetalation can be controlled by electronic
effect of the CaHMeR (R = phenyl, vinyl, or alkyl) and sizes of the substituent and ligand.
2. Original Papers(1) Ryoichi Fukuda, Nozomi Takagi, Shigeyoshi Sakaki, and Masahiro Ehara,“On the Structures of Bimetallic Copper-Ruthenium Nanoparticles: Incoherent Interface andSurface Active Sites for Catalytic Nitric Oxide Dissociation”
J. Phys. Chem. C, 121, 300-307 (2017)..
(2) Vijay Singh, Yoshiaki Nakao, Shigeyoshi Sakaki, and Milind M. Deshmukh," Theoretical Study of Nickel-Catalyzed Selective Alkenylation of Pyridine: Reaction Mecha- nism
and Crucial Roles of Lewis Acid and Ligands in Determining the Selectivity”
J. Org. Chem. 82, 289−301 (2017).
(3) Tao Yang, Ryoichi Fukuda, Saburo Hosokawa, Tsunehiro Tanaka, Shigeyoshi Sakaki, and Masahiro
Ehara“A Theoretical Investigation on CO Oxidation by Single-Atom Catalysts M1/γ-Al2O3 (M = Pd, Fe,
Co, and Ni)”
ChemCatChem, 9, 1222 – 1229 (2017).
(4) Takako Muraoka, Haruhiko Kimura, Gama Trigagema, Masayuki Nakagaki, Shigeyoshi Sakaki,
and Keiji Ueno,“Reactions of Silanone(silyl)tungsten and -molybdenum Complexes with MesCNO, (Me2SiO)3,
MeOH, and H2O: Experimental and Theoretical Studies”
Organometallics, 36, 1009−1018 (2017)..
(5) Yue Chen and Shigeyoshi Sakaki,“Mo−Mo Quintuple Bond is Highly Reactive in H−H, C−H, and O−H �‑Bond Cleavages
Be-cause of the Polarized Electronic Structure in Transition State”
Inorg. Chem., 56, 4011−4020 (2017).
(6) Hong Zheng, Xiang Zhao, Shigeyoshi Sakaki, “[2+2]-type Reaction of Metal-Metal sigma-Bond－ 64 －

Ⅳ 研究業績 (2017)with Fullerene Forming an 1-C60 Metal Complex: Mechanistic Details of Formation Reaction andPrediction of a New 1-C60 Metal Complex”
Inorg. Chem., 56, 6746-6754 (2017)..
(7) Hajime Kameo, Yuki Baba, Shigeyoshi Sakaki, Didier Bourissou, Hiroshi Nakazawa, Hiroyuki
Matsuzaka“Iridium Hydride Mediated Stannane-Fluorine and -Chlorine sigma-Bond Activation: Re-versible
Switching between X-Type Stannyl and Z-Type Stannane Ligands”
Organometallics, 36, 2096-2106 (2017).
(8) Yue Chen, Jyun-ya Hasegawa, Kazuya Yamaguchi, Shigeyoshi Sakaki,“A coordination strategy to realize a sextuply-bonded complex”
Phys. Chem. Chem. Phys., 19, 14947-14954 (2017).
(9) Kenji Hirano, Hiroshi Nakano, Yoshihide Nakao, Hirofumi Sato, Shigeyoshi Sakai,“Photo Absorption of p-Coumaric Acid in Aqueous Solution: RISM-SCF-SEDD Theory Approach”
J. Comp. Chem., 38, 1567-1573 (2017).
(10) Shinji Aono, Masayuki Nakagaki, Shigeyoshi Sakaki,“Theoretical study of one-electron-oxidized salen complexes of group 7 (Mn(III), Tc(III), andRe( III)) and group 10 metals (Ni(II), Pd(II), and Pt(II)) with the 3D-RISM-GMC-QDPT method:
localized vs. delocalized ground and excited states in solution”
Phys. Chem. Chem. Phys., 19, 16831-16849 (2017).
(11) M. Ramu Yadav, Masahiro Nagaoka, Myuto Kashihara, Rong-Lin Zhong, Takanori Miyazaki,
Shigeyoshi Sakaki, Yoshiaki Nakao,“The Suzuki–Miyaura Coupling of Nitroarenes”
J. Am. Chem. Soc., 139, 9423-9426 (2017).
(12) Shuwei Tang, Odile Eisenstein, Yoshiaki Nakao, and Shigeyoshi Sakaki,“Aromatic C-H σ-Bond Activation by Ni0, Pd0, and Pt0 Alkene Complexes: Concerted Oxida-tive
Addition to Metal vs Ligand-to-Ligand H Transfer Mechanism”
Organonetallics, 36, 2761-2771 (2017).
(13) Nozomi Takagi, Kazuya Ishimura, Masafuyu Matsui, Ryoichi Fukuda, Masahiro Ehara, andShigeyoshi Sakaki,“Core−Shell versus Other Structures in Binary Cu38−nMn Nanoclusters (M = Ru, Rh, Pd, Ag, Os,
Ir, Pt, and Au; n = 1, 2, and 6): Theoretical Insight into Determining Factors”
J. Phys. Chem. C, 121, 10514−10528 (2017).
(14) Jingui Duan, Masakazu Higuchi, Jiajia Zheng, Shin-ichiro Noro, I-Ya Chang, Hyeon-Deuk Kim,
Simon Mathew, Shinpei Kusaka, Easan Sivaniah, Ryotaro Matsuda, Shigeyoshi Sakaki, Susumu
Kitagawa,“Density Gradation of Open Metal Sites in the Mesospace of Porous Coordination Polymers”
J. Am. Chem. Soc., 139, 11576-11583 (2017).
(15) Jiajia Zheng, Shinpei Kusaka, Ryotaro Matsuda, Susumu Kitagawa, and Shigeyoshi Sakaki,“Characteristic Features of CO2 and CO Adsorptions to Paddle-Wheel-Type Porous Coordination
Polymer”
J. Phys. Chem. C, 121, 19129-19139 (2017).
(16) Masafuyu Matsui and Shigeyoshi Sakaki,“Embedded Cluster Model for Al2O3 and AlPO4 Surfaces Using Point Charges and Periodic
Electrostatic Potential”
J. Phys. Chem. C, 121, 20242-20253 (2017).
(17) Longfei Li, Ming Lei, and Shigeyoshi Sakaki,“DFT Mechanistic Study on Alkene Hydrogenation Catalysis of Iron Metallaboratorene:
Characteristic Features of Iron Species”
Organometallics, 36, 3530-3538 (2017).
(18) Hong Zheng, Kazuhiko Semba, Yoshiaki Nakao, and Shigeyoshi Sakaki,“How to Control Inversion vs. Retention Transmetallation between PdII-Phenyl and CuI-Alkyl
Complexes: Theoretical Insight”
J. Am. Chem. Soc., 139, 14065-14076 (2017).
3. Presentation at academic conferences－ 65 －

Ⅳ 研究業績 (2017)(1) S. Sakaki,
Catalysis by Combined System of Transition Metal Complex with Lewis Acid: Theoretical Insight
into Crucial Role of Lewis Acid,
SouthEast Asia Catalysis Conference, May 22-23, 2017, Nanyang Technological University,
Singapore (Kyenote)(2) S. Sakaki
Theoretical Approach to CO2 Adsorption to Flexible PCPJST ACCEL R&D Project International Symposium, November 27-28, 2017; Kyoto (Invited).
(3) S. Sakai,
Theoretical Chemistry of Complex System of d Element: From Molecule to Functional Materials
2nd International Caparica Christmas Congress on Translational Chemistry, Dec. 5-7, 2017, Lisbon,
Portogalu (Keynote)(4) S. Sakaki
Theoretical Approach to Solid Systems such as MOFs and Metal Oxide Surface
The 8-th Asia-Pacific Confernece on Theoretical and Computational Chemistry, Indian Institute ofTechnology Bombay, Mumbai, India, Dec. 15-17, 2017. (Invited)）－ 66 －

Ⅳ 研究業績 (2017)

田中
田中

一義
一義

シニアリサーチフェロー

シニアリサーチフェロー
1. 今年度の研究の要約
有機金属錯体における水素貯蔵の可能性探索は燃料電池の水素源確保の探索に向けて重要である。今年度は PH3 を配位子とするメタロセン錯体 (M = TiIII, CrIII, ScIII および VIII) における水素分子との反応と吸着について、遠距離および分散力補正を含めた DFT 計算(wB97XD/aug-cc-pVDZ)解析に基づく理論的検討を行った。特に Kubas 錯体の形成と余剰の水素分子の吸着に着目して反応および吸着エンタルピーの算出を行い、それぞれの金属錯体 に お け る 水 素 吸 蔵 能 の 評 価 を 行 っ た 。 [Cp2TiIII(PH3)]+, [Cp2ScIII(PH3)]+ お よ び[Cp2VIII(PH3)]+の場合には良好な水素分子吸着能が発現することが明らかになった。さらに
VIII 錯体の場合には３重項状態が優勢となるという知見も得られた。一方、[Cp2CrIII(PH3)]+
では PH3 が解離する傾向にあり、錯体そのものが形成されにくい。なおこの研究はトヨタ
自動車と豊田中研との共同研究であり、平成 30 年 3 月の日化春季年会で発表済みの部分である。
【始めに】 燃料電池を搭載した自動車(FCV)における水素ガス供給法としては、通常の航続距離等を考慮した場合 700 気圧程度に加圧充填した水素タンクを積載する必要がある。これは必ずしも安全とは言えず、また高圧に耐える容器の重量および体積軽減など改善すべき問題点をいくつか含んでおり、その改善に向けた可能性を探ることが重要な課題となっている。その方策の一つとして、有機金属錯体における水素分子貯蔵の可能性を明らかにすることは意味があると考えられる。
有機金属錯体への水素分子付加反応について、従来は図１に示すような付加体（Kubas 錯体）の生成が知られている 1)。この錯体では付加した水素分子が解離して金属 M との間に結合生成が起こるとされている。Kubas の原論文では明瞭にはふれられていないが、以下に述べるように、このKubas 錯体には横(horizontal)Kubas 錯体と縦(vertical)Kubas 錯体がある。

R

R

(a)

M

H

(b)

H
Fig. 1

M

H
H

Two kinds of Kubas complexes: (a) horizontal Kubas complex, and (b) vertical Kubas

complex, where M stands for a transition metal of valence III state and R for an appropriate
ligand.

－ 67 －

Ⅳ 研究業績 (2017)

本研究では R をホスフィン(PH3)とし、M を TiIII, ScIII, CrIII および VIII とするメタロセン錯体について水素分子付加に関する計算を行い、付加しうる水素分子数やその電子状態に関する解析を行った。
【計算方法】 計算は密度汎関数理論(DFT)に基づく wB97XD 法によって行い、基底としては
aug-cc-pVDZ を用いて開殻系に対しては非制限法を適用した。計算には Gaussian09 ソフトを使用した 2)。具体的には[Cp2TiIII(PH3)]+, [Cp2ScIII(PH3)]+, [Cp2CrIII(PH3)]+ および[Cp2VIII(PH3)]+について構造最適化を行い、これらの金属錯体に対する水素分子付加の可能性、最大付加数、付加錯体の構造最適化、さらに水素分子の電子状態等に関する知見を得るための解析を行った。
【[Cp2TiIII(PH3)]+の解析結果
水素分子が付加する前のこの錯体は図 2(a)の形状であり、この錯体には最高で水素３分子が付加することが明らかとなった（図 2(b), (c)）。

(a)Fig. 2(c)(b)

Optimized structures of (a) [Cp2TiIII(PH3)]+ complex and (b) that with three additional H2molecules. An H2 molecule with red-broken oval makes a horizontal Kubas complex and thosewith blue-broken ovals are adsorbed ones.

In (c) is indicated the same with (b) from a different

angle.
TiIII は 3d14s0 の電子状態を持つとされるが、この錯体の多重度は１重項であった。横 Kubas 錯体形成によるエンタルピー安定化は 23.61 kJ/mol（298.15 K, 1 atm; 以下同じ）、第 2 および第 3 の水素分子付加によるエンタルピー安定化はそれぞれ 2.58, 1.65 kJ/mol であり、Kubas 錯体形成による値の１割程度である。H1-H2 距離は 0.777 Å（WBI = 0.804）で、単一水素分子の結合距離 0.758 Å (WBI =1.000)に比較してかなり緩んでいて、図 1(a)のような横 Kubas 錯体を作っていることが分かる。また Ti からの H1 と H2 への距離は 2.039 Å と 2.051 Å である。
一方、H3-H4 および H5-H6 の結合距離は 0.758 Å (WBI = 0.987)および 0.757 Å (WBI = 0.997)で単一
水素分子からの変化がほとんどなく、また Ti からの距離も遠い（3.496～4.581 Å 程度）など、この錯体に吸着されていると見てよいことが分かる。したがって、これら第 2 および第 3 の水素分子は
燃料電池の水素源として使用できる可能性があることになる。
【[Cp2ScIII(PH3)]+の解析結果】－ 68 －

Ⅳ 研究業績 (2017)

水素分子が付加する前のこの錯体は図 3(a)の形状であり、この錯体にも最高で水素３分子が付加することが明らかとなった（図 3(b), (c)）。

Fig. 3

(c)

(b)

(a)

Optimized structures of (a) [Cp2ScIII(PH3)]+ complex and (b) that with three

additional H2 molecules.

An H2 molecule with red-broken oval makes a horizontal Kubas

complex and those with blue-broken ovals are adsorbed ones.

In (c) is indicated the samewith (b) from a different angle.
ScIII は 3d04s0 の電子状態を持つとされ、この錯体の多重度は１重項であった。Sc 錯体の場合は縦Kubas 錯体が形成されており、これによるエンタルピー安定化は 16.97 kJ/mol、第 2 および第 3 の水素分子付加によるエンタルピー安定化はそれぞれ 1.87, 1.38 kJ/mol である。H1-H2 距離は 0.769 Å（WBI = 0.875）で、単一水素分子に比較してやはり緩んでいて、図 1(b)のような縦 Kubas 錯体を作っている。また Sc からの H1 と H2 への距離は 2.280 Å と 2.281Å である。
一方、H3-H4 および H5-H6 の結合距離はともに 0.757 Å (WBI = 0.988 および 0.996)で単一水素分子からほとんど変化がなく、また Sc からの距離も遠い（3.602～4.597 Å 程度）などから、この錯体でも第２および第３の水素分子は吸着されていると見てよいことが分かる。
【[Cp2CrIII(PH3)]+の解析結果】
この錯体は図 4 の形状をしており、P-Cr 間の距離は4.467 Å と遠くて PH3 リガンドが脱離傾向にあり、この錯体自体の形状保持が困難である。ちなみに CrIII は
3d34s0 の電子状態を持つとされ、実際に２重項と４重項状態があるが、この錯体の多重度としては４重項状態が安定であった。さらに水素分子の付加を調べても構造は安定化せず、Cr が中心金属である場合には水素分
Fig. 4

Optimized structure of [Cp2

CrIII(PH3)]+.

子付加が困難であったので、これ以上の解析は中止した。

【[Cp2VIII(PH3)]+の解析結果】
水素分子が付加する前のこの錯体は図 5(a)の形状であり、この錯体には最高で水素２分子が付加－ 69 －

Ⅳ 研究業績 (2017)

することが明らかとなった（図 5(b), (c)）。ただし V の場合には Kubas 錯体は形成せずに、第１水素分子から吸着されることも分かった。

(a)Fig. 5(c)(b)

Optimized structures of (a) [Cp2VIII(PH3)]+ complex and (b) that with two additional

H2 molecules.

Both the two H2 molecules with blue-broken ovals are adsorbed.

In (c) is

indicated the same with (b) from a different angle.
VIII は 3d24s0 の電子状態を持つとされ、実際に１重項と３重項状態があるが、この錯体の多重度
としては３重項状態が安定であった。V 錯体の場合には上記のように、そもそも Kubas 錯体が形成されず、第 1 および第 2 の水素分子付加によるエンタルピー安定化はそれぞれ 3.14, 3.02 kJ/mol であった。H1-H2 および H3-H4 の結合距離はともに 0.758 Å (WBI = 0.979 および 0.980)で単一水素分子からほとんど変化がなく、また V からの距離も遠い（3.253～3.960 Å 程度）ことなど、この錯体でも第１および第２の水素分子が吸着されていると見てよい。
【まとめ】
以上のように PH3 を配位子とするメタロセン錯体 (M = TiIII, CrIII, ScIII および VIII) における水素分子との反応と吸着については、中心金属によってそれぞれの電子状態挙動には違いがあり、TiIII,
ScIII および VIII 錯体には２個の水素分子が吸着しうることが明らかとなった。この吸着には分散力などが効いていることが考えられ、それ自体興味深い問題を提供している。また Kubas 錯体の形成
状況にもそれぞれ差異があることが分かった。これは d 電子状態の特性の違いによるものと考えられる。これらの知見は燃料電池における水素源の開発にとって有用なものと期待できる。ここで解析した金属錯体の実際の使用法としては粉体状態での利用などを含めて今後考慮すべき点が多くあり、それらに関する検討も必要である。また同時に金属種や分子骨格の軽量化に向けても検討を広げる予定である。
【文献】 1) G. J. Kubas, Acc. Chem. Res., 21, 120-128 (1988). 2) Gaussian 09, Revision D.01, M. J. Frisch etal., Gaussian Inc., Wallingford, CT (2009).

2) Gaussian 09, Revision D.01, M. J. Frisch et al., GaussianInc., Wallingford, CT (2009).

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Ⅳ 研究業績 (2017)

2. 論文
(1)
Kensuke NAKA, Takuji KATO, Koushi ABE, Makoto ISHIDOSHIRO, Shintaro NISHIYAMA,
Susumu TANAKA, Hiroaki IMOTO, Seiji WATASE, Kimihiro MATSUKAWA, Hiroyuki FUENO,
and Kazuyoshi TANAKA,“Stereoisomerization of 1,4-dihydroarsinetetracarboxylic acid diimides
under non-acidic condition from cis- to trans-forms”
Heterocycles 94(5), 923-937 (2017).
(2)
Joji OHSHITA, Toshiyuki TSUCHIDA, Kenji KOMAGUCHI, Kazuki YAMAMOTO, Yohei
ADACHI, Yousuke OOYAMA, Yutaka HARIMA, and Kazuyoshi TANAKA,“Studies of spherically distributed LUMO and electron-accepting propertiesof caged hexakis(germasesquioxanes)”
Organometallics 36(14), 2536-2540 (2017).
(3)
Toshiaki IKEDA, Hiroaki ADACHI, Hiroyuki FUENO, Kazuyoshi TANAKA, and Takeharu
HAINO,“Induced-dipole-directed,
cooperative
self-assemblyofabenzotrithiophene”
J. Org. Chem. 82(19), 10062-10069 (2017).
(4)
Katsunori SUZUKI, Yasuyuki NUMATA, Naoko FUJITA, Naoki HAYAKAWA, Tomoharu
TANIKAWA, Daisuke HASHIZUME, Kohei TAMAO, Hiroyuki FUENO, Kazuyoshi TANAKA,
and Tsukasa MATSUO,
A stable free tetragermacyclobutadiene incorporating fused-ring bulky EMindgroupsChem. Commun. 54(18), 2200-2203 (2018).
3. 総説
(1)
田中一義
「化学つれづれ草 第一回 理屈っぽい化学？」
化学 72, No. 5, 55 (2017).
(2)
田中一義「化学つれづれ草 第二回 福井研究室の日常」
化学 72, No. 6, 31 (2017).
(3)
田中一義「化学つれづれ草 第三回 博士課程 考」
化学 72, No. 7, 29 (2017).
(4)
田中一義「化学つれづれ草 第四回 米国のベンチャー企業」
化学 72, No. 8, 27 (2017).
(5)
田中一義「化学つれづれ草 第五回 米国の研究資金事情」－ 71 －

Ⅳ 研究業績 (2017)

(6)

(7)

(8)

(9)

(10)

(11)

化学 72, No. 9, 18 (2017).
田中一義「化学つれづれ草 第六回 日本の大学と研究資金」
化学 72, No. 10, 29 (2017).
田中一義「化学つれづれ草 第七回 妄想と基礎研究資金」
化学 72, No. 11, 46 (2017).
田中一義「化学つれづれ草 第八回 企業と大学の研究」
化学 72, No. 12, 28 (2017).
田中一義「化学つれづれ草 第九回 オリジナルな研究」
化学 73, No. 1, 59 (2018).
田中一義「化学つれづれ草 第十回 理論化学と計算化学」
化学 73, No. 2, 29 (2018).
田中一義「化学つれづれ草 第十一回 分割統治と化学」
化学 73, No. 3, 24 (2018).

4. 学会発表(1)
Kazuyoshi Tanaka, Hiroyuki Fueno, Hiroyuki Suto, Takuji Kita, Mitsuru
Matsumoto, and Takashi Kuzuya,“Theoretical Examination on Absorption of Hydrogen Molecules to Metallocene
Complex”
日本化学会第 98 春季年会(2018) 船橋 2018/3/21 2PA-132
5. その他田中一義(1)「計算化学はどのように役立つか」京都グリーンケミカル・ネットワーク若手人材交流事業、京都（京都市成長産業創造センター）2017/11/2 （講演番号なし）－ 72 －

Ⅳ 研究業績 (2017)

４．リサーチリーダー

Kazuo Takatsuka
Kazuo Takatsuka
Research Leader
Research Leader
Summary of the research of the year
We have been developing a basic framework of theoretical chemistry, which we call the theory of
nonadiabatic electron wavepacket dynamics with an aim to cultivate new fields of theoreticalchemistry. One outcome of such theoretical developments in this year is a novel formalism ofmolecular nonadiabatic electron dynamics in condensed phases such as in solvents. Also, we havediscussed the notion of nonadiabatic dynamics beyond the frame work of quantum theory. Indeed aseries of hierarchical subsystems of different time-scales in classical mechanics have beenformulated, which are shown to have much similarity to quantum nonadiabatic dynamics.
In the aspect of applications of the theory of nonadiabatic dynamics, one of the major progresses
made in this year of period is the analysis and proposal of photocatalytic cycle of water splittingwith small manganese oxides and the roles of water cluster as a direct resource of oxygen molecules.
We have also shown a mechanism of collision induced charge separation in ground-state water
splitting dynamics. These findings are really epoch making in the field of charge separation
dynamics in biological and/or organic systems. Another important branch of the applications is thenonadiabatic electron dynamics in molecular ionization such as multiphoton photoionization, auto
ionization, and so on. The theoretical challenge made in our group has demonstrated that electron
detachment dynamics can be treated in terms of ab initio scheme of nonadiabatic electron
wavepacket dynamics just as in the standard quantum chemistry.
We are further developing a new concept of chemical bonding, which we call “dynamical chemicalbond” or “hyper-resonance”, which will be published soon. Development of the theory of
relativistic electron dynamics is also in progress. Besides, we have been constructing amethodology and algorithm for describing nuclear wavepackets besides the electron wavepakets
simultaneously.

(i) Theory of molecular nonadiabatic electron dynamics in condensed phases. [1]In light of the rapid progress of ultrafast chemical dynamics driven by the pulse lasers having
width as short as several tens of attoseconds, we have developed a theory of nonadiabatic electron
wavepacket dynamics in condensed phases, with which to directly track the dynamics ofelectronic-state mixing such as electron transfer in liquid solvents. Towards this goal, we combineda theory of path-branching representation for nonadiabatic electron wavepacket dynamics invacuum [a mixed quantum-classical representation, Yonehara and Takatsuka, J. Chem. Phys.,129,134109 (2008)] and a theory of entropy functional to treat chemical dynamics in condensed phases－ 73 －

Ⅳ 研究業績 (2017)[a mixed dynamical-statistical representation, Takatsuka and Matsumoto, PCCP, 18, 1771 (2016)].
Difficulty and complexity in the present theoretical procedure arise in embedding the Schrödinger
equation into classically treated statistical environment. Nevertheless, it has been shown that theresultant equations of motion for electronic-state mixing due to the intrinsic nonadiabaticinteractions and solute-solvent interactions, along with the force matrix that drives nuclear
branching paths, both turn out to be clear enough to make it possible to comprehend the physicalmeanings behind. We also discussed briefly nonvalidness of naive application of the notion of
nonadiabatic transition dynamics among free energy surfaces.

ii) On photocatalytic cycle of water splitting with small manganese oxides and the roles ofwater cluster as a direct resource of oxygen molecules. [2]We theoretically have studied chemical principles behind photodynamics of water splitting; 2H�O
+ 4hν + M → 4H⁺ + 4e⁻ + O� + M. To comprehend this simple looking but very complicatedreaction, the mechanisms of at least three crucial phenomena, among others, need to be clarified,each of which is supposed to constitute the foundation of chemistry: (i) Charge separation 4H⁺ +4e⁻ , (ii) catalytic cycle for essentially same reactions to be repeated by each of four photon
absorptions with a catalyst M, and (iii) generation of oxygen molecule of spin triplet. We clarified
before the photodynamical mechanism of charge separation, which we refer to as coupled proton
electron-wavepacket transfer (CPEWT), based on the theory of nonadiabatic electron wavepacket
dynamics [K. Yamamoto and K. Takatsuka, 2017, ChemPhysChem, 18, 537]. CPEWT gives an idea
on how charge separation can be materialized at each single photon absorption. Yet, this mechanism
alone cannot address the above crucial items (ii) catalytic cycle and (iii) O� formation. In thestudies on these fundamental processes, we constructed a minimal possible chemical system andperform semi-quantitative quantum chemical analyses, with which to attain the insights about
possible mechanisms of photochemical water splitting. The present study has been inspired by theidea underlying the so-called Kok cycle, although we do not aim at simulation of photosystem II in
biological systems in nature. For instance, we here assumed that a catalyst M, actually simple
manganese oxides in this particular study, is pumped up to its excited states leading to charge
separation by four-time photon absorption, each excitation at which triggers individual series ofchemical reactions including the reorganization of hydrogen-bonding network (cluster) of watermolecules surrounding the photocatalytic center. It was shown that in the successive processes ofrestructuring of the relevant water cluster, O=O bond is formed and consequently oxygen moleculeof spin triplet can be isolated within a range of given photon energy of about 3.0 eV.

iii) Collision induced charge separation in ground-state water splitting dynamics. [3]
In one type of photocatalytic dynamics of water splitting formally summarized as－ 74 －

Ⅳ 研究業績 (2017)

2H�O + 4hν + MH → 2H�O + M*H → 4H⁺ + 4e⁻ + O� + MH
the catalytic center M mainly composed of Mn oxides (clusters) along with supporting molecules
like proteins is directly photoexcited and discharges electrons and protons from it. The mechanism
can be comprehended in terms of the coupled proton electron-wavepacket transfer (CPEWT). In
another type proposed in the literature, M is not directly photoexcited, and instead, the lights areabsorbed somewhere other than M, thereby creating complicated sequential steps (a ladder) of
oxidation-reduction potential, thus sucking electrons successively from one molecular site to thenext, and the final place providing electrons and protons is the catalytic center M. During the charge
separation dynamics, M is assumed to remain in the electronic ground state, and this type can be
schematically summarized as
MH + Ω⁺ → M⁺ + HΩ,
where Ω indicates a cation species (a hole carrier) the site of photon absorption. It is widelybelieved that the latter mechanism is responsible for water splitting in plants and cynobacteria, andM in photosystem II (PSII) is known to include Mn�CaO�. However, heavy questions about thismechanism of ground-state charge separation in the latter reaction arise as to whether it is quantum
mechanically possible and what is it, if indeed possible. Besides, the time-constant for this reaction
reported in the literature is so long, actually far longer than the time-scale for energy dissipation forinter- and intra-molecular vibrational energy redistribution, that the quantum mechanical coherenceof the reaction should not be able to be maintained. More seriously, we wonder how the protons andelectrons can be isolated in the ground state, if any, and how they can be transferred unidirectionally(with no return)? We have addressed these fundamental questions and clarified them affirmatively
by proposing a general chemical principle; collision induced charge separation dynamics in groundstate.

iv) Time-resolved photoelectron signals from bifurcating electron wavepackets propagatedacross conical intersection in path-branching dynamics. [4]A computational scheme of energy- and geometry-dependent photoelectron signals from the
dynamics near a conical intersection based on a simplified path-branching representation of
nonadiabatic electron wavepacket dynamics has been proposed. Taking the NO� X/A conicalintersection as an example, the results of the present scheme compared to those from previous study
based on the method of full quantum vibrational wavepacket shows qualitative agreement
suggesting promising application to computation in larger systems intractable to full quantum exact
methods.

－ 75 －

Ⅳ 研究業績 (2017)v) Nonadiabatic electron wavepacket dynamics behind molecular autoionization. [5]A theoretical method for real-time dynamics of nonadiabatic reorganization of electronic
configurations in molecules has been developed, with dual aim that the intramolecular electron
dynamics can be probed by means of direct and/or indirect photoionizations and that the physicalorigins behind photoionization signals attained in the time domain can be identified in terms of thelanguage of time-dependent quantum chemistry. In doing so, we first formulated and implemented a
new computational scheme for nonadiabatic electron dynamics associated with molecular ionization,
which well fits in the general theory of nonadiabatic electron dynamics. In this method, the total
nonadiabatic electron wavepackets are propagated in time directly with complex natural orbitals
without referring to Hartree-Fock molecular orbitals, and the amount of electron flux from amolecular region leading to ionization is evaluated in terms of the relevant complex natural orbitals.
We have applied the method to electron dynamics in the elementary processes consisting of theAuger decay to demonstrate the methodological significance. An illustrative example was takenfrom an Auger decay starting from the 2a� orbital hole-state of H₂ O⁺ . The roles of nuclear
momentum (kinematic) couplings in electronic-state mixing during the decay process wereanalyzed in terms of complex natural orbitals, which are schematically represented in theconventional language of molecular symmetry of the Hartree-Fock orbitals.

vi) Adiabatic and nonadiabatic dynamics in classical mechanics for coupled fast and slow
modes: sudden transition caused by the fast mode against the slaving principle. [6]Adiabatic and nonadiabatic dynamics in classical systems composed of fast and slow modes havebeen formulated. Theoretical consequences from both adiabatic and nonadiabatic dynamics havealso been discussed. In particular, we aimed to identify a possible physical origin for drastic changeof the slow dynamics to be induced by instability that happens to emerge in the fast mode. The
Haken slaving principle and other theories like the adiabatic elimination method focus on the orderformation led by the growth of the slow modes, with slaving the fast modes so as to faithfully
follow the system dynamics. In this context, the fast modes are quite often regarded as "noise" or afactor of small fluctuation. However, in molecular nonadiabatic dynamics due to the breakdown of
the Born-Oppenheimer approximation, the roles of the fast mode (due to electron dynamics) is far
from that of "noise", and sometimes bring about a qualitative bifurcation of the dynamics of theslow subsystem, which we usually refer to as nonadiabatic transition. We have shown the similarsudden change can be caused by the fast mode in classical mechanics too. The similarity anddifference between quantum and classical nonadiabatic dynamics were discussed. Recursive
equations of motion for general hierarchical dynamics composed of three and more modes havebeen also given.

－ 76 －

Ⅳ 研究業績 (2017)

2. Original papers[1] Theory of molecular nonadiabatic electron dynamics in condensed phases.
Kazuo Takatsuka, J. Chem. Phys. 147, 174102 (13 pages) (2017).
https://doi.org/10.1063/1.4993240[2] On photocatalytic cycle of water splitting with small manganese oxides and the roles of water
cluster as a direct resource of oxygen molecules.
Kentaro Yamamoto and Kazuo Takatsuka, PCCP, 20, 6708-6725 (2018)
DOI:10.1039/c7cP0717j[3] Collision induced charge separation in ground-state water splitting dynamics
Kentaro Yamamoto and Kazuo Takatsuka, PCCP, 20, 12229-12240 (2018).
[4] Time-resolved photoelectron signals from bifurcating electron wavepackets propagated acrossconical intersection in path-branching dynamics.
Yasuki Arasaki and Kazuo Takatsuka, Chem. Phys. 493, 42-48 (2017)
DOI: 10.1016/j.chemphys.2017.06.008[5] Nonadiabatic electron wavepacket dynamics behind molecular autoionization.
Takahide Matsuoka and Kazuo Takatsuka, J. Chem. Phys. 148, 014106 (15 pages) (2018).
https://doi.org/10.1063/1.5000293[6] Adiabatic and nonadiabatic dynamics in classical mechanics for coupled fast and slow modes:
sudden transition caused by the fast mode against the slaving principle.
Kazuo Takatsuka, Mol. Phys. (Michael Baer Festschrift issue), accepted on line
(2018.2.13).

3. Presentation at academic conferences［国際研究集会］
1. “Time-Domain Quantum Chemistry”
Kazuo Takatsuka, Nonadiabatica2018, Jerusalem, Israel, 2018. 3. 15(Invited)

2. “Electron Dynamics in Chemical Reactions: Time-Domain Quantum Chemistry.”(Mizushima-Raman Lecture)，Kazuo Takatsuka, CRSI, Raipur, India 2018. 2. 3 (Invited)－ 77 －

Ⅳ 研究業績 (2017)

3. “Molecular Science beyond the Born-Oppenheimer Paradigm.” (Sadhan Basu Memorial
Lecture) Kazuo Takatsuka, IACS, Kolkata India 2018.3.5 (Invited)
4. “Nonadiabatic electron dynamics in chemical reactions: Basic theory for chemical reactions in
the age of real-time observation.”
Kazuo Takatsuka, APCTCC8. Mumbai, 1. 15-17. 2018 (Invited)
5. “Photocatalytic cycle of water splitting with small manganese oxides and the roles of water
cluster as a direct resource of oxygen molecules.”Kentaro Yamamoto and Kazuo Takatsuka, Sanibel Symposium, 2018. 2.14
6. “Auger Decay Process in Water Molecule: A Nonadiabatic Electron Dynamics Treatment.”
Takahide Matsuoka and Kazuo Takatsuka,2nd_International_Symposium_on_Attosecond_Science，
2017.8, 24 Riken
7. “Molecular Science of Nonadiabatic Electron Wavepackets: Trying to bridge between ultrafast
nonadiabatic dynamics and chemistry”
Kazuo Takatsuka , Okazaki Conference, Okazaki, 2017.3.6. (Invited)
8. “Photodynamical electron-wavepacket mechanism of water-splitting catalyzed by manganeseoxides involving hydrogen-bond network”
Kentaro Yamamoto and Kazuo Takatsuka, Okazaki Conference, Okazaki, 2017. 3.6.

［国内研究集会］
1)“古典動力学における時間階層性と非断熱過程－隷従原理と隷従者の反乱－”
高塚和夫, 分子科学討論会2017.15-18 東北大学
2)“高強度レーザー中の非断熱電子波束の対称性の破れについて”
松岡貴英，高塚和夫, 分子科学討論会 2017.15-18 東北大学
3)“生物系から着想を得た単純な系における衝突誘起の逐次的な電子移動; 非断熱の電子波束による研究”山本 憲太郎，高塚 和夫, 第 11 回分子科学討論会, 2017/09/15 – 18, 東北大 川内北キャ
ンパス4)“配位空間の幾何学と量子波束ダイナミクス”－ 78 －

Ⅳ 研究業績 (2017)

高橋 聡，高塚 和夫, 第 11 回分子科学討論会, 2017/09/15 – 18, 東北大 川内北キャンパス5)“Time-Domain Quantum Chemistry －電子の運動が観える時代の化学理論－”
高塚和夫 近畿化学協会コンピュータ化学部会公開講演会 大阪科学技術センター
10.27.2017
6)“水分子のイオン化の背景にある非断熱電子動力学：Auger 電子と高強度レーザーによる光電子について”
松岡貴英，高塚和夫, 第 20 回理論化学討論会, 2017/05/16 – 18, 京大時計台国際交流ホール7)“電子波束動力学的な電荷分離の機構によって駆動される Mn 酸化物中の水の光分解サイクル”
山本 憲太郎，高塚 和夫, 第 20 回理論化学討論会, 2017/05/16 – 18, 京大時計台国際交流ホール－ 79 －

Ⅳ 研究業績 (2017)

５．博士研究員

Mitsusuke Tarama
Mitsusuke Tarama
FIFC
Fellow
FIFC Fellow

1. Summary of the research of the year
Mechanics of cell crawling by means of force-free cyclic motion

Dynamics of active particles have attracted much attention from physicists over the
past decade. In contrast to passive particles, active particles exhibit spontaneous motion
such as directional translation without external forcing. This property of a vanishing force
monopole is known as the force-free condition. Therefore, it is not trivial how active
particles can achieve a net translational motion from an internal cyclic motion.
In his pioneering lecture, Purcell shed light on the importance of breaking the timereversal symmetry [1]. His idea was theoretically investigated later by using a simple
model swimmer composed of three linked spheres at low Reynolds number. The timereversal symmetry can be broken by a phase shift between the periodic oscillations of atleast two active linkers. This study was extended to include autonomous oscillation of thebond length and swimming in a viscoelastic suspension. All these studies are concerning
microswimmers, i.e., microscopic objects that are moving in a fluid environment.
In contrast to microswimmers that swim through a fluid environment, there also exist
microorganisms that migrate on a substrate. Such crawling motion is often observed foreukaryotic cells, such as Dictyostelium cells and keratocyte. Typically, the mechanism of
crawling motion is widely believed to consist of the following four steps [2]:1. Protrusion of the leading edge due to actin polymerization
2. Adhesion of the leading edge to the substrate underneath
3. Deadhesion of the trailing edge from the substrate
4. Contraction of the cell body due to actomyosin contraction
Despite a number of studies on each of these steps, the cycle of crawling mechanism itself
has not been verified systematically. Therefore, we investigated the basic mechanism ofcell crawling with a focus on the cycle of protrusion and contraction, as well as adhesion to
the substrate underneath.
To this end, we proposed a mechanical model, where a cell is described by a set ofsubcellular elements connected by a viscoelastic bond [3]. The bond consists of a damperand an elastic spring, as well as an actuator that elongates cyclicly, as depicted in Fig. 1(a).
The cyclic elongation of the actuator ���� represents the protrusion and contraction, which
we modelled by a simple sinusoidal function with the frequency �, ���� � ��� �������.
In addition, the adhesion to the substrate underneath and the deadhesion from it areincluded as a cyclic change in the strength of the substrate friction �� ��� , where thesubscript i indicates the one of the two elements i=1,2. We assumed that the substrate
friction takes the adhered stick state �� and the deadhered slip state �� for the sameintervals, which represents the adhesion-deadhesion transition. We keep the frequency of
the friction change same as the actuator elongation but with phase shift �� . The phase shifts
�1 and �2 are the two key parameters in this study, which may differ from each other. See
Fig. 1(b). Then, the equations of motion are given by�1 ����� � ���1 � �2 � � ����12 � ��0 � ������
�2 ����� � ���2 � �1 � � ���12 � ��0 � ������
where �1 and �2 are the velocity of the element 1 and 2, respectively, and their distance is－ 80 －

Ⅳ 研究業績 (2017)(a)element 2
x2,v2

k

l(t)

element 1
x1,v1



1(t)

2(t)
adheredstick state
-l1
a
f
a
f
0 T1 T2

l(t)

(c)
0.4

-

1(t)

Z

(b)
l1

0
+

2(t)
t T3 T4

deadheredslip state

-0.4
T

0

Q

0.4

Fig. 1: (a) Schematics of the two-element model of a cell crawling on a substrate (grey). The redand cyan elements are connected by a viscoelastic bond (blue), which consists of a spring ofelasticity k, a dashpot with dissipation rate ξ, and a linear actuator with time-dependent lengthl(t). The substrate friction ζi(t) of each element switches between the stick and slip states. (b) An
example of the time series for l(t), ζ1(t), and ζ2(t), and (c) the corresponding trajectory in the Q–
Z space, where the signed area enclosed by the curve denotes the distance over which the celltravels during the corresponding time interval. In panel (c), the black arrows show the time
evolution direction and the plus and minus signs indicate the temporal forward and backward
migration, respectively. This figure is reproduced from Ref. [3].

given by �12 � |�2 � �1 |. � and ℓ0 are the elastic constant and free length of the spring and� is the dissipation rate of the damper. Here, since the typical size of a cell is of order oftens of micrometers, the inertia term was neglected.
We measured the migration distance�in one cycle ��, which is calculated as�� � � �� ��� � ���� �
where �� � �12 ��� � � ℓ0 and �� � �����
2 ��� � � �1 ��� ���2��1 ��� � � �2 ��� �� represent theactual elongation of the cell and the symmetry breaking of the substrate friction at time �� ,respectively. Here, the time �� (n=1,2,3,4) is the boundary of the time sections, within eachof which both substrate frictions �1 and �2 are constant. See Fig. 1(b). Here, we assumed asteady state. This formula of �� indicates that the migration distance is given by the signed
area enclosed by the trajectory in Q-Z space. The analytical formula of the solution �� isprovided in Ref. [3].
In addition, we measured the efficiency of the crawling motion, which is definedby� � ������� ������������ �. ��� is the input energy, which comes from the work
done by the actuator. Since the cell moving horizontally on a flat substrate does not do any
work, the output work is evaluated under an additional infinitesimal external force �� as�� ��. Note that the efficiency is normalized by the maximum value to eliminate �� . The
exact formula of � was also obtained in Ref. [3].
The resulting �� and � are plotted against the phase shifts �1 and �2 in Fig. 2. The
difference of the substrate friction at the adhered and deadhered states are set as �� � 10��and �� ��� � 0�2�. The other parameters are fixed as � � 2��� � 1, � � 1, ℓ0 � 1��, andℓ1 � 0��.
If the two elements are in phase indicated by the thick black line in Fig. 2, then the cellonly oscillates its length around the stationary centre of mass as in Fig. 3 (b). Apart form thein-phase line, the cell starts to migrate. If the two elements are in anti-phase, there are
optimum set of phase shifts ��� � �� � indicated by the plus and cross symbols in Fig. 2,－ 81 －

Ⅳ 研究業績 (2017)

Fig. 2: The net crawling displacement of the two-element cell over one period ∆R and theefficiency η as functions of the phase shift ψ1 and ψ2 for different values of the intracellulardissipation rate: (a) ξω/k = 0.2π and (b) 20π. The red (cyan) colour corresponds to the forward(backward) motion, i.e., the motion towards element i = 1(2). The phase shifts that give themaximum and the minimum of ∆R and η are indicated by the plus and the cross signs,
respectively. The diagonal thick black lines and the thin black lines represent the in-phaseoscillatory motion and the reciprocating motion, neither of which show a net locomotion. This
figure is reproduced from Ref. [3].

x

Z

x

Z

x

Z

corresponding to the optimum forward and backward motions, respectively. The forward
optimum crawling motion is depicted in Fig. 3(a). However, even if the anti-phase case, thecell cannot achieve a net migration if it undergoes reciprocating motion, i.e. back-and-forthmotion, as displayed in Fig. 3(c).
In summary, we investigated the mechanism of cell crawling by focusing on how to
obtain a net migration from the internal cyclic (a) 2
0.4
motion under the force-free condition. We
1introduced a mechanical model where a cell00
is described by two subcellular elements-0.4
connected by a viscoelastic bond. The activity
-1
0
1
2
-0.4
0 Q 0.4tof the cell is included in the actuator (b)0.4
1elongation of the bond and the switch of thesubstrate friction, which represent the00
protrusion and contraction and the adhesion-1-0.4
to the substrate underneath and deadhesion
0
1
2
-0.4
0 Q 0.4tfrom it, respectively. We highlighted the (c)0.41importance of the phase shift of the substrate
friction of each subcellular element with
00
respect to the bond elongation to achieve a-1-0.4
net migration.
0

References:[1] E. M. Purcell, Am. J. Phys., 45, 3 (1977).
[2] R. Ananthakrishnan and A. Ehrlicher, Int. J.
Biol. Sci. 3, 303 (2007).
[3] M. Tarama and R. Yamamoto, J. Phys. Soc.
Jpn. 87, 044803 (2018).

1

t

2

-0.4

0 Q 0.4

Fig. 3: Two-element cell for ξω/k = 0.2π and(a) ψ1 = 0.27π and ψ2 = 1.27π, (b) ψ1 = ψ2
= π, and (c) ψ1 = 0.778794π and ψ2 =1.778794π. In each panel, the left subfigure
shows the spatiotemporal plot for two
periods. The right subfigure displays thecorresponding trajectory in the Q–Z space.
This figure is reproduced from Ref. [3].

－ 82 －

Ⅳ 研究業績 (2017)

2. Original papers(1) Mitsusuke Tarama“Swinging motion of active deformable particles in Poiseuille flow”
Phys. Rev. E 96, 022602 (2017).
(2) Mitsusuke Tarama“Dynamics of Deformable Active Particles under External Flow Field”
J. Phys. Soc. Jpn. 86, 101011 (2017).
(3) Mitsusuke Tarama and Ryoichi Yamamoto“Mechanics of cell crawling by means of force-free cyclic motion”
J. Phys. Soc. Jpn. 87, 044803 (2018).
3. Presentation at academic conferences(1) Mitsusuke Tarama,“Swinging motion of active deformable particles in Poiseuille flow”
9th International Conference Engineering of Chemical Complexity, Neàpolis Auditorium,
Vilanova i la Geltrú, Barcelona, Spain, 19 Jun, 2017 (oral).
(2) Mitsusuke Tarama,“Dynamics of active deformable particles in Poiseuille flow”
10TH LIQUID MATTER CONFERENCE, Cankarjev dom Cultural and Congress Centre,
Ljubljana, Slovenia, 17-18 Jul, 2017 (poster).
(3) Mitsusuke Tarama,“Active Deformable Particles in Poiseuille Flow”
International Symposium on Fluctuation and Structure out of Equilibrium 2017, Sendai
International Center, Sendai, Japan, 21 Nov, 2017 (poster).
(4) 多羅間充輔,“生物細胞のメカノケミカル・モデル”
札幌非線形現象研究会 2017, 北海道大学 電子科学研究所, 30 Aug, 2017 (oral).
(5) Mitsusuke Tarama, Kenji Mori, and Ryoichi Yamamoto,“Mechano-chemical modelling of biological cells”
A02 班 A03 班合同研究会「アクティブマターの概念で繋ぐ生命機能の階層性」“Hierarchy of biological functions connected by concept of active matter”, 函館

グリー

ンピア大沼, 11 Sep, 2017 (oral).
(6) 多羅間充輔,“ポワズイユ流れ中のアクティブソフトマターのダイナミクス”
第 7 回ソフトマター研究会, 京都大学・北部研究総合棟・益川ホール＆理学研究科
セミナーハウス, 25 Oct, 2017 (oral: invited).
(7) 多羅間充輔,“変形する自己推進粒子のポワズイユ流れの中での運動”
生物流体力学における基礎問題と応用問題, 京都大学 数理解析研究所, 31 Oct, 2017
(oral).

－ 83 －

Ⅳ 研究業績 (2017)(8) 多羅間充輔,“ポワズイユ流れ中のアクティブソフトマターの運動”
第 27 回 非線形反応と協同現象研究会, 福岡工業大学 FIT ホール, 9 Dec, 2017
(poster).
(9) Mitsusuke Tarama、Ryoichi Yamamoto,“A minimal model of crawling cells under force-free condition”
Active Matter Workshop 2018, FIFC, Kyoto University, 19 Jan., 2018 (oral).
(10) 多羅間充輔,“Deformable swimmers in Poiseuille flow”
15th FIFC Symposium, FIFC, Kyoto University, 2 Feb., 2018 (poster).
(11) 多羅間充輔,“基盤上の細胞の這走運動”
京都若手ソフトマター研究会, 京都大学 セミナーハウス, 7 Mar., 2018 (oral).
(12) 多羅間充輔,“基盤上を運動する細胞の力学モデル”
研究会 凝縮系の理論化学, 琉球大学 沖縄青年会館, 13 Mar., 2018 (oral: invited).
(13) 多羅間充輔,“基盤上を這行する細胞運動の力学メカニズム”
日本物理学会(oral).

第 73 回年次大会, 東京理科大学 野田キャンパス, 23 Mar., 2018

4. Others(1) 多羅間充輔“Nonlinear Dynamics of Active Deformable Particles: From Liquid Droplets to Biological
Cells”
第１５回 福井センターセミナー, 京都大学福井謙一記念研究センター, 2017/5/25.
(2) 多羅間充輔“微生物の力学：水中での遊泳から基盤上への這行へ”
山口大学

理学部

学術講演会、2018/3/5。

(3) 多羅間充輔“Mechano-chemical modelling of crawling cells based on sub cellular element model”
山口大学 岩楯研究室セミナー、2018/3/6。

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Ⅳ 研究業績 (2017)

MasatoMasato Itami
Itami
FIFC Fellow
FIFC Fellow
1. Summary of the research of the year
Singular Behavior of Time-Averaged Stress Fluctuations on Surfaces
In equilibrium statistical mechanics, fluctuations of thermodynamic quantities and their spatial
correlations near a critical point universally characterize a continuous phase transition. In non-equilibrium
statistical mechanics, fluctuations of time-averaged quantities and time correlations in equilibrium systems
are related to responses to small perturbations or transport coefficients, following the linear response theory.
Fluctuations and correlations in fluids have been investigated in the framework of fluctuatinghydrodynamics with Faxen’s law or Green's function method. However, it remains difficult to calculate
time-averaged surface stress fluctuations in a finite space. The main purpose of the present work is to
propose a new approach to calculating the time-averaged stress fluctuations on surfaces by using thecontraction principle, which is consistent with the linear response theory.
We consider a viscous incompressible fluid between two parallel plates, and study fluctuations oftime-averaged shear stress per unit area on the top plate at equilibrium. We assume that (i) the fluctuatingtime-averaged stress is balanced in equilibrium at each position and that (ii) the fluctuating time-averaged
stress obeys a Gaussian distribution on the restricted configuration space given by (i). Using theseassumptions with the Green–Kubo formula for the viscosity, we can derive the large deviation function of thetime-averaged stress fields. Then, using the saddle-point method for the large deviation function, or thecontraction principle, we obtain the surface shear stress fluctuations. We show that the surface shear stressfluctuations are inversely proportional to the system size. Thus, we may evaluate the distance between theplates by only measuring the time- and surface-averaged stress fluctuation on the top plate at equilibrium.

Setup
We consider a viscous incompressible fluid between two parallel plates of length �� and width �� .

The plates are oriented horizontally in the ��-plane and separated by a distance �� . We impose periodic

boundary conditions in the �- and �-directions. Let ��� ��, �� denote the ��-component of the fluctuating

viscous stress tensor ��� of the fluid at position � � ��, �, �� and time � in Cartesian coordinates.

According to the conservation of angular momentum, the stress tensor is symmetric. Thus, we identify ���with ��� . Let �micro denote the correlation time of the force acting on the top plate at � � �� . Throughout
this report, for any physical quantity A��, ��, we define the finite time-averaged quantity as���� ≡A1 �
� ���A��, ��,� �

where � is taken to satisfy � � �micro . We define the ��-component of the time-averaged stress tensor per

unit area on the top plate as－ 85 －

Ⅳ 研究業績 (2017)

��∗ ≡

��
��
1
� �� � �� ���� ��, �, �� �.
�� �� ���1�In accordance with the method of our previous paper, we study fluctuations of �∗ in the equilibrium systemat temperature �, whose intensity is denoted by 〈��∗� 〉eq .

withFor later convenience, we decompose ���� into traceless and trace parts:���� ��� � ��̅ ������ � �̅�� ����̅ ��� � ����� ��� � ���� ��� � ���� ���,
3

where � and � are called the mean pressure and the stress deviator tensor, respectively. Because the stressdeviator tensor is traceless, we have�̅�� ��� � �̅�� ��� � �̅�� ��� � �.

Assumptions

We assume that (i) the fluctuating time-averaged stress is balanced in equilibrium at each position,
which is expressed as����� � �.
� ��

�2�

We also assume that (ii) � obeys a Gaussian distribution on the restricted configuration space given by thetraceless condition and the assumption (i). Because � is obtained by integrating a microscopic stress over a

suitable region, it is reasonable, by considering the central limit theorem, to assume (ii). In this subsection,
we derive the probability density of the time-averaged stress fields in the equilibrium viscous fluids.

According to the Green--Kubo formula, the shear viscosity of the fluid � is related to the stressfluctuation in the bulk of the fluid as〈���� ������� ��� �〉eq �

2�B ����� � �� �,�where �B is the Boltzmann constant and � is assumed to be much larger than the correlation time of ��� .

Using the traceless condition, the Green--Kubo formula, the symmetric property of the stress tensor, and theisotropic property, we obtain the statistical property of �:with〈�̅�� ����̅�� �� ��� �〉eq �

2�B ��
����� �� ��� � �� ��2����� �� � ���� ���� � ���� ���� � ��� ��� �� .
3

For later convenience, we express ����� �� � ��� with ����� � � and ������� � �, where ����� � 1,����� � 2, ����� � 3, ����� � ����� � �, ����� � ����� � �, and ����� � ����� � �. That is, �

is interpreted as a � � � matrix. From the assumptions (i) and (ii), the probability density of thetime-averaged stress tensor in equilibrium is given by������
������� ����� � �e������������ ������ � � �� � ��－ 86 －

Ⅳ 研究業績 (2017)with������� ����� �

��
��
��
1
���,
� �� � �� � �� � �̅�� ������
���� � � �̅�� � ���B �� �
�
�
�,�

��

where � is a normalization constant and �

is the pseudo-inverse of �.

Results

From ������� �����, we formally obtain the probability density of ��∗ :����∗ � � � � ����� ������� ������ ���∗ �
�

��
��
1
� �� � �� ���� ��, �, �� ����� �� ��In the asymptotic regime � � �micro , the functional integral may be accurately evaluated by the saddle-point
method. By introducing the Lagrange multiplier field ���� � ��� ���, �� ���, �� ���� to take the constraint(i) into account, we obtain����∗ � � �∗ ����������∗ ��

with����∗ � �

and

��
��
��
1
� �� � �� � �� ������� �����,��� �� ����,��� ��B �� �
�
�

mi�

��� � � ���� ����� ���� ���,������� ����� � � �̅�� ������
���� � � �̅�� ��
�,�

�,�

where �∗ is a normalization constant. Note that the saddle-point method for the large deviation function has

been rigorously verified under certain conditions. This is called the contraction principle in probability
theory.

As boundary conditions of the variational problem, the natural boundary conditions are given by
��

��

��

� �� � �� � �� � �� ��� �������� ���� � �,
�

�

�

�

where ����� ��� is a variation of ���� ���. Recalling (1), we impose the following boundary conditions:���, �, �� � �, �� ��, �, �� � � �� , �� ��, �, �� � � �� ��, �, �� � � �,

where �� is a constant.

With this setup, the surface contribution of the variation vanishes, and we obtain the Euler–Lagrange

equationswhich are equivalent to����� � �,� � �� ���������� ���� ������ � ��̅ ��� � ���� �� � �� �� �����Note that the definition of �̅ is equivalent to � � � � � in the expression of the above equation. The set of
equations (2), (3), and � � � � � coincide with the Stokes equations �� � � � ��̅ and � � � � � with (3).

Thus, we may interpret ���� as the virtual velocity fields of the fluid generated by the most probable stressfields for given ��∗ . Note that the natural boundary conditions are not related to boundary conditions for thereal velocity fields of the fluid. (If the boundary conditions for the virtual velocity fields are related to those－ 87 －

Ⅳ 研究業績 (2017)

for the real velocity fields, the fluctuations of ��∗ depend crucially on whether the top plate is fixed or
movable in equilibrium.)

By referring to the solution of the Stokes equations with the natural boundary conditions and (1), we

obtain�� ��� �

��∗ �
,
�

�� ��� � �� ��� � �,

where �� is a constant. These results with (3) lead to���� ��� � ���� ��� � ���� ��� � ��� ,Thus, we obtain����∗ � �

which leads to�̅ ��� � �� ,���� ��� � ���� ��� � �,�� �� �� ��� ,��B �� ∗〈��∗� 〉eq ���B ��.
�� �� �� �〈��∗� 〉eq ∝1,�� �� ����� ��� � ��∗ .

���

Because ��∗ is the time- and surface-averaged quantity, we naively expect the central limit theorem:

where ∝ implies that we only focus on the �� �� and � dependencies of a function. With regard to thesedependencies, the result (4) is consistent with the above expectation. In addition to this standard behavior, (4)implies that the fluctuations of ��∗ are inversely proportional to �� , which may originate from thelong-range stress correlations via the virtual Couette flow generated by the most probable stress fields forgiven ��∗ . Such �� dependence is singular because the fluctuations vanish in the limit �� → ∞ .

Furthermore, we may evaluate the vertical system size �� by only measuring the time- and surface-averaged

stress fluctuation on the top plate in equilibrium. We stress that the assumption (i) expressed as (2) isessential to the long-range stress correlations.

We can check the validity of (4) or the assumptions (i) and (ii) in terms of the linear response theory.
When the top plate moves at constant velocity � which is assumed to be much slower than the soundvelocity of the fluid (and the bottom plate is attached to a heat bath of temperature �), the surface average of��� ��, �, �� � in the steady state is given by������ �� � �
1〈�� 〉 �.
� �� � �� 〈���� ��, �, �� �〉st ���B � ∗ eq�� �� ��This equation and (4) lead to

��
��
1
��
� �� � �� 〈���� ��, �, �� �〉st � ,�� �� ����which is consistent with the standard hydrodynamics, namely the shear stress in Couette flow at low
Reynolds numbers with stick boundary conditions.

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Ⅳ 研究業績 (2017)

2. Presentation at academic conferences(1) Masato Itami and Shin-ichi Sasa
“Universal form of stochastic evolution for slow variables in equilibrium systems”
30th Marian Smoluchowski Symposium on Statistical Physics, Kraków, Poland, Sep. 4-8,
2017 (poster).
(2) 伊丹將人、佐々真一「ソレー効果と断熱ピストン問題における熱誘起力の差異」
日本物理学会2017年秋季大会、岩手大学、2017年9月21-24日（口頭）(3) 伊丹將人、佐々真一「平衡流体における時間平均応力ゆらぎの超均一性II」
日本物理学会第73回年次大会、東京理科大学、2018年3月22-25日（口頭）3. Others(1) Masato Itami and Shin-ichi Sasa
“The difference between the heat-induced forces of the Soret effect and the adiabatic piston”
The 15th symposium of Fukui Institute for Fundamental Chemistry, Kyoto, Feb. 2, 2018
(poster).

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Ⅳ 研究業績 (2017)

Shunsuke Yabunaka
Shunsuke Yabunaka
FIFC Fellow
FIFC Fellow

1. Summary of the research of the year
Emergence of epithelial cell density waves
Pattern‐forming instabilities play a pivotal role in the morphogenesis and spatio‐temporalorganization of living organisms. Paradigmatic examples include the morphogen patterns ofdeveloping embryos and the cooperative behavior of large assemblies of microorganisms, forinstance in bacterial colonies. At the scale of the tissue, Serra‐Picamal et al. discovered that the
expansion into free space of Madin‐Darby canine kidney (MDCK) epithelial cell monolayers isaccompanied by traveling mechanical waves of the velocity, strain rate, traction force and stressfields (X. Serra Picamal et. al., Nature Physics 8 628, 2012).
By employing our hydrodynamics model of cellular tissues including (1) active contractile force (2)cell motility (3) cell polarity, we investigated pattern formation in epithelia. Previously, we havefound that mechanical wave appears via Hopf bifurcation above threshold of active parameters when
there is uniform polarity initially[4]. As shown in Fig. 1, in this study, we found that mechanicalwave appears as a result of the secondary bifurcation after the first bifurcation where standing wave
appears, for cases where there is no uniform polarity initially. We also found that a chaotic pattern
can appear with even stronger activity[5].

Fig. 1 Mechanical wave as a result of the secondary bifurcation(left) and chaotic pattern (right).

Critical adsorption profiles around a sphere and a cylinder in at criticality
We study universal critical adsorption on a solid sphere and a solid cylinder in a fluid at bulk criticality,
where preferential adsorption occurs. We use a local functional theory proposed by Fisher et al. [M. E.
Fisher and P. G. de Gennes, C. R. Acad. Sci. Paris Ser. B 287, 207 (1978); M. E. Fisher and H. Au-Yang,
Physica A 101, 255 (1980)]. We calculate the mean order parameter profile ψ(r), where r is the distance fromthe sphere center and the cylinder axis, respectively [2]. The resultant differential equation for ψ(r) is solved
exactly around a sphere and numerically around a cylinder. A strong adsorption regime is realized except forvery small surface field h1, where the surface order parameter ψ(a) is determined by h1 and is independentof the radius a. If r considerably exceeds a, ψ(r) decays as r−(1+η) for a sphere and r−(1+η)/2 for a cylinder inthree dimensions, where η is the critical exponent in the order parameter correlation at bulk criticality.
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Ⅳ 研究業績 (2017)

Fig. 2 Normalized order parameter as a function of x=r/a as a function of the distancefrom the sphere center r around a solid sphere with radius a at criticality. Here η is set
to 0.

Nonperturbative fixed points in O(N) and tensor models
It is by now widely believed that everything is known about the criticality of the O(N) models
either exactly or with an accuracy that is limited only by our finite computational ability. For
the Wilson-Fisher fixed point, almost all the theoretical formalisms have been tested and they
all yield consistent result.
However, for the multicritical fixed points, the situation is less clear. For example, anontrivial multicritical fixed point with two unstable directions, which we call T_2, branchesfrom the Gaussian fixed point at d=3 dimension, below which the six-order term becomesrelevant. The same scenario also repeats in each critical dimension d_n=2+2/n: a nontrivial
multicritical fixed point with n unstable directions branches from the Gaussian fixed point.
However, in the large N limit, only the gaussian and WF fixed points have been found ingeneric dimension 2<d<4 so far.
In this study, we investigate the multicritical fixed point structure of the O(N) models bymeans of nonperturbative (also called functional) renormalization group (NPRG) and findsome surprising features. In particular, we find new nonperturbative fixed points in three
dimensions (d=3) as well as at N=\infty, as shown in Fig. 3 [1]. These fixed points cometogether with an intricate double-valued structure when they are considered as functions of dand N, as shown in Fig. 4. Many features found for the O(N) models are shared by the
O(N)�O(2) models relevant to frustrated magnetic systems.

Fig. 3. Two curves dc(N) and d’c(N). We foundthat T2 vanishes at d= dc(N) by colliding withanother nonperturbative fixed point, which wecall C3, when decreasing d starting from d=3 forN>18. We followed C3 increasing d and foundthat it disappears at d=d’c(N) by colliding with
yet another nonperturbative fixed point, which
we call C2, with two unstable directions.

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Ⅳ 研究業績 (2017)

Fig. 4. Singular point S and the two lines Nc(d) (red squares) and N′c(d) (blue stars). Startingfrom P, the FP T2 is followed along a clockwise (left) or anticlockwise (right) closed pathsurrounding S. On the clockwise path, T2 becomes C2 after a full rotation. On the anticlockwise
path, T2 collides with C3 on Nc(d) and disappears. It actually becomes complex-valued andremains so all along the dashed path. On N′c(d) it becomes real again but is now C2. The pathjoining Nc(d) and N′c(d) at fixed N=33 is also shown in panel (a). In panel (b), we indicate which(real) multicritical FPs exist in each region. In the white region, there is only one multicritical FP
with two directions of instability that can be continuously followed from both T2 and C2
depending on the path followed.

2. Original papers(1) Shunsuke Yabunaka and Bertrand Delamotte, “Surprises in O (N) Models: Nonperturbative
Fixed
Points,
Large
N
Limits,andMulticriticality”
Physical review letters 22, 19, 191602 1-5(2) Shunsuke Yabunaka and Akira Onuki, "Critical adsorption profiles around a sphere and acylinder
in
a
fluid
at
criticality:
Local
functional
theory”
Physical review E, 96, 3 032127 1-7 (2017)(3) Shunsuke Yabunaka and Akira Onuki, “Electric double layer composed of an antagonistic
salt in an aqueous mixture: Local charge separation and surface phase transition” Physicalreview letters 19, 118001 1-5 (2017)(4) Shunsuke Yabunaka and Marcq Philippe, “Cell growth, division, and death in cohesive
tissues: A thermodynamic approach”, Physical review E, 96, 2, 022406 1-9, 2017(5) Shunsuke Yabunaka and Marcq Philippe, “Emergence of epithelial cell density waves”,
Softmatter, 13, 39, 7046-7052 (2017)
3. Presentation at academic conferences(1) 藪中俊介、“増殖するアクティブマターの連続体理論”、 生物流体力学における基礎問題と応用問題, Kyoto,Oct. 31, 2017.
(2) 藪中俊介、小貫明、”二元混合系中の選択的溶媒和効果を持つ塩で構成された電気二重層:局所電荷分離と表面相転移”、ソフトマター研究会、Kyoto, Oct. 23,2017(3) 藪中俊介、小貫明、”二元混合系中の選択的溶媒和効果を持つ塩で構成された電－ 92 －

Ⅳ 研究業績 (2017)

気二重層:局所電荷分離と表面相転移”、日本物理学会 2017 年秋季大会 24pN23-3,
Morioka, Sep.24, 2017(4) 藪中俊介、Bertrand Delamotte,“非摂動くりこみ群による Large N での多重臨界現象の研究”
日本物理学会 2017 年秋季大会 24aJ25-4, Morioka, Sep.24, 2017(5) 藪中俊介、Philippe Marcq, ”増殖するアクティブマターの連続体理論”,日本物理学会 2017 年秋季大会 22pJ16-1 Morioka, Sep.22, 2017
4. Others(1) Shunsuke Yabunaka“Surprises in O (N) Models: Nonperturbative Fixed Points, Large N Limits, andMulticriticality” Theory Group seminar at Institut Curie, March 1, 2018(2) Shunsuke Yabunaka“Surprises in O (N) Models: Nonperturbative Fixed Points, Large N Limits, andMulticriticality” 京大佐々研セミナー, November 13, 2018

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Ⅳ 研究業績 (2017)

Simon
K.K.
SchnyderSimon
SchnyderFIFC
FIFCFellow
FELLOW
1. Summary of the research of the year
Collective motion of cells
Contact inhibition plays a crucial role in cell motility, wound healing, and tumour formation. By
mimicking the mechanical motion of cells crawling on a substrate, we constructed a minimal model ofmigrating cells that naturally gives rise to contact inhibition of locomotion (CIL). Despite the simplicity ofthe model, the collective behaviour of the cells is highly non-trivial and depends on both the shape of thecells and whether CIL is enabled.
The model cell consists of two disks, a front disk (a pseudopod) and a back disk (cell body), which areconnected by a finite extensible spring, see Fig. 1. CIL is achieved my coupling the migration force Fmig
linearly to the cell extension rbf. For comparison, we also worked with no-CIL cells by making the migration
force constant. CIL cells with a small front disk (i.e., a narrow pseudopod) form immobile colonies, see Fig.
2a. In contrast, cells with a large front disk (e.g., a lamellipodium) exhibit coherent migration without any
explicit alignment mechanism in the model, see Fig. 2b. This result suggests that crawling cells often exhibit
broad fronts because this helps facilitate alignment.
When investigating the collective dynamics in more detail, we find that the CIL model naturally
reproduces the strong linear decrease of the cell speed when the cells are packed at high densities, in contrast
to the no-CIL cells which barely adjust their speed, see Fig. 3a. The CIL cells’ response closely matches thatof real cells, as can be inferred from experimental data, see Fig. 3b. In addition, the typical log-normal
distribution of cell speeds which can be observed in experiments, only arises in the CIL version of the model,
i.e. when contact inhibition is enabled.

Fig. 1: Illustration of the cell model. (a) Schematic of a cell with a finite extensible non-linear elastic spring
connecting the disks and exerting the force ‫ܨ‬௙௘௡௘ , the migration force ‫ܨ‬௠௜௚ acting on the front disk (Eq. 2), and thefriction forces െߞ‫ݒ‬௕ and െߞ‫ݒ‬௙ . (b) The forces acting on the two disks composing a cell separated by a distance ‫ݎ‬௕௙ .
(c) Cell extension ‫ݎ‬௕௙ (red line segment) and migration force (black arrow) for the CIL cells in the steady state and acompressed state in which the disks are fully overlapping.
Fig. 2: Dynamic states. Snapshots of CIL
cells for a range of cell shapes. Cell
velocities are given as arrows and color.
Hue indicates deviation from average
direction, and slower cells are lighter incolor. The cells undergo a transition from aclustering/disordered state to an orderedstate upon change of the cell shape.
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Ⅳ 研究業績 (2017)

Collective alignment is typically measured with the polar order, the average orientation of the cells.
The alignment transition visible in the snapshots of Fig. 2 persists over nearly the full density range, see Fig.
4a. This is unrealistic, since, typically, cells only start coherently migrating at higher densities, while theyshow random behavior at low densities. We find the correct behavior by adding noise to the motion of thecells, which models the erratic motion of cells more accurately. In this way, at low densities, the collective
cell dynamics become dominated by the random motions of single cells, while at high densities frequent cellcollisions lead to collective alignment, see black line in Fig. 4a. This is precisely what is observed inexperiments. We also find that the alignment transition is qualitatively the same for CIL and no CIL cells,
only that it occurs earlier for CIL cells. Therefore we conclude that contact inhibition enhances alignment.
In the transition toward the arrest of cells with ߪ௕ / ߪ௙ = 0.80, areas of dynamic arrest begin tocontinuously form and dissolve. The arrested areas grow in size with density until they form systemspanning waves (Fig. 5a), which suggests that there is a growing length scale. The waves travel against thedirection of motion of the cells (Fig. 5d), akin to traffic jams in models of car traffic. In this state, the cell
speed distribution shows a peak at or near 0 and a long tail (see data for ϕ = 1.0 in Fig. 3c). The onset ofsystem-spanning arrest waves roughly coincides with the decrease in the order parameter at ϕ ≈ 0.85. We do
not observe such waves in the non-CIL systems (Fig. 5b). Thus, the waves are directly associated with the
CIL. Furthermore, the waves only occur when contact inhibition is strong; the cells withߪ௕ / ߪ௙ = 0.44,
which have a weaker slowdown at high densities (Fig. 1c), always travel coherently (Fig. 5c). Because they

Figure 3. Cell speeds. (a) Average cell speed, normalized by the steady-state speed of a solitary cell ‫ ݒ‬௦௦ , with (closed
symbols) and without (open symbols) contact inhibition for a range of cell shapes. (b) Speed of MDCK cells in a
growing cell colony and in confluent monolayers. (c) Speed histograms at ߪ௕ / ߪ௙ = 0.80. Black lines are fit to the datawith a log-normal distribution.

Figure 4. Collective alignment. (a) Polar order p as a function of area fraction for a range of cell shapes. Simulations
with cell noise at ߪ௕ / ߪ௙ = 0.44 are shown in black. (b) Polar order p as a function of cell shape at area fraction φ ≈0.18.
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Ⅳ 研究業績 (2017)

Fig. 5: Velocity waves. (a–c) Simulation snapshotsof CIL and no-CIL cells at area fraction φ = 0.92
with cell velocities shown as arrows. Hue indicatesthe deviation from the average direction, andslower cells are lighter in colour. (d) Kymographof simulation shown in (a). Average of cell
velocities in the y-direction, see arrow in (a), as afunction of time. Trajectory of one cellsuperimposed in black. (e) Velocity correlation
functions for simulations shown in (a–c).

slow down less abruptly, they never fully jam. The correlation function of cell speed fluctuations of the CIL
cells becomes negative on the length scale of the extent of the traffic jam with a minimum at approximately
10 Rmax, see Fig 5e. The VACF of corresponding no-CIL cells decays on the length scale of a few Rmax andnever becomes negative. This result reveals that cells move in small correlated clusters.

Anomalous transport in heterogeneous media
Transport of mesoscopic particles in simple solvents is often dominated by thermal motion. First
observed by Robert Brown in 1827 in the motion of organelles and later theoretically described by Albert
Einstein, this Brownian motion is found practically everywhere in soft matter and biological physics. The
key insight in understanding this motion was that the particles perform many frequent and uncorrelated
collisions with the fluid molecules. This leads to trajectories which can be seen as composed of independent
increments. As a generic result, we find that such trajectories become diffusive, in which the mean-squared
displacement (MSD) grows linearly in time, δr²(t) ~ t.
Since the assumptions for this theory are seemingly so simple and general, it may come as a surprisethat so many systems exhibit anomalous diffusion, i.e. the MSD grows with a (often time-dependent) power
γ(t) that is not 1, i.e. δr²(t) ~ ‫ ݐ‬ఊሺ௧ሻ . Many experiments show that transport is subdiffusive, γ(t) < 1, such as

crowding phenomena in biology, ion conduction in silicate glasses and other situations. These systems havein common that they consist of at least two components, characterized by a strong separation of time scales.
The more mobile component often exhibits anomalous diffusion over long periods of time.
The question driving my research has been whether the observed exponents merely represent transient
behavior, or whether they can be connected to a universal behavior with a well-defined exponent.
A paradigm for the modeling of transport in heterogeneous media is the Lorentz model (LM), where
the anomalous diffusion arises as a universal long-time limit: In its simplest version, a single mobile particle
moves in the static void space formed by overlapping hard disk obstacles. At low obstacle density, themobile particle freely explores the system and exhibits regular diffusion. At high densities, it becomestrapped in finite pockets of obstacles. In between, there is a localization transition, where the void space ofthe system stops to percolate, the system becomes self-similar, and anomalous diffusion occurs. Thistransition is a dynamic critical phenomenon and the exponent of the anomalous diffusion is universal.
The LM can be generalized by introducing interacting mobile particles and soft instead of hardinteractions, making it more comparable to realistic porous materials. But how such generalizations change
the dynamics is not well understood. One the one hand, an extension of the mode coupling theory (MCT) of
the glass transition predicted the LM localization transition to persist for interacting fluids in porous media,
i.e., that the nature of the transition is unchanged by the interactions, and that the critical behavior is－ 96 －

Ⅳ 研究業績 (2017)

Fig. 6: Anomalous transport. Mean-squared displacements δr²(t) and effective exponents γ(t) for a range of matrix∗
densities ��and fluid densities ��∗ . Fluid densities are ��∗ = 0, 0.016, 0.094, 0.313 for (a), (b) (��∗ = 0.016 in purple for∗clarity); �� = 0, 0.013, 0.264 for (c), (d); and ��∗ = 0, 0.020, 0.160, 0.400 for (e), (f). In (b), (d), (f), the criticalexponent of the two-dimensional LM 2/z = 2/3.036 is shown as a black line as a guide to the eye.

qualitatively the same. On the other hand, evidence from simulations of model porous media with interacting
particles, both with hard and soft interactions, has been inconclusive. While a localization transition andextended anomalous diffusion are observed, the exponents seldom match the predictions. Still, so far, it
seemed to be evident that porous media with soft or hard potentials are qualitatively equivalent, even thoughenergy barriers in systems with soft potentials are finite and, therefore, are crossable by soft particles.
We performed molecular dynamics simulations of interacting soft disks confined in a soft
heterogeneous matrix of obstacles. By systematically moving away from the single-particle case, weinvestigated how interactions between the mobile particles influence the dynamics. With increasing obstacle
density, the system exhibited a gradual transition from delocalized to localized dynamics, see Fig. 6.
Subdiffusion with constant exponents could be identified for up to three decades in time.
However, our results showed that the system exhibits fundamentally different dynamics from the LM.
Whereas, for the single-particle case, a mapping onto the LM transition was still possible, we found, here,that the universality of the dynamics breaks down. The interaction of particles with each other makes eachparticle’s energy time-dependent; the free area available to it changes with each collision with other mobile
particles. In that sense, the free volume in soft systems is dynamic—not static as in the LM—with drastic
consequences. Mobile particles help each other over potential barriers, speeding up the dynamics when themobile particle density is increased. This is impossible for interacting hard disks, thus, giving a rare example
where soft and hard interactions are qualitatively different.
The soft interactions are therefore responsible for a breakdown of the universality of the dynamics.
Even though exponents similar to the LM exponent may occur, we show that they merely represent effective,
non-universal exponents which are highly tunable via the particle interactions. Thus, they should not belinked to the anomalous exponent of the LM. In experiments, where interactions are typically quite complex,
the LM can, therefore, at best, serve as a tool for qualitative interpretation. Our work demonstrates that thewide range of exponents seen, e.g., in crowding experiments of cellular fluids is likely a result of the softinteractions between the components of those systems. Therefore, we expect that such crowding phenomena
cannot be associated with universal anomalous diffusion.

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Ⅳ 研究業績 (2017)

2. Original papers(1) S. K. Schnyder, & J. Horbach, “Crowding of interacting fluid particles in porous media throughmolecular dynamics: breakdown of universality for soft interactions”, Physical Review Letters, 120(7),78001 (2018).
(2) J. Horbach, N. H. Siboni, & S. K. Schnyder, “Anomalous transport in heterogeneous media“, The
European Physical Journal Special Topics, 226(14), 3113–3128 (2017).
(3) S. K. Schnyder, J. J. Molina, Y. Tanaka, R. Yamamoto, “Collective motion of cells crawling on asubstrate: roles of cell shape and contact inhibition“, Scientific Reports 7, 5163 (2017).

3. Presentations at academic conferences(2) S. K. Schnyder, J. J. Molina, and R. Yamamoto,“Colony growth of cells on a substrate”,
Active Matter Workshop,
Fukui Institute for Fundamental Chemistry, Kyoto (19/01/2018).
(3) S. K. Schnyder, J. J. Molina, and R. Yamamoto,“Colony growth of cells on a substrate”,
International Symposium on Fluctuation and Structure out of Equilibrium,
Sendai (21/11/2017).
(4) S. K. Schnyder, J. J. Molina, and R. Yamamoto,“Collective motion of cells crawling on a substrate: roles of cell shape and contact inhibition”,
10th Liquid Matter Conference, Ljubljana, Slovenia (17-21/7/2017).
(5) S. K. Schnyder, J. J. Molina, and R. Yamamoto,“Colony growth of cells on a substrate”,
4th Research Area Meeting, Tokyo (6/2017).

4. Others(6) S. K. Schnyder, J. J. Molina, and R. Yamamoto,“Colony growth of cells on a substrate”,
The 15th Symposium of Fukui Institute for Fundamental Chemistry, Kyoto (02/02/2018).
(7) Seminar: S. K. Schnyder“Collective motion of cells: roles of cell shape and contact inhibition”,
Groups of Prof. Joachim Rädler and Prof Erwin Frey, LMU Munich, Germany (7/2017).

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Ⅳ 研究業績 (2017)

Miho Isegawa
FIFC Fellow
31 Jan. 2018)
FIFC(To
Fellow
1. Summary of the research of the year
DFT Study on Fe(IV)-Peroxo Formation and H-Atom Transfer Triggered O2 Activation by
NiFe Complex
Hydrogenases are some of the most extensively studied metalloenzymes because of its catalytic ability toconvert the hydrogen molecule
into protons and electrons, or

(a)

O

in

the

reversereaction. This diverse group of
metalloenzymes can be classified

NN

16.3 (11.4)
1.1 (–6.0)–2.9 (–9.0)–5.1 (–10.8)
37.0 (30.9)
25.2 (18.1)
14.4 (6.4)
14.1 (7.1)
H

N
N

NiII

O

S
S
1D

H
H

inactivation

B

S=1

S
S

S=2
S=3

FeIII
H

3TS-F-F’

O
NiII

FeIV

3E

H

–31.7 (–37.6)–41.3 (–48.8)–45.2 (–54.1)–45.5 (–53.9)–48.0 (–53.6)–62.2 (–67.3)–63.5 (–69.9)–68.7 (–74.5)–54.3 (–51.9)–68.6 (–68.0)–70.8 (–70.5)–74.2 (–72.6)

0N
N NiII

H

NiII

B

3D’

–80.5 (–86.1)–88.9 (–95.7)–92.7 (–98.3)–95.7 (–
104.7)OSS

H
N
N NiII

3F

Hydrogen atom transfer and
O–O bond cleavage

FeII–70.5 (–76.1)–83.5 (–90.1)–87.1 (–94.3)–88.5 (–96.5)

O
S
S

B

H
H

H

FeII

H

O

N
N NiII

B

S
S

H–76.0 (–74.8)–89.5 (–87.0)–93.1 (–92.6)–93.3 (–93.8)

0

H

FeII

Hydrogen atom transfer
and Fe reduction

BH3OH removal(b)
O1(FeII(OH)NiIII), has been trapped
Most of the experimental and

S
S

1F’’

Ni-A (FeII(O–OH)NiIII) and Ni-B
in experiment.

N
N NiII

1B

1 F’

under

distinctive inactive oxidized states,–69.1 (–75.3)–82.9 (–90.2)–85.8 (–93.5)–86.9 (–95.6)

0
H

FeIV

shows

oxygen exposure. Further, two

H

FeII

H

N
N NiII

FeIV

S
S

B

H

O
S
S

O

H

1TS-F’-F’’

0
H

H

O H
N
N

known to be the most robust forreversible

O
N
N NiIISS

FeIII

Among them, NiFe hydrogenase is
it

S=0

H

B
H

–53.1(–58.0)–58.6 (–66.1)–65.3 (–72.1)–72.5 (–79.3)

H

O

composition of catalytic center.

and

H
H

FeIII

N
N

0

H
B
H

Fe-only hydrogenase, based on theoxygen,O

S
S+

into three groups, NiFe, FeFe and

the

NiII

3TS-D-D’∆G (kcal/mol)electrons

H

B
Hhydrogen evolution from protons
and

H
H

O1
O2

O2

1D

Ni−Fe = 3.20
Ni−O1 = 2.98
Ni−O2 = 3.43
Fe−O1 = 2.76
Fe−O2 = 1.75

3TS-D-D’ρ(Ni) = 0.01
ρ(Fe) = –0.36
ρ(O1) = 0.18
ρ(O2) = 0.10
ρ(B) = 0.00

Ni−Fe = 3.21
Ni−O1 = 2.81
Ni−O2 = 3.45
Fe−O1 = 2.81
Fe−O2 = 1.82
O1−H = 1.27

ρ(Ni) = 0.01
ρ(Fe) = 0.90
ρ(O1) = 0.31
ρ(O2) = 0.20
ρ(B) = 0.62

O1
O1
O2
O2

3 D’

Ni−Fe = 3.06
Ni−O1 = 4.66
Ni−O2 = 2.98
Fe−O1 = 4.18
Fe−O2 = 1.68
O1−H = 0.99

3Eρ(Ni) = 0.00
ρ(Fe) = 1.51
ρ(O1) = 0.01
ρ(O2) = 0.60
ρ(B) = 0.00

Ni−Fe = 2.95 ρ(Ni) = 0.02
Ni−O = 2.77 ρ(Fe) = 1.47
Fe−O = 1.67 ρ(O) = 0.62

3F

Ni−Fe = 3.03
Ni−O = 2.92
Fe−O = 1.67
O−H = 4.07

ρ(Ni) = 0.01
ρ(Fe) = 1.47
ρ(O) = 0.63
ρ(B) = 0.00

theoretical studies have targeted
the activation and formation ofhydrogeninenzymeandbiomimetic models. However, areaction between NiFe catalytic
center and dioxygen, which relates
to the generation of inactive states
and reactivation, has not been wellstudied. Therefore, elucidation ofthemechanismfordioxygen

3TS-F-F’

Ni−Fe = 2.73
Ni−O = 2.01
Fe−O = 1.79
O−H = 1.37

ρ(Ni) = 1.15
ρ(Fe) = 0.99
ρ(O) = –0.17
ρ(B) = –0.32

1F’

Ni−Fe = 3.25 ρ(Ni) = 0.00
Ni−O = 3.32 ρ(Fe) = 0.00
Fe−O = 2.08 ρ(O) = 0.00
ρ(B) = 0.00

1TS-F’-F’’

Ni−Fe =
3.12
Ni−O = 3.45
Fe−O = 3.18

ρ(Ni) = 0.00
ρ(Fe) = –0.01
ρ(O) = 0.00
ρ(B) = 0.00

1F’’

Ni−Fe = 3.11
Ni−O = 3.46
Fe−O = 3.64

ρ(Ni) = –0.02
ρ(Fe) = –0.02
ρ(O) = 0.00
ρ(B) = 0.00

1B

Ni−Fe = 2.77 ρ(Ni) = 0.00
ρ(Fe) = 0.00

Figure 1. (a) Free energy profiles of (i) the first hydrogen atom transfer
and O–O bond cleavage, (ii) the second hydrogen atom transfer and Fe
center reduction, and (iii) BH3OH– removal in four spin states (S = 0, 1,
2, and 3). G and H (in parentheses) are given in kcal/mol. (b)Optimized stationary points with selected bond lengths (Å) and the
Mulliken spin densities (ρ) for the lowest energy spin state.

－ 99 －

Ⅳ 研究業績 (2017)activation is essential for the development of novel biomimetic catalysts, and understanding the reactivation
process of NiFe hydrogenase. In this study, the mechanism for dioxygen activation using the biomimetic
model

complexof[NiLFe(η5-C5Me5)]+[NiFe]-hydrogenase,[L=

N,N’-diethyl-3,7-diazanonane-1,9-dithiolato] was established using density functional theory (DFT) andartificial force-induced reaction (AFIR) methods. Our computational results suggest that O2 binds to the FeII
center in an end-on fashion and forms a high-valent iron complex, NiFe–peroxo (NiIIFeIV(η2–O2)), which has
been experimentally observed. The O–O bond cleavage occurs in the presence of borohydride (BH4–)
through hydrogen atom transfer (HAT). Once the HAT occurs, the generated BH3 radical anion (BH3.–) binds
to the terminal oxygen of NiFe–OOH, giving rise to BH3OH– and NiIIFeIV=O. The second HAT from BH4–
to the oxygen of NiIIFeIV=O leads to BH3OH– and Fe reduced NiIIFeII complex. Importantly, the dioxygen
activation is triggered by HAT, not by proton transfer or hydride transfer. The O2 is activated by the Fe
center and the oxidation state of Fe varies during the process, while the oxidation state of Ni is conserved.
These mechanistic insights into O2 activation are essential in understanding the formation of the inactive
state and reactivation process in hydrogenase.

DFT Investigation on Electron and Hydride Transfer in NiFe Hydride Complex
(a)

(b)

promising candidate of the next
generation

of

clean

energyFe2+
H
N
N NiIIII P(OEt)3
S Fe P(OEt)3
S P(OEt)3

resource alternative to the fossil+ [Fe(III)L2]+ + [Fe(III)L2]+ + [Fe(III)L2]+

fuel which is finite and emits

ET1

undesirable

chemicalcompounds, CO2, NOx, and SOx
into

the

environment.

Thedevelopment of the catalyst
which

can

efficiently

andselectively splits or generates
thehydrogenmolecule,ishighly demanded. It is known
that

the

biologicalhydrogenase

found

0
PT1

N
N NiIITS-E–2 1 B(–3 4.1 2
6.5
)
HA
T

1E1

–38.6
(–35.9)H
N
N NiIIIII P(OEt)3
S Fe P(OEt)3
S P(OEt)3

been performed to reveal thefunctionandmechanism.

thereaction

N
N NiII

P(OEt)3I
S Fe P(OEt)3
S P(OEt)
3

2E2

TS
-E
–2 2 B(–4 6.7 1
0.4
)
HA
T

+ [Fe(II)L2]0 + [Fe(III)L2]+ + [Fe(III)L2]+–50.9(–50.0)2B2+ [Fe(II)L2H]+ + [Fe(III)L2]+ + [Fe(III)L2]+–26.7(–40.4)

2+

N
N Ni

ET4

H
Fe

S
S

–57.1
(–54.5)P(OEt)3P(OEt)3

2+

P(OEt)3

2E2

3+
H
N
N NiII
IV P(OEt)3
S Fe P(OEt)3
S P(OEt)3
1E3+ [Fe(II)L2]0 + [Fe(II)L2]0 + [Fe(II)L2]+–34.9(–35.7)

2+
PT3

TS
-E
– 3
(– 6.4 B1
23
PT .6)
4

N
N NiII

P(OEt)3P(OEt)3
S P(OEt)
3
II
S Fe

N
N Ni

+

FeIII

1B1

+ [Fe(II)L2]0 + [Fe(III)L2H]+ + [Fe(III)L2]+

(c)

Fe

P(OEt)3P(OEt)3

Fe2

II P(OEt)3
S Fe P(OEt)3
S P(OEt)

R (Fe1–H)

3

1B1+ [Fe(II)L2]0 + [Fe(II)L2]0 + [Fe(III)L2H]2+

FeII

1

2+

–31.4
(–28.7)S
S

P(OEt)3

1B1–57.1(–54.5)N
N NiII

ρ (Ni) = 0.18
ρ (Fe1) = 0.47
ρ (Fe2) = –0.81–50.9(–50.0)–34.5(–32.9)ET2

cyanobacteria can catalyze thistheoretical investigations have

1 TS-E2B1+
PT2

R1(Fe1–H) = 1.72
R2 (C–H) = 1.50

38.4
(42.2)
ET3

innumber of experimental and

Fe1

Ni

3

1B3

+ [Fe(III)L2H]2+ + [Fe(III)L2]+ + [Fe(III)L2]+

2+

enzymeprocess. For this enzyme, aC
H

0 P(OEt)3
S Fe P(OEt)3
S P(OEt)

N
N Ni

H
S
S

Fe1

P(OEt)3P(OEt)3P(OEt)3

Spin density (ρ)

a∆G [kcal/mol]is+hydrogen+Molecular

H

+

H

0.5
0

1TS-E2B1-1-1.5

R (Fe1–H) (�)Figure 2. (a) Schematic depiction of the redox states and ET, HAT and PT
reaction of interested. The most plausible pathway is represented by stickarrows. The free energy (kcal/mol) is calculated relative to complex 1A1, andenthalpy is given in parenthesis. (b) Free energy profile (kcal/mol) of HAT
with optimized TS structure (1TS-E2B1), where the selected bond lengths are
given in angstrom. (c) Plots of spin densities of two irons, Fe1 and Fe2, along
the reaction coordinate.
－ 100 －

Fe1
Fe2

-0.5

Ⅳ 研究業績 (2017)

Despite of the remarkable catalytic ability of the hydrogenase, the molecular catalyst with higher catalytic
efficiency is further demanded for the industrial application. For this purpose, it is sensible to create thecatalyst using non-precious metals such as Ni, Fe, and Mn which are involved in metalloenzymes. For thecreation of the ideal catalyst, many bio-inspired models to mimic the function of hydrogenase have beendeveloped and analyzed.
We investigated mechanistic details in formation of NiFe hydride complex and electron and hydride transfer
processes from the hydride complex using density functional theory and artificial force induced reaction
methodology. The NiFe hydride complex derived from NiFe complex ([NiII(L)FeII(MeCN)[P(OEt)3]3], L =N,N'-diethyl- 3,7-diazanonane-1,9-dithiolato) with reaction H2 is the first reported hydride complex which
conducts three reactions, electron, hydride, and proton transfers (Ogo et al. Science, 2013, 339, 682-684). In
the generated hydride complex, the hydride binds to Fe, which is different from Ni-R state in hydrogenase inwhich hydride locates between Ni and Fe. In the reaction with ferrocenium ion, our calculation suggested
that the first electron transfer occurs from NiFe hydride complex into ferrocenium ion, then the hydrogen
atom transfer takes place subsequently. The oxidation state of Fe varies during the redox process, which
differs from the NiFe hydrogenase where oxidation state of Ni varies. Singlet step hydride transfer occurs in
the presence of 10-methylacridinium ion (AcrH+) which is kinetically feasible compared with the HAT.
While, the proton transfer occurs barrierlessly from protonated diethyl ether. The revealed reaction
mechanism guides the interpretation of the catalytic cycle of NiFe hydrogenase and development of efficientbiomimetic catalyst for H2 generation and electron/hydride transfer.

2. Presentation at academic conferences(1) 伊勢川 美穂, WMC Sameera, Akhilesh K. Sharma, 小江誠司, 諸熊奎治

“ヒドロゲナーゼモ

デル錯体による水素分子活性化の理論的研究”, 第 20 回理論化学討論会, 5 月 16-18, 2017,
京都.
(2) Miho Isegawa “DFT Study on Fe(IV)-Peroxo Formation and H-Atom Transfer Triggered O2
Activation in a Bio-Inspired Model of [NiFe]-Hydrogenase”, I2CNER International Workshop,
Catalytic Materials transformation division, Feb 2, 2018, Fukuoka.

－ 101 －

Ⅳ 研究業績 (2017)

Satoshi Suzuki

Satoshi Suzuki
FIFC Fellow
1. Summary of the research of the year
1.1 チオフラビン T の発光特性について
チオフラビン T（図 1）は溶媒粘度に応答する発光分子で、低粘度の溶媒中ではほとんど蛍光を示さないのに対し、粘性の高い溶媒中では強く発光する。そのため、軸に沿った回転により非発光性の“ねじれた分子内電荷移動（TICT）状態”に到達する速度が溶媒に依存するのではな
いかと考えられている。
また、チオフラビン T はアルツハイマー病患者によく見られるアミロイドβ、特にβシート構造に強く結合し、蛍光を示す。アミロイドβと結合した際に蛍光を示すメカニズムについても、溶媒粘度依存性と同じようなメカニズムではないかと考えられる。
そこで、タンパク質環境においてどのようにチオフラビン T が発光性を獲得するのかを調査した。まず、気相での TICT 状態の構造最適化を行い、その近傍の円錐交差構造を探した。
過去の報告では、ねじれ角に対しての TDDFT による一次元 scan が行われているが円錐交差
近傍で TDDFT が正しくない振る舞いをすることがあるため、本当にそこに極小値があることは保障されない。本研究では MCSCF により円錐交差と TICT 状態の構造を最適化した。
次に、チオフラビン T とアミロイドβの結合状態での同様の計算を試みた。アミロイドβ（PDB
ID：2BEG）とチオフラビン T に対し分子ドッキングシミュレーションを行い、アミロイドβへの結合
サイトを推測した。最高ランクの構造から ONIOM(HF/6-31G(d):MM)レベルで構造最適化を行った。
気相中での計算の結果、TICT 状態の安定構造が得られた。また、この構造の近くに円錐交差（図 2）が存在することがわかった。この円錐交差は CASSCF レベルでは TICT 構造より 30ｋ
J/mol 程度高いが、それでも垂直励起状態よりはエネルギーが低い。また TICT 状態から基底状態への遷移双極子モーメントは小さく、したがって、この構造からの発光は起こりにくく、円錐交差を経由した無輻射失活が起こりやすいことがわかる。
一方、たんぱく質中（図 3a）では TICT 状態、円錐交差共に大きく不安定化されることがわかった（表）。これは、TｈT の近くにあるフェニルアラニンとの衝突を避けるためにチアゾール環が大きく変形することに由来する（図 3b）。また、TICT 状態での遷移双極子モーメントは 1 程度と大きい。結果として、円錐交差を経由した無輻射失活が起こりにくく、発光の方が起こりやすいことが説明される。

図 1 チオフラビン T－ 102 －

Ⅳ 研究業績 (2017)

N
S

NMe2

図 2 チオフラビン T の円錐交差

N
S

NMe2

図 3 a)アミロイドβ中におけるチオフラビン T の円錐交差 b)近接するフェニルアラニンから立体障害を受けて大きく歪んだ円錐交差

isolated ThT
S FC

S MIN

S /S MECI

S FC

S MIN

S /S MECI

0.0

28.1

389.1

0.0

17.5

473.1

405.5

360.3

389.2

411.9

373.3

473.3

1

S
S

0
1

表

ThT+Amyloid

1

1

0

1

1

1

0

(4,4)CASSCF/6-31G(d)による各構造のエネルギー

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, 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., 138, 8194-8206－ 103 －

Ⅳ 研究業績 (2017)(3) S.Sasaki, S.Suzuki, K. Igawa, K. Morokuma, G. Konishi,“The K-Region in Pyrenes as a Key Position to Activate Aggregation-Induced Emission:
Effects of Introducing Highly Twisted N,N-Dimethylamines”
J. Org. Chem., 2017, 82 (13), pp 6865–6873
3. Presentation at academic conferences(1) “凝集誘起発光を示すアルキルアミノアレーンにおける発光挙動の理論化学的解析”◯鈴木聡 諸熊奎治 理論化学討論会 2017(2) “凝集誘起発光を示すアルキルアミノアレーンの理論的解析と分子設計指針”◯鈴木聡 諸熊奎治 分子科学討論会 2017(3) “最小エネルギー円錐交差に着目した凝集誘起発光材料の開発：理論化学で内部転換を視る(1)” (特別企画講演・招待講演)
第 98 回日本化学会春季年会

4. Others－ 104 －

Ⅳ 研究業績 (2017)

Akhilesh Kumar Sharma
Postdoctoral Fellow
1. Summary of the research of the year 2017
1.1

Mechanism and Selectivity in PdSIPr-Catalyzed Ring-Opening and Cross-Couplingof 2-Arylaziridines with Arylboronic Acids
The strained small ring compounds such as oxiranes, aziridine, are being utilized in organic synthesis

for variety of transformations. The aziridines are important synthons for formation of variety of N-containing
compounds of synthetic importance, such as β-amino-functionalized motifs. The organometalic catalysts are
effective for regioselective and stereospecific ring-opening of aziridines. The formed adducts after
ring-opening can be further functionalized or used to generate products with regio- or chemo- orstereo-selectively. Recently, Takeda et al. reported a Pd/NHC-catalyzed enantiospecific and regioselective
ring-opening and cross-coupling of 2-arylaziridines with arylboronic acids to give β-aryl β-phenethylamine
derivatives (Scheme 1).
Incurrent

study

we

have

explored mechanism of this reaction.
Besidesstudyingmechanismofcross-coupling, we have also studied
active species generation viz., Pd(II)to Pd(0) conversion. The aziridine
ring-openingisstudiedby

Scheme 1. Stereospecific and regioselective Suzuki-Miyaura
coupling of 2-arylaziridines.

multicomponent artificial force induced reaction method (MC-AFIR) to explore possible reaction paths
systematically and explain regioselectivity and stereospecificity.
Active Catalytic Species Generation
The reaction involves first generation of active catalytic Pd(0) species. The mechanism of Pd(0)generation is not well studied in Pd-NHC catalyzed reactions. The reported computational studies propose
direct reductive elimination from catalyst or after replacement of chloride with base (O-tBu –). However, incurrent reaction we found that reductive elimination from catalyst have high activation barrier (32.3
kcal/mol). Reaction barrier for Pd(0) generation is lowered in presence of phenylboronic acid, base and water.
The highest activation barrier is for reductive elimination (TS3) from intermediate I4 (~20 kcal/mol). Hence,
the Pd(0) generation also involve mechanism similar to Suzuki-Miyaura couling reaction.
Cross-Coupling Reaction Mechanism
The different steps in the current cross-coupling reaction involve oxidative addition (aziridine ring
opening), protonation, transmetalation and reductive elimination.
From the exhaustive sampling of TSs (transition states) for aziridine ring opening, we found that oxidative
addition occurs by SN2 attack of Pd(0) to benzylic-carbon (type B) of aziridine (Fig. 1). It is important to－ 105 －

Ⅳ 研究業績 (2017)

Fig 1. Type of Transition states for the aziridine ring opening with calculated free energy inkcal/mol (Enthalpy is given in parenthesis).

note that, in the lowest energy TS phenyl group of substrate is coordinated anti to the NHC ligand andbenzylic carbon is in syn-orientation. The phenyl group of substrate helps the reaction to proceed
regioselectively. Hence, the reaction occurs through type B TSs, which lead to desired product and explains
the regioselectivity and enantiospecificity of reaction.
Regioselective aziridine ring-opening by TS type B leads to higher energy intermediate I8 (-17.1
kcal/mol, Fig. 2). The intermediate is stabilized by water through H-bonding. Upto three water molecules
were used to stabilize the intermediate, in accordance with previous study. The intermediate with two water,
I8.2H2O (-25.3 kcal/mol) is more stable. The TSs for the proton transfer involve relatively low barrier. It
leads to lower energy intermediate I9.
Next step is transmetalation, it involved coordination of PhB(OH)2 to hydroxyl group leading tointermediate I10. From I10 intermediate transmetalation occurs leading to lower energy intermediate I11.
After decoordination of B(OH)3 intermediate I12 undergo reductive elimination leading to cross-couplingproduct. The activation barrier for this process is ~15 kcal/mol. Hence, in this study we have revealed the fullmechanism of the reaction, which will be further helpful in development of the reaction.
L
Pd

H

N

Ts

‡

L

+
Pd

H

+ H
Pd
H

TS4A

‡

L

–
N Ts

O

I8

H
H
O

TS5

+2H2O

L
Pd H

N

Ts

L
H
+
Pd

H

L

H

N
–

H O

O O
S

Ar

H

–2H2O
–
N Ts
H

O H
H

O

H

Pd

I8.3H2O

+ H
Pd
H O
H

‡
L

H

H

L

H O

O

+H2O

I8.2H2O

L =SIPr

–
N Ts

HO
I9

H
N

Ts

HO

Pd

HO B
HO

Ph

H

H
N

Ts
‡
L

TS6

Pd

L
Pd

H

O

H

H
O

H

O

H

L
Pd

HO Pd

H

H
N

HO B
Ph
HO
H

H

HO

Ts

I10

L

N Ts
H

H
N

Ph
TS7

I9.3H2O

H

H

L
O

Pd

B Ph
OH

H

+
Ts

H
N

H
Ph

-51.8 (-71.1)
I11
Ts

L
Pd
Ph

H
N
P

Ts

I12
H

H
N

Ts

L Pd
H
Ph

H
N

Ts
I13

Fig 2. Free energy profile at PCMToluene/B3LYP-D3/SDD(Pd),cc-pVTZ//PCMToluene/B3LYP-D3/SDD(Pd);6-31+G(d)(B,N,O,S;6-31G(d)(C,H) for cross coupling . Relative energies are in kcal/mol.
－ 106 －

Ⅳ 研究業績 (2017)

1.2 Theoretical Study on the Mechanism of Phoshoranide-Trihydroborate Reaction withMethyl Iodide
Phoshorous-Borane, Lewis acid-base complexes are isoelectronic to C-C bond. Phoshino-Boranes are
now getting more attention as reagent, hydrogen storage material and polymer precursors, beside theirimportance in coordination chemistry. Formation of tetra- or penta-coordinated phosphorus complex withboron is difficult. The first compound (1) having trihydroborate coordinating to a pentacoordinatedphosphorus was synthesized and crystallized recently by Kano et al.. In one of recent results of Kano et al.,the reaction of trihydroborate 1 with an excess of methyl iodide (MeI) in toluene at room temperature gives a
1:1 mixture of bicylic compound 2 and the P-methylated derivative 3 (Scheme 2). Interestingly, if thereaction occurs at 100°C the P-methylated bicyclic compound 3 has been obtained exclusively without
compound 2.

Scheme 2.

In this study the mechanism of this reaction is studied through computational methods. The reaction
path was explored by AFIR (artificial force induced reaction) method available in GRRM program. The
stationary points was further optimized using Gaussian 09 program and with SMD(Toluene)/B3LYP-D3BJ/
6-311++G(2d,p), 6-311G**(for Iodine) method.
F3C CF3
O

16.6 (6.6)

Formation of intermediate 2

P

From AFIR search, fivedifferent paths were found forreaction of MeI with 1. The
lowest energy paths involve SN2
attack of hydride on methylgroup of MeI (TS1) leading toformation of methane (Fig. 3).

‡
H
B H

H
O
F3C CF3 CH3
1

TS1-2

F3C

CF3
O

I
P

F3C CF3
O

H
B H
H
O
F3C CF3
0.0 (0.0)P

kcal/mol)andthermodynamically (ΔG = 60.0
kcal/mol)lesslikelyasitinvolves formation of highly
unstable methyl-anion.
The intermediate 5 and I ¯

TS5-2

CH4, I
22.9
F3C

I-atom of MeI is kinetically68.1

H-12.2 (-5.2)

The SN2 attack of hydride on
(ΔG‡=

B

OH
F3C CF3

‡

F3C

CF3
O
H P B H
O
CF3
F3C

I

-35.1 (-34.7)
CF3 -31.6 (-24.4)
O
F3C CF3
H
O
P B
H
H
P B H
O
F3C CF3 5IO
F3C CF3 6

2-42.5 (-35.5)

Fig 3. Free energy (kcal/mol) profile for intermediate 2 formation.
Enthalpy is given in parenthesis.

－ 107 －

Ⅳ 研究業績 (2017)

can easily isomerize to intermediate 6. 6 is 3.5 kcal/mol lower in energy than 5. The intermediate 5 can also
isomerize to 2 by hydride transfer from boron to phosphorus. The activation barrier for this process is 22.9
kcal/mol leading to formation of lower energy 2. Hence, formation of 2 is thermodynamically more probableand explains the experimental detection of this intermediate (Scheme 1).
Reaction of 2 with MeI. We have further studied reaction of 2 with MeI. The process involves SN2 attack of
P on methyl group of MeI with Iodide removal. The next step involves proton abstraction from phosphorus
leading to formation of HI and product 3. The highest barrier for 2 to 3 conversion is 31.3 kcal/mol. The
attack of hydride from B-H of 2 to methyl group of MeI is 0.5 kcal/mol lower in energy. Hence, the SN2
attack by P and hydride of B will be competitive. The SN2 attack by hydrogen of phosphorus on MeI is bothkinetically and thermodynamically unfavorable. As the activation barrier for all these processes are very high(>30 kcal/mol), these processes are less likely.
Reaction of 5 with MeI. For the SN2 attack by P-atom of 5 to MeI, involve first isomerization of 5 to higher
energy species 19 with B-atom decoordinated from P-atom. The B-atom further interact with iodide formed infirst step leading to formation of 20. The reaction of MeI with 20 has 27.6 kcal/mol activation barrier and lead toformation of intermediate 21. 21 is almost of same energy as 5. Since the barrier for TS20-21 is higher than TS
5-2 (Fig. 3), this process is less likely than formation of 2.

Formation of H2
The HI formed during theprocess for formation of 3, canfurther react with the substrate (1)(Fig. 4). The HI can directly reactwith hydride and lead to formationof 11 or the proton from HI firsttransferred to oxygen leading tolower energy intermediate 12.
From 12 transfer of H fromoxygen

to

boron

lead

to

formation of 11 through 11.4

Fig. 4. Free energy (kcal/mol) profile for H2 formation. Enthalpy isgiven in parenthesis.

kcal/mol barrier. The 11 is aunique species with σ-bond of H2 interacting with empty p-orbital of B. The 11 is easily converted to 5 byremoval of H2 from B. This reaction have low barrier and lead to formation of H2 and intermediate 5. This
result agrees with experimental detection of H2 during the reaction.
In current computational study we have explained mechanism for formation of 2 and H2. Exploration
Mechanistic study for product 3 formation is currently in progress.

－ 108 －

Ⅳ 研究業績 (2017)

2. Original papers(1) Akhilesh K. Sharma, W. M. C. Sameera, Masayoshi Jin, Laksmikanta Adak, Chiemi
Okuzono, Takahiro Iwamoto, Masako Kato, Masaharu Nakamura, and Keiji Morokuma,“DFT and AFIR Study on the Mechanism and the Origin of Enantioselectivity in
Iron-Catalyzed Cross-Coupling Reactions”
J. Am. Chem. Soc. 139, 16117-16125 (2017).
(2) Miho Isegawa, Akhilesh K. Sharma, Seiji Ogo, and Keiji Morokuma,"DFT Study on Fe(IV)-Peroxo Formation and H Atom Transfer Triggered O2 Activation
by NiFe Complex”
Organometallics 37, 1534-1545 (2018).
3. Presentation at academic conferences(1) Akhilesh K. Sharma, W. M. C. Sameera, Masaharu Nakamura, Keiji Morokuma“Computational Insights on Mechanism Iron-SciOPP-Catalyzed Alkyl-Aryl Coupling
Reaction”
20th Annual Meeting of Theoretical Chemistry Society, Kyoto, May 16-18, 2017.
4. Others(1) Akhilesh K. Sharma, W. M. C. Sameera, Masaharu Nakamura, Keiji Morokuma“Theoretical Study on the Mechanism of Phoshoranide-Trihydroborate Reaction withMethyl Iodide”
The 15th symposium of Fukui Institute for Fundamental Chemistry, Kyoto, Feb. 2, 2018.

－ 109 －

Ⅳ 研究業績 (2017)

Maneeporn Puripat
ResearchResearch
Fellow (To
15 Sept. 2017)
Fellow
1. Summary of the research of the year
Theoretical Investigation of Catalytic Hydrocarboxylation of Olefins with CO2[Abstract] Carboxylic acids can be directly formed from CO2, H2, and simple olefins by using
rhodium(I) catalyst. In this reaction, the addition of iodide compounds, such as CH3I, is indispensable toincrease the yield of the product. To understand the role of the iodide additives, we studied the mechanism of
the catalytic hydrocarboxylation of cyclohexene with CO2 and H2 by using an automated reaction searchmethod, called multi-component artificial force induced reaction (MC-AFIR) method. The reaction can bedivided into two parts. First, CO and H2O is obtained from CO2 and H2 through the formation of formic acid.
Then, the CO and olefin convert to the carboxylic acid. The iodide additive plays two important roles. One is
the formation of cyclohexyl iodide to promote the oxidative addition to the rhodium(I) catalyst. Another isthe stabilization of intermediates and transition states through the interaction with phosphine ligands.

Fig. 1 Catalytic hydroxycarbonylation of olefins with CO2 and H2
catalyzed by the rhodium complex. [1][Introduction] The CO2 is an attractive C1 building block which leads carboxylic acids and theirderivatives. To establish the catalytic systems to form the carboxylic acids from CO2, the mechanicalunderstanding is indispensable. Leitner et al. reported an effective catalytic system for thehydroxycarbonylation of simple olefin with CO2 and H2 leading the carboxylic acid as shown in Fig. 1 [1]Several experimental measurements were performed to discuss the mechanism of this catalytic system. First,
it was found that the carboxylic group was constructed not by CO2 but by CO and H2O according to the
nuclear magnetic resonance spectroscopy. Second, the yield of the carboxylic acid increased dramatically by
the addition of iodide compounds, such as CH3I. Third, the formation and consumption of cyclohexyl iodide
was observed by the mass spectrometry, which implied that the role of the CH3I additive was the conversionof cyclohexene to cyclohexyl iodide and cyclohexyl iodide could be a reactant instead of cyclohexene. Forth,to discuss the effect of the intermediates, the same reaction starting from other reactants, such as cyclohexyl
iodide, cyclohexanol, and cyclohexyl acetate, were performed. Contrary to the expectation, the product yielddepended on the reactant. Cyclohexanol and cyclohexyl acetate provided high product yield as cyclohexene.
Whereas, the product yield starting from cyclohexyl iodide was only 21 %, even though cyclohexyl iodide
was assumed to be formed and consumed during the catalytic reaction. To get the more detailed insights of－ 110 －

Ⅳ 研究業績 (2017)

this catalytic system, we performed one of the methods in the Global Reaction Route Mapping (GRRM)
strategy, called the artificial force induced reaction (AFIR) method,[2] to search systematically all possible
reaction pathways. In this study, we also discuss about the role of iodide additives and the reason of the
product yield dependency on the reactants based on the calculated Gibbs free energy profile.
[Methods] First, approximate reaction pathways were explored by the MC-AFIR method, in which the
AFIR functions were minimized with γ = 300-400 kJ mol-1. The initial AFIR search was carried out at
M06-L/Def2SV level of theory. Then, all the obtained approximate local minima and transition states (TSs)were re-optimized without artificial force at the B3LYP-D3/SDD (for Rh and I) and 6-31g(d) (for otheratoms) levels. Single point energies were calculated at B3LYP-D3/SDD (for Rh and I); 6-31+g(d,p) (forother atoms) levels of theory. The solvation free energy was included by the PCM model with a dielectric
constant of 6.3 (acetic acid) for all the calculations. The intrinsic reaction coordinate (IRC) was calculated toconfirm the reaction pathway. All these AFIR search, optimizations and IRC calculations were performed
with the GRRM program[3] using energies, first, and second energy derivatives computed with theGaussian09 program.
[Results and Discussion] The reaction system can be divided into two catalytic cycles. One is for theformation of CO and H2O from CO2 and H2 (Cycle I) and the other cycle is for the producing the carboxylic
acid from CO and olefin (Cycle II). The Cycle I starts from the oxidative addition of H2 to the Rh(I) complex,
followed by the CO2 insertion. Thus, we firstly investigated about the stability and the catalytic ability of themononuclear Rh(I) complexes with different number of PPh3 ligands (RhCl(CO)n(PPh3)m: n, m = 0, 1, 2).
The reaction barrier of the oxidative addition of H2 depended on the coordination number of phosphine
ligands. The most stable complex was the Vaska-type RhCl(CO)(PPh3)2 complex, which was detected by the
NMR spectroscopy. [4] The most favorable pathway started from the dissociation of the phosphine ligandfrom the Vaska-type Rh(I) complex RhCl(CO)(PPh3)2, followed by the oxidative addition of H2. The
activation barrier of the oxidative addition of H2 to the Vaska-type complex and the following CO2 insertion,
however, was too high. To reduce the activation barrier, the CH3I additive played an important role. The
CH3I additive promoted the dissociation of one of the PPh3 ligands from the Vaska-type complex by theformation of the phosphonium iodide [Ph3P(CH3)]I. The activation barrier of the oxidative addition of H2 andinsertion of CO2 was lowered by the dissociation of PPh3 ligand from the Vaska-type complex, which wasconsistent with the experimental result that the yield reduced dramatically without addition of CH3I. [1,4]Then, the CO2 and H2 in the Rh(I) complex converted to formic acid, which can be decomposed into CO andH2O. Although, the formation of CO and H2O from CO2 and H2 (Cycle I) was the endothermic reaction, thiscatalytic reaction could take place because of the exothermicity of the following Cycle II.
The Cycle II started from the formation of the cyclohexyl iodide from cyclohexene and CH3I topromote the following oxidative addition to the Rh(I) catalyst. Then, the insertion of the CO, which was
obtained from the Cycle I, took place, followed by the transformation leading to the desired carboxylic acid.
The rate-determining step (RDS) of the overall catalytic process was the carbonylation step in Cycle I, withan activation barrier of 33.7 kcal mol-1.
It should be noted that the hydrido-Rh(III) intermediate, which was obtained by the oxidative additionof H2, could give cyclohexane (the by-product shown in Fig. 1) with the activation barrier of 35.7 kcal mol-1,－ 111 －

Ⅳ 研究業績 (2017)

which was only 2.0 kcal mol-1 higher than that of the CO2 insertion. It means that the Cycle I causes theformation of the by-product, cyclohexane. Therefore, the yield of cyclohexane could decrease by changing
the reactant from CO2 and H2 to HCOOH. It was confirmed by the experimental study. [4][Acknowledgements] This presentation is based on results obtained from a project (P16010)
commissioned by the New Energy and Industrial Technology Development Organization (NEDO).
[References][1] T.G. Ostapowicz, W. Leitner et al. Angew. Chem. Int. Ed. 52, 12119-12123 (2013).
[2] S. Maeda, K. Ohno, K. Morokuma, Phys. Chem. Chem. Phys. 15, 3683-3701 (2013).
[3] GRRM14: S. Maeda, Y. Harabuchi, Y. Osada, T. Taketsugu, K. Morokuma, and K. Ohno,
http://grrm.chem. tohoku.ac.jp/GRRM/index_e.html.
[4] T. Oku, M. Okada, M. Puripat, M. Hatanaka, K. Morokuma, J. Choi. J. CO2 Util. 25, 1-5 (2018).

2. Original papers(1) Tomoharu Oku, Masaki Okada, Maneeporn Puripat, Miho Hatanaka, Keiji Morokuma, and
Jun-ChulChoi“Promotional effect of CH3I on hydroxycarbonylation of cycloalkene using homogeneousrhodium catalysts with PPh3 ligand”
J. Co2. Util. 25, 1-5(2018).
3. Presentation at academic conferences(1) Maneeporn Puripat, Miho Hatanaka, and Keiji Morokuma“Theoretical Investigation of Catalytic Hydrocarboxylation of Olefins with CO2”
The 11th Annual Meeting of Japan Society for Molecular Science (1P095), Sendai,
September 15-18, 2017
4. Others(1) -－ 112 －

Ⅳ 研究業績 (2017)

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
今年度は電子移動錯体について研究を行った。
【序】金属サレン錯体の一電子酸化体は、金属、置換基、溶媒分子の種類によって、ラジカル中心がサレン配位子内で局在化もしくは非局在化した原子価異性状態を示し、電子状態の観点からも興味深い。Ni(II)や Mn(III)の四配位平面型錯体では、サレン内の２つの(OPh-CN)基が同じ置換基 R を持つ場合、Ni(II)では２つの(OPh-CN)間にラジカル中心が非局在化したクラス３（Robin-Day の分類）、Mn(III)では片方の(OPh-CN)に局在化したクラス
２に分類される。[1] これらの電子状態の違いと溶媒依存性について、我々は溶媒分布を積分方程式で決定する 3D-RISM 法を多参照電子状態理論の GMC-QDPT 法を組み合わせた
3D-RISM-GMC-QDPT 法を用いて、第７族３価、第１０族２価の金属のを中心に持つ一電子酸化サレン錯体について系統的に調べてきた。[2]一方、Co(II)の五配位四角錐型錯体（Fig. 1）の一電子酸化体は第７族、第１０族のものに比べて複雑な振る舞いを示し、DMSO のような強い配位性溶媒中では金属の酸化状態
CoIII(salen)が観測されるが、CH2Cl2 のような無配位性溶媒中では、L = トリフラート(OTf)
やトシル(OTs)の場合、CoIII(salen)状態とサレン配位子が酸化した状態 CoII(salen‧)+の両方の性質を示す事が、近年、実験的に明らかになっている。[3]Fig. 1: Co-salen complex
NMR 測定から三重項が基底状態である事は明らかであるが、その分解能では CoIII(salen)と CoII(salen‧)+の共存が共鳴効果（Fig. 2）と熱平衡のどちらに由来するのか、結論付けられていない。この電子状態を精査するには、多参照電子状態理論が必要不可欠であり、本研究では GMC-QDPT 法を用いて検討を行った。また溶液中での配位子 L による電子状態の違いについても調べた。

－ 113 －

Ⅳ 研究業績 (2017)【方法】CH2Cl2 溶媒中の錯体構造と溶媒和構造は 3D-RISM- DFT/M06 法で求めた[2]。また結晶構造は対称性の観点からそれを構成する最小ユニットを QM（DFT/M06）に、それ以外の周期的な部分を MM に選び、MM 分子の点電荷は QM 分子のそれから自己無撞着的に決める QM/MM 法によって決定した。[4] なお、結晶の格子定数は実験値を使用した。励起エネルギーE と振動子強度 f は、構造最適化で定めた溶媒効果、結晶効果を考慮に入れ、４状態平均(4SA) GMC-QDPT 法で求めた（Fig.2）。計算コスト削減の為、-C6H10-を-C2H4に、t-Bu を Me に置き換えてモデル化した。以下、(R1, R2) =(OMe, OMe)、(Cl, OMe)を持つ
四配位 Co 錯体を 1a、1b、配位分子 L（OH2, OTf, OTs）を持つ場合、1a-L、1b-L と称す。

Fig. 2 : Important triplet configurations in resonance.

【結果・考察】Co-salcn 錯体 1Ra-OTf の分子性結晶は OTf の配向の異なる２つの構造
1Ra-OTf-I と 1Ra-OTf-II から構成されており、salcn を salen と置き換えた両者 1a-OTf-I と
1a-OTf-I の構造は、実験値に比べて誤差 0.05Å 程度で良く再現されている。更に３重項の他、これらの１重項、５重項の構造および結晶エネルギーを DFT レベルで調べた（Table 1）。
Table 1: Geometry and stability of spin states at DFT/M06. Units are in [Å] and [kcal/mol]
Orient.
Co-O1 Co-O2 Co-N1 Co-N2
Co-L Spin(Co) EQM/MM
Calc.
1a-OTf-I
1et
1.87
1.88
1.88
1.89
1.93
24.2
3et
1.86
1.86
1.87
1.88
2.16
1.60
0.0
5et
1.87
1.88
1.99
1.99
2.09
2.99
0.8
R
Expt. 1 a-OTf-I
3et
1.86
1.83
1.87
1.88
2.12
Calc. 1a-OTf-II
1et
1.88
1.88
1.88
1.89
1.92
22.8
3et
1.85
1.87
1.87
1.87
2.17
1.63
0.0
5et
1.86
1.89
2.01
2.00
2.09
2.99
-0.2
R
Expt. 1 a-OTf-II
3et
1.84
1.86
1.87
1.87
2.13
Table 1 が示す通り、計算によって得られた３重項構造は実験結果を良く再現しているが、１重項構造は Co-L 間の距離が観測値よりも 0.2 Å ほど短く、５重項構造は Co-N 間の距離が 0.1 Å ほど長い結果となっており、理論的にも実験で測定される構造は３重項構造である事を示唆している。また DFT/M06 の計算結果によると、３重項状態は Co(III)-salen 性が60 %、Co(II)-salen•+性が 40 %という結果を示しているのに対し、５重項状態は Co(II) -salen•+
性がほぼ 100 %の割合となっている事を Co 上のスピン数が示唆している。
－ 114 －

Ⅳ 研究業績 (2017)

M06 汎関数による DFT は３重項構造を良く再現しているが、３重項構造と５重項構造のエネルギーがほぼ等しい結果となっており、３重項構造のみが観測される実験結果とは一致していない。このスピン状態についての相対安定性を調べる為に、B3LYP*、B3LYP、B3LYP-D3、B3PW91、PBE0、M06、M06-L、M06-2X、M06-HF、GMC-QDPT による相対エネルギー計算した（Table 2）。Table 2 によると１重項が３重項よりも不安定である事はどの計算レベルでも変わらないが、ハートリーフォック交換項(HF ex)の割合が少ない DFT では３重項の方が５重項よりも安定であるのに対して、HF ex の割合が増加すると５重項の方が３重項よりも安定となっている。また GMC-QDPT では DFT 計算とは異なり、５重項構造が最も不安定であるという結果になっている。
GMC-QDPT 計算によると Fig. 2 に挙げた主配置の CI 係数から算出された CoIII(salen)とCoII(salen‧+)状態は、1a-OTf-I、1a-OTf-II の両者とも 30 %と 50 %であり、実験値の 60 %と40 %[3]に近い結果が得られ、２つの構造 1a-OTf-I、1a-OTf-II の間に CoIII/CoII 性の差はな
く、CoIII と CoII の共存は共鳴効果による事が示された。
Table 2: Dependence of EQM/MM on DFT and GMC-QDPT in 1a-OTf-I. unit is in [kcal/mol].
HF ex.
1et
3et
5et
HF ex.
1et
3et
5et
B3LYP*
15 %
0.0
-15.7
-2.8
PBE0
25 %
0.0
-20.4
-16.1
B3LYP-D3
20 %
0.0
-15.0
-7.2
M06
27 %
0.0
-24.2
-23.4
B3LYP
20 %
0.0
-16.8
-8.4
M06-L
0%
0.0
-15.2
-5.4
B3PW91
20 %
0.0
-18.6
-10.9 M06-2X 54 %
0.0
-24.7
-35.5
GMC-QDPT
0.0
-16.8
20.3
M06-HF 100 %
0.0
-32.1
-49.7
次に L による電子状態の違いを調べる為、CH2Cl2 溶媒中の 1a-L（L=none, OH2, OTf-, OTs-,
OAc-）および、DMSO 溶媒中の 1a-DMSO について溶質、溶媒和構造を 3D-RISM-DFT/M06
法で求め、B3LYP-D3 汎関数で自由エネルギーを求めた。まず 1a に対して１つの配位子 Lを加えた５配位構造について調べた（Table 3）。ただし、L = OAc-の場合のみ OAc-の２つのO 原子が Co に配位した６配位構造 1a-2-OAc を取り得るため、これも比較した。
３重項状態における配位エネルギーによると配位力は OH2 < OTf- < OTs- < OAc-である事が示唆されており、この順で Co-L 間の距離も短くなっている事、この順で Co 上のスピン数が増加して Co(III)性が増加している事が分かる。
Table 3: G of 5-coordinated 1a-L at B3LYP-D3
G
Spin (Co)
L
1et
3et
5et
3et
5et
None
0.0
-6.2
-3.7
1.30
2.81
OH2
0.0
-24.1
-21.5
1.40
2.84
OTf
0.0
-19.9
-10.5
1.53
2.88
OTs
0.0
-11.3
-7.4
1.68
2.90
OAc
0.0
-4.4
-1.2
1.76
2.95
2-OAc-5.3
-2.7
-1.4
1.74
2.97
DMSO
0.0
-10.6
-5.5
1.65
2.90

－ 115 －Co-L
3et

G3et(1a-L) G3et(1a + L)[with BSSE corr.]

2.21
2.18
2.08
1.94
2.08, 2.26
2.10

-1.7
-8.8
-13.7
-14.6
-13.4
-4.7

Ⅳ 研究業績 (2017)５配位構造では３重項状態が最も安定という結果になっているが、L = OAc-の場合に
1a-OAc の３重項よりも 1a-2-OAc の１重項の方が安定な結果となっている。この事から他の L についても６配位構造と５配位構造での相対安定性の比較を行った（Table 4）。配位力が弱い OH2、OTf-、OTs-、Cl-では５配位３重項構造が安定であるが、配位力の強い OAcでは６配位１重項2 構造が安定であり、DMSO では２つの DMSO による６配位１重項構造が安定である事が分かり、この結果は実験結果に良く合っている。
Table 4: G of 6-coordinated 1a-2L vs. 5-coordinated 1a-L at B3LYP-D3
1a-2L and 1a-L + L
1et
3et
5et
1a-2L and 1a-L + L
1et
1a-2OH2
0.0-11.3-9.1 1a-2Cl
0.0
1-OH2 + OH2(1et)11.0-13.1 -10.5 1a-Cl + Cl-(1et)5.1
1a-2OTf
0.0-14.4-2.1 1a-2OAc
0.0
2
1-OTf + OTf (1et)
10.4
-17.0
-4.9 1a- -OAc + OAc (1et)-0.6
1a-OAc + OAc (1et)5.0
1a-2OTs
0.0
-1.4
4.9
1a-2DMSO
0.0
1a-OTs + OTs-(1et)
10.1
-1.7
2.8
1a-DMSO + DMSO(1et)
13.2

3et
-2.2
-3.8
4.6
2.3
0.6
1.5
2.7

5et
6.8
0.1
7.3
3.4
3.8
17.5
7.6

CH2Cl2 溶媒中の 1a-L、1b-L（L = OH2, OTf, OTs）について溶質および、溶媒和構造を3D-RISM-DFT/M06 法で求め、4SA-GMC-QDPT 計算を行った（Table 5）。1a-L（L = OH2, OTf,OTs）の場合、第一励起への f が第二、第三励起への f より非常に大きい。これは実験の吸収スペクトルが低エネルギー領域において１つのピークを示す特徴[3]と一致している。またE の実験値が OH2 (0.93 eV) < OTf (1.08 eV) < OTs (1.23 eV)の順に大きくなる傾向[3]も再現された。基底状態は、L = OH2, OTf, OTsの順に CoIII 性が増大している。しかし、Lのない 1a の基底状態では CoIII(salen)性が示されなかった。
一方、1b-OTf の場合、1.03、1.24 eV に２つのピークが実験的に観測されているが[3]、4SA-GMC-QDPT 計算でもE = 1.05、1.53 eV に２つの吸収が示され、それらの f は同程度の値となっており、実験結果を再現した。これは第一励起への f のみが大きい 1b や 1b-OH2の場合とは異なる特徴であり、共鳴効果の程度の違いから生じている。ただし 1b-OTs に関しては 1a-OTs と異なり基底状態の Co(II)性の大きな減少が見られるが、これは４状態平均
MCSCF における問題であり、平均状態数を増やすと 1b-OTf の結果に近付く事も分かった。
Table 5: Excitation energy E, oscillator strength f, and weight of CoII/CoIII character in CH2Cl2.
L
OH2

OTf

OTs

E [eV]f [au]
III/II [%]E [eV]f [au]
III/II [%]E [eV]f [au]
III/II [%]State0


9/69


33/47


46/36

1a-L
State1 State2
0.723
1.663
0.390
0.046
/78
81/
1.027
1.668
0.423
0.107
11/68
69/13
1.105
1.825
0.481
0.080
7/72
75/9

State3
2.057
0.014
70/11
2.198
0.015
31/51
2.414
0.023
37/44

－ 116 －

State0


22/60


37/42


(8/73)

1b-L
State1 State2 State3
0.936
1.540
2.076
0.349
0.075
0.020
14/67
77/
51/30
1.046
1.531
2.179
0.243
0.188
0.038
32/47
59/24
33/47
(0.889) (1.210) (1.638)(0.209) (0.178) (0.011)(31/51) (56/25) (74/10)

Ⅳ 研究業績 (2017)【引用文献】[1] T. Kurahashi and H. Fujii, J. Am. Chem. Soc. 133, 8307 (2011).
[2] S. Aono et al., J. Chem. Theory Comput. 10, 1062 (2014); Phys. Chem. Chem. Phys. 19, 16831(2017).
[3] T. Kurahashi and H. Fujii Inorg. Chem. 52, 3908 (2013).
[4] S. Aono and S. Sakaki, J. Phys. Chem. B 116, 13045 (2012).
2. 論文(1) Shinji Aono, Nakagaki Masayuki, and Shigeyoshi Sakaki" Theoretical Study of One-Electron-Oxidized Salen Complexes of Group 7(Mn(III), Tc(III), and Re(III)) and Group 10 Metals (Ni(II), Pd(II), andPt(II)) with 3D-RISM-GMC-QDPT Method: Localized vs. Delocalized Ground andExcited States in Solution”

Phys. Chem. Chem. Phys. 19, 16831-16849, (2017).
3. 学会発表(1) 青野信治○ 中垣雅之 榊茂好
７族、１０族金属サレン錯体の一電子酸化体の局在/非局在性電子状態：吸収スペ
クトルと溶媒効果
第２０回理論化学討論会 京都 2017/05/16 P29(2) 青野信治○ 中垣雅之 榊茂好「五配位四角錐型コバルトサレン錯体の局在・非局在性電子状態と吸収スペクトルにおける結晶・溶媒効果」
第１１回分子科学討論会 仙台 2017/09/17 3D08
4. その他(1) 青野信治○ 中垣雅之 榊茂好「結晶、溶媒中における五配位四角錐型コバルトサレン錯体の混合原子価電子状態と吸収スペクトル」
福井謙一京都大学第１５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 2018/2/2 P10－ 117 －

Ⅳ 研究業績 (2017)

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】ケイ素化合物は最近、遷移金属錯体類似の反応性を示すことが報告され注目されている。
例えば、ルイス塩基によって安定化されたシリレン(スキーム 1)は、室温においてフェニルシランの可逆的な S-H 結合の切断・再生反応を行う 1。
これは遷移金属における酸化付加・還元脱離反
応に類似しており触媒反応などへの応用も期待されている。ルイス塩基による始原系の安定化が可逆性に寄与していると定性的に説明されているが、どのような機構で進行するのか、何故、反応障壁が低く、又、可逆反応であるのかなど
詳細な解明は行われていない。本研究では、理論計算により反応機構と電子的過程を明らかにし、電子構造の観点から反応の理解を深め、効率的な分子設計の提案を目的とした。

スキーム１【モデル及び計算方法】実験で用いられたシリレン(a)は大きな置換基を持つことからスキーム１に示すようにモデル化(b)した。構造最適化には B3LYP-D3 法を、エネルギーの評価には SCS-MP2法を用いた。基底関数は DFT には 6-31G*を用い、SCS-MP2 法には 6-311G**を用い、SiH3Ph にdiffuse 関数を加えた。また、溶媒効果（ベンゼン）は PCM 法で考慮した。
【結果及び考察】モデル分子(b)を用い、反応経路として直接生成物に至る経路及び中間体を経由する経路を検討した(スキーム２)。孤立系でのギブズエネルギー変化を図１に示す。最も安定な遷移状態(TSSi-Si)において、Si1-Si2 結合長は 2.348Å と生成物の結合長(2.359Å)に非常に近い。一方、解離する水素原子はシランケイ素(Si2)からは 1.715 Å、シリレンケイ素(Si1)からは 1.972 Å に位置しており、シリレンケイ素との結合は形成されていないことから Si1-Si2 結合生成は Si1-H2 結合生成に先行して起こる。また P 原子は生成物ではシリレンケイ素からは解離するが、遷移状態での Si1-P
結合長(2.285 Å)は反応物(2.334 Å)よりも短い。エネ
ルギーに SCS-MP2 法を用
い、溶媒効果を加えた反応
障壁は 25.6 kcal/mol であり、室温で起こるという実験結果と矛盾しない。以降、この遷移状態に関して考察を
行う。
スキーム２
－ 118 －

Ⅳ 研究業績 (2017)

図１

1b の複数の反応経路の Gibbs エネルギー変化

ルイス塩基を持たないシリレン(c)の遷移
構造及びエネルギー変化を図２に示す。cの遷移状態(TS1c-2c)では、Si1-Si2 結合長は
TS1b-2b よりわずかに長い(2.383Å)。一方、
Si1-H2 = 1684Å、Si2-H2 = 1760Å と Si1-H2
結合は Si1-Si2 結合と協奏的に生成される。
この違いは H2 原子が TS1b-2b では Si1-N の図２

1c の構造及び Gibbs エネルギー変化

σ*軌道に配位するのに対し、TS1c-2c では Si1 の空の p 軌道に配位することに由来する。
遷移状態近傍の IRC に沿った結合変(a) Reaction of 1b(b) Reaction of 1c化及び電荷変化を図３に示す。1b から
IRC ≈ 4.0 に進むに従って Si1-P 結合長は僅かに減少するが Si1-P 結合長距離は増加する。これは負電荷をもった H2 原子が Si-Nσ*軌道に作用するためである。また遷移状態近傍でシラン側に負電
荷、シリレン側に正電荷の電荷移動が起こる。これらの結合・電荷の変化は次のように理解できる。初めに Si1 の非共有電子対によって Si1-Si2 結合が生成されSi2 が５配位構造をとる(スキーム 3a)。
その後、Si1-H2 結合が生成され Si1 が５配位構造をとり(スキーム 3b)、最後に

図３

IRC に沿った反応座標の結合及び電荷変化

ルイス塩基(P)が解離する(スキーム 3c)。
これらはルイス塩基が配位したシリレンに特徴的な反応機構であり、1c ではその特徴は見られない(図 3b)。
スキーム 3－ 119 －

Ⅳ 研究業績 (2017)

ルイス塩基が活性化エネルギーに及ぼす影響を調べるため、強さの異なるルイス塩基をもつシリレン(1b, 1d, 1ex, x = CF3, CH3, Pr, Et)と塩基を持たない 1c の反応エネルギー及び活性化エネルギーを求めた(表１)。ルイス塩基とシリレンの結合エネルギー(∆ESi-L)は 1eCF3 < 1e CH3 < 1ePr < 1e Et < 1b <1d の順序で強くなり、その結果始原系が安定化されるため同様の順序で反応エネルギーが正へシフトする。一方、活性化エネルギーはルイス塩基が配位することにより 1c(18.4 kcal/mol)に比べ増加する。
弱いルイス塩基が配位した 1eCF3 が最も高く(30.0 kcal/mol), 1ePr で最も低くなる(21.2 kcal/mol)が,より強い塩基である 1b(25.6 kcal/mol)や 1d(24.4 kcal/mol)では再び増加する。これは電子供与であるルイス
塩基が配位することにより遷移状態におけるシリレン→シランの電荷移動が促進され，より安定化するためと考えられる。

表１.

様々なルイス塩基を用いた反応エネエネルギー(∆G°),[a] 活性化エネルギー (∆G°‡),[a] LP 軌

道エネルギー(εLP),[b] 及び シリレンとルイス塩基の結合エネルギー(∆ESi-L)( in kcal/mol)。
Compound

−L

1c

1eCF3

1eCH3

-H

−P(CF3)2−P(CH3)2−10.895.3

εLP∆ESi-L
∆Gº

‡

∆Gº

18.4
−24.6

30.0

1ePr

1eEt

1b

1d

−8.80

−8.04

−7.99

−7.83

−9.85

14.2

17.5

18.2

18.9

38.8

24.4

[c]

24.4

[c]

4.3

26.3

−25.1

−14.4

21.2
−11.6

−8.9

25.6

−9.8

-1

[a] SCS-MP2/6-311G** (in kcal mol ). [b] The εLP (in eV) was evaluated for free Lewis-base at the levelof Hartree-Fock/6-311G**; see Scheme S2 in SI. [c] These values differ from those of Figure 1 because
SCS-MP2-calculated values are presented here.
カルベン(N-heterocyclic carbine, NHC)は非常に強いルイス塩基であり、カルベンの配位したシリレン(1d)の反応は吸熱的(∆G° = 4.3 kcal
mol-1)になる。生成物の構造を見ると、リン化合物のルイス塩基とは異なり Si1 は N-Si1-H2
を C3 軸とした C 両三角錐 5 配位構造をとっている(図 4)。1b と同様に活性化エネルギーが低く、また反応エネルギーが大きく異なる

図４ 1d の構造及び Gibbs エネルギー変化

ことから 1d に関しても 1b 同様に詳細な検討を行う。
より低い活性化エネルギーの達成のため、フェニルシランへの置換基導入の効果を検討した。フェニル基のパラ位により強い電子吸引基を導入することにより、反応エネルギーと活性化エネルギ
ーはともに低下する(CH3 > Ph ≳ PhFp ≳ PhCNp > PhNO2p) (表 2)。従って 1b と H3SiPhNO2p を反応させた場合の活性化エネルギーは∆G°‡ = 19.1 kcal mol-1 まで低下し反応の進行が期待されるが、反応－ 120 －

Ⅳ 研究業績 (2017)

エネルギーは∆G° = -13.4 kcal mol-1 と大きく発熱的になることから逆反応は起こりにくくなる。一方、
1d と H3SiPh の反応は吸熱的であることから、H3SiPhNO2p を用いた時には∆G°‡ = 19.2 kcal mol-1、∆G°= -0.8 kcal mol-1 と可逆的な酸化還元反応が期待できる。

表 2. フェニルシランの置換基導入による反応エネルギー (∆G°)及び活性化エネルギー (∆G°‡)変化(in kcal/mol)。
−X

CH3

Ph

PhFp

PhCNp

PhNO2pA) silylene complex with a phosphine ligand (1b)
∆Gº‡

31.3

25.6

24.7

22.7

19.1

∆Gº

−6.6

−9.8

−10.3

−10.6

−13.4

B) silylene complex with a NHC ligand (1d)
∆Gº‡

32.3

24.4

24.2

21.5

19.2

∆Gº

8.9

4.3

4.3

3.0

−0.8

96.9

97.1

94.8

93.3

C) Bond energies of reactants
Si2-H2

93.7

D) Bond energies of products
Si1-H2

88.8

88.3

88.8

88.8

88.8

Si1-Si2

72.5

77.5

78.1

75.9

77.8

Si-C 結合の活性化は一般的に Si-H 結合の活性化よりも困難であるが重要な反応であることから、メチル基(−CH3)、ビニル基(−CH=CH2)、エチニル基(−C≡CH)をもつトリメトキシシラン(TMS)を用いて検討を行った。1b と TMS の Si-C 結合の活性化エネルギーG°‡は −CH3 > −CH=CH2 > −C≡CH
基の順に低下していき、HC≡C-Si(OMe)3 では∆G°‡ = 26.4 kcal mol-1 とフェニルシランの Si-H 結合の活性化エネルギー(25.6 kcal mol-1)と近い値が得られた(表 3)。従って HC≡C-Si(OMe)3 の Si-C 結合はルイス塩基安定化シリレンを用いることで温和な反応条件下での切断が期待できる。Si-C 結合の活性化反応の遷移状態(TS1b-4b)においても Si-H 結合の遷移状態(TS1b-2b)と類似した構造の特徴が見られた(図 5)。Si1-Si2 結合は既に形成されており (2.300 Å)、Si1-C 結合(2.487 Å)は Si2-C 結合(2.283 Å)
よりも長くエチニル基はシランケイ素(Si1)に近い。生成物(4b)において Si-P 結合は 2.318Å と Si1 原子から解離しておらず、Si1 は N-Si-C を C3 軸とする両三角錐の５配位構造をとる(図 5)。
表３. 1b 及び 1d とメチル-, ビニル-, エチニル-トリメトキシシランとの Si-C 結合の反応エネルギー(∆G°)及び活性化エネルギー (∆G°‡) 及び遷移状態における歪み(DE)・相互作用(INT)エネルギー(inkcal/mol)。
A) phosphine ligand (1b)B) NHC ligand (1d)

−R

−CH3

−CH=CH2

−C≡CH

−CH3

−CH=CH2

−C≡CH

∆Gº‡

45.4

34.9

26.4

45.1

37.1

24.3

∆Gº

9.6

4.1

3.4

15.7

8.8

4.2

DE(silane)

71.5

67.7

73.5

74.3

71.5

78.1

DE(silylene)

7.7

7.9

7.8

12.3

12.9

13.4

INT

52.4

56.0

72.5

58.3

63.1

82.8

－ 121 －

Ⅳ 研究業績 (2017)

遷移構造における歪みエネルギー及び相互作用エネルギーの解析から HC≡C-Si(OMe)3ではメチル基やビニル基に比べ、エチニル基とシランの間の相互作用エネルギーが大きい(72.5 kcal mol-1)ことが分かった。これはエチニル基によって求電子性が増したために、シリレン→シラン(Si1→Si2)の電荷移動相互作用が増加したと考えられる。実際、エチニ
1b とエチニル-トリメトキシシランの反応のル基のもつ電荷は、反応物から遷移状態に

図5

向かうにつれて−0.55 e から−0.70 e へと増加

構造及び Gibbs エネルギー変化

し、これはメチル基(−0.52e から−0.60 e)やビニル基(−0.51 e から−0.60 e)の増加量と比べて大きい。
遷移状態や生成物において、５配位構造である Si1 は陰イオン的であることから、最も電子吸引的であるエチニル基が Si1 の安定化に最も寄与すると考えられる。1d を用いた場合、HC≡C-Si(OMe)3の Si-C 結合の活性化エネルギーは 24.3 kcal/mol であり、1b の活性化エネルギー(26.4 kcal/mol)よりも低く Si-C 結合の活性化反応により有効であると考えられる。
本研究によりルイス塩基安定化シリレンの可逆的な Si-H 結合活性化反応の反応機構を明らかにした。本反応では、ルイス塩基をもたないシリレンでは見られない遷移状態におけるシリレン→シランの電荷移動相互作用が活性化エネルギーの減少に寄与している。このことから、ルイス塩基の選択やフェニルシランへの電子吸引性置換基の導入により活性化エネルギーを下げることができることを示した。また同様の反応機構により、ルイス塩基安定化シリレンを用いたエチニルトリメ
トキシシランの Si-C 結合の活性化反応の可能性を理論的に示唆した。
【文献】[1] R. Rodriguez et al., Angew. Chem. Int. Ed., 55, 14355 (2016).

2. 論文(1) Masayuki Nakagaki, Antoine Baceiredo, Tsuyoshi Kato, and Shigeyoshi Sakaki“Reversible Oxidative Addition/Reductive Elimination of Si-H bondto Base-stabilized
Silylenes: A Theoretical Insight”
Chem. Eur. J., accepted3. 学会発表(1) 中垣 雅之，Ricardo Rodriguez，加藤 剛，榊茂好「ルイス塩基安定化シリレン分子を用いた可逆的 Si-Si(H)結合生成反応の機構解
明と制御」
第 20 回理論化学討論会, 京都, 2017/5/16-18, P28 ポスター
(2) 中垣雅之, 中谷直輝, 榊茂好「金属多重結合錯体の分子内電荷移動励起状態の理論的研究」
第 11 回分子科学討論会 2017 仙台, 仙台, 2017/9/15-18 2P94 ポスター
(3) 青野信二, 中垣雅之, 榊茂好－ 122 －

Ⅳ 研究業績 (2017)「五配位四角錐型コバルトサレン錯体の局在・非局在性電子状態と吸収スペクトルにおける結晶・溶媒効果」
第 11 回分子科学討論会 2017 仙台, 仙台, 2017/9/15-18 3D08 口頭
4. その他(1) 中垣 雅之， Antoine Baceiredo，加藤 剛，榊茂好「ルイス塩基安定化シリレン分子を用いたSi-H結合の可逆的酸化的付加/還元的脱離反応の機構解明と制御」
第15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, 2018/2/2－ 123 －

Ⅳ 研究業績 (2017)

Jing Lu
FIFC
Fellow
FIFC Fellow
1. Summary of the research of the year
Catalytic ability of Ru13@Pt42 and Pt55 toward oxygen reduction reaction: a DFT study
Proton exchange membrane fuel cells (PEMFCs) are regarded as a leading candidate of clean andsustainable energy source to cope with the growing energy need and environmental concern. Pt-based
clusters/particles have attracted immense interest in catalysis for oxygen reduction reaction (ORR, 1/2O2 +2H+ + 2e- → H2O) at the cathode in PEMFCs. Pt alloys with core-shell structure (M@Pt) is expected to be
useful for the new generation ORR catalyst due to their higher activity and lower cost than pure Pt. In ourprevious work, 55-atom Pt-based particles were investigated. For bimetallic Pt42Ru13 cluster, theicosahedron-like core-shell structure (Ru13@Pt42) exhibited much higher stability than the non-core-shellstructures (Ptcore-1Ru12@Pt41Ruedge and Ptcore-1Ru12@Pt41Ruvertex). Furthermore, the potential of Ru13@Pt42 asless expensive catalyst for ORR was predicted. However, the current knowledge of catalytic performance of
Ru13@Pt42 and Pt55 for ORR and corresponding reaction mechanism is rather limited. In this work, thepreferential sites on the Pt42 surface for interaction with oxygen species (O2, OH, O, and OOH), as well as
possible mechanism of O-O bond activation catalyzed by Ru13@Pt42 and Pt55 were studied using
first-principle calculations.
All spin-polarized calculations were performed with the Vienna Ab initio Simulation Package (VASP).
The PBE-D3 method was employed for geometry optimizations with an energy cutoff of 400 eV. The clusters
were placed in a sufficiently large supercell (25 Å × 25 Å × 25 Å) to ensure enough separation by vacuum.
The thresholds for energy and force were set to 0.0001 eV and 0.01 eV/Å, respectively. Reaction barrier was
calculated using Nudged Elastic Band (NEB) method.

Scheme 1. (a) Models of 55-atom icosahedron-like cluster (green: core-1; red: core-2; blue: vertex; grey:edge). (b) Binding sites of icosahedron-like Pt42 shell.
Binding sites. As shown in Scheme 1, there are 20 triangular facets on the Pt42 surface of－ 124 －

Ⅳ 研究業績 (2017)

icosahedron-like 55-atom cluster. On each facet, there are three types of binding sites: top (t), bridge (b), andhollow (h) sites. The binding site notations are illustrated as follows: Top site: adsorbate binds with one Pt atom at the edge or vertex position, denoted as t1 or t2.
 Bridge site: adsorbate binds with two adjacent Pt atoms at the edge and vertex positions, or at bothedge positions, denoted as b1 or b2.
 Hollow site: fcc-like position between three Pt atoms at the edge positions, denoted as h1; hcp-likeposition between both Pt atoms at the edge positions and one Pt atom at the vertex position, denoted as h2.
Binding energy (Eb) is defined as the energy difference between the species adsorbed on the catalyst
and the sum of the catalyst and species. The more negative Eb value indicates the stronger binding ability.
O2 binding. The binding energy (Eb) for O2 adsorption at different sites is listed in Table 1. In the caseof Pt55 and Ru13@Pt42, Eb(O2) value decreases in the order of h1–η1 > t1-η1 > t2-η1 > b2-η2 > b1-η2 and h1-η1> b2-η2 > t1-η1 > t2-η1 > b1-η2, respectively. The O2 species are found to migrate from h2-η1 to t2-η1. The
expression of “A/x” (A = adsorbate, x = binding site) represents that the adsorbate is located at the x sitehereafter. Obviously, O2 is preferentially adsorbed at the b1 site with η2-side-on orientation (O2/b1-η2). The
Eb(O2/b1-η2) values are -1.70 eV and -0.95 eV for Pt55 and Ru13@Pt42, respectively. The most stable
O2/b1-η2-binding species will be further discussed as the initial structure for the process of O-O bondactivation, O2 → O.
Notably, Eb(O2) for Ru13@Pt42 is less negative than that for Pt55 at the same site, indicating that theO2-binding ability of Ru13@Pt42 catalyst is weaker than that of Pt55. These results suggest that the O2
adsorption on the Pt42 surface is significantly influenced by the presence of Ru13 core. The reason for thestronger O2 adsorption on the surface of Pt55 than Ru13@Pt42 will be elucidated in the latter section.
Table 1 Binding energies (Eb, in eV) for O2 and OOH/x-binding species.
Site xPt55

Ru13@Pt42

Pt55

O2

Ru13@Pt42
OOH

1-1.05 (11et)a-0.37 (9et)-4.18 (10et)-3.57 (6et)t2-η1-1.13 (13et)-0.72 (7et)-4.30 (14et)-3.98 (6et)

1

h1–η

-0.25 (13et)

0.42 (7et)-3.75 (14et)-3.15 (8et)

h2–η1

t2-η1

t2-η1

t2-η1

t2-η1

b1-η2

-1.70 (11et)-0.95 (7et)-b-3.89 (6et)b2-η2-1.41 (11et)-0.19 (9et)

t1-η1

t1-η1

t1-η

a

The most stable spin state is given in parentheses.

b

OOH decomposes into O and OH at the top sites, where O is connected at t2 site and OH is connected at t1 site.

OOH-binding. The OOH-binding species is one of the important intermediates for ORR process. As
listed in Table 1, the stability of OOH/x-binding species increases in the order of OOH/h1-η1 < OOH/t1-η1 <OOH/t2-η1 for Pt55 and OOH/h1-η2 < OOH/t1-η1 < OOH/b1-η1 < OOH/t2-η1 for Ru13@Pt42, respectively.
The adsorbed OOH at the h2 (b2) site could be easily converted to t2 (t1) site. For Pt55, OOH-binding at the－ 125 －

Ⅳ 研究業績 (2017)

b1 site with η2-side-on orientation is unstable. Spontaneously, OOH decomposes into O and OH, where O
and OH are located at the t2 and t1 sites, respectively. Also we found that the OOH-binding with Ru13@Pt42
is weaker than that with Pt55 at the same adsorption site.
O-binding. Single O atom is preferentially adsorbed at the fcc-like h1 site with Eb(O/h1) of -5.01 eV
and -4.41 eV for Pt55 and Ru13@Pt42, respectively, as listed in Table 2. For Pt55, the Eb(O) decreases in theorder of O/t1 > O/t2 > O/b1 > O/h2 > O/h1. The adsorbed O atom at the b2 site could easily slide off to
hcp-like h2 site due to the minuscule activation barrier of the reaction pathway between b2 and h2 sites. For
Ru13@Pt42, the Eb decreases in the following order: O/t1 > O/b1 > O/t2 > O/h2 > O/h1. The O atom migrates
from b2 to h2 site, similar to the Pt55 case discussed above. The binding ability of single O at the same site on
the surface of Ru13@Pt42 is found to be weaker than that of Pt55.
OH-binding. For OH-binding, the ability increases in the order of OH/h1 < OH/t1 < OH/t2 ≈ OH/b1
for Pt55 and OH/h1 < OH/t1 < OH/b1 < OH/t2 for Ru13@Pt42, respectively. Both t2 and b1 sites are proved tobe the preferred sites for Pt55 with Eb of -3.35 eV and -3.38 eV, respectively, while only t2 is the mostfavorable site for Ru13@Pt42 with Eb(OH/t2) of -3.06 eV, as listed in Table 2. Similarly, the ability to bindwith OH species in the case of Ru13@Pt42 is weaker than that of Pt55. The weak OH and O-binding aredesirable because it is advantageous for H2O desorption.
H-binding. In order to discuss the whole ORR mechanism, it is likely that Had is available as areactant on the surface as discussed in previous results. As shown in Table 2, b1 is the preferred site with
Eb(H/b1) of -3.07 eV for Pt55 and -2.70 eV for Ru13@Pt42, respectively. The H-binding ability increases in
the orders of h1 ≈ t2 < t1 < h2 < b1 for Pt55 and t1 < t2 < h1 < h2 < b1 for Ru13@Pt42, respectively.
Table 2 Binding energies (Eb, in eV) for O, OH, and H/x-binding species.
Site xPt55
Ru13@Pt42
Pt55
Ru13@Pt42
O

a

a

OH

Pt55

b

Ru13@Pt42
Hct1-4.14 (15et)-3.30 (9et)-3.19 (12et)-2.59 (6et)-2.95 (12et)-2.45 (8et)t2-4.46 (15et)-4.25 (7et)-3.35 (12et)-3.06 (6et)-2.77 (14et)-2.55 (6et)h1-5.01 (11et)-4.41 (7et)-2.94 (14et)-2.35 (8et)-2.76 (14et)-2.60 (8et)h2-4.91 (11et)-4.33 (7et)t2

t2-3.00 (12et)-2.63 (8et)b1-4.84 (13et)-4.22 (9et)-3.38 (10et)-2.86 (8et)-3.07 (12et)-2.70 (8et)bc

O migrates from b2 to hcp-like h2. OH migrates from b2 to fcc-like h1. H migrates from b2 to hcp-like h2.

O2 adsorption The band structure is one of important factors to explain the ability of O2 adsorption.
The calculated d-band center for Ru13@Pt42 (-2.18 eV) is lower than that for Pt55 (-2.02 eV), indicating theweaker O2 binding for Ru13@Pt42 compared with Pt55, with reference to the prediction of Hammer-Nørskov
model. The density of states (DOS) analysis for Pt55, Ru13@Pt42 and corresponding O2/(b1-η2)-binding
species was shown in Figure 1. d-DOS of Pt42 shell makes a large contribution to the total d-DOS for Pt55,
Ru13@Pt42, and their corresponding O2/(b1-η2)-binding species. O2 binding decreases the DOS of band-top
near the Fermi level, suggesting that the CT occurs from Pt55 (Ru13@Pt42) to O2 fragments.
O-O bond activation. The O-O bond activation (cleavage) can occur via two mechanisms: one isdirect O-O bond cleavage of O2 (O2→2O), and the other is OOH formation followed by O-OH cleavage－ 126 －

Ⅳ 研究業績 (2017)(O2+H→OOH→OH+O). Direct O-O bond cleavage of O2 is difficult to occur with the activation barrier of
0.49 eV and 0.33 eV in gas phase for Ru13@Pt42 and Pt55, respectively. However, the O-OH bond cleavage of
OOH occurs with lower activation barriers of 0.18 eV and 0.12 eV for Ru13@Pt42 and Pt55, respectively.

Pt55

Pt55-O2/b1-η2

Ru13@Pt42

Ru13@Pt42-O2/b1-η2

Figure 1 Density of states for Pt55, Ru13@Pt42, and their corresponding O2/(b1-η2)-binding species.
These results reveal that Ru13@Pt42 is capable of activating O2 molecule but does not bind with oxygen
species too strongly, which leads to facile and rapid H2O desorption. In addition, the O-OH bond cleavage inthe case of Ru13@Pt42 occurs easier than that of Pt55. Such characteristic behaviors of Ru13@Pt42 could render
it potentiality as a promising heterogeneous catalyst for ORR like Pt55.

2. Original papers(1) Jing LU, Kazuya ISHIMURA, and Shigeyoshi SAKAKI,“Theoretical Insight into Core–Shell Preference for Bimetallic Pt-M (M = Ru, Rh, Os, andIr) Cluster and Its Electronic Structure.”
J. Phys. Chem. C 122 (16), 9081-9090 (2018).
3. Presentation at academic conferences(1) Jing LU, Kazuya ISHIMURA, and Shigeyoshi SAKAKI,“Understanding segregation behavior and electronic structures in 38, 55 and 147-atombimetallic Pt-Tc and Pt-Re nanoclusters: a first-principles study”
The 11th Annual Meeting of the Japan Society for Molecular Science (2P107), Sendai,
September 15–18, 2017

－ 127 －

Ⅳ 研究業績 (2017)

Rong-Lin Zhong
Rong-Lin Zhong
Research Fellow
Research Fellow
1. Summary of the research of the year
How to Perform Suzuki-Miyaura Reaction of Nitroarene or Nitration of Bromoarene Using
Pd0(Phosphine) Complex: Theoretical Insight and Prediction
The Pd-catalyzed Suzuki-Miyaura reaction is one of the most efficient and versatile methods
for constructing carbon-carbon bond. Aryl halides are employed as electrophilic coupling reagent inthis reaction. To broaden its application scope, a lot of efforts have been made to use alternative
compounds such as aryl ethers, aryl esters, and arenols. However, the use of nitroarenes has notbeen succeeded for a long time despite of weak Ar-NO2 (Ar = aryl) bond. Notably, theSuzuki-Miyaura reaction of nitroarenes was very recently succeeded by us using Pd0(BrettPhos) asa catalyst, as shown in Scheme 1. Usual monodentate phosphine could not be used in this reaction.
On the other hand, Fors and Buchwald succeeded Pd-catalyzed nitration of aryl halides using asimilar Pd0(tBu-BrettPhos) as a catalyst. In this reaction, the last step should be reductive
elimination of Ar-NO2 bond from PdII(Ar)(NO2)(tBu-BrettPhos). This is reverse to the oxidative
addition of Ar-NO2 which is the first step of the Suzuki-Miyaura reaction. Considering these tworeports by Buchwald group and us, we address following points; (1) why the Ar-NO2 bond cleavage
is more difficult than the Ar-Br bond cleavage, (2) why usual monodentate phosphine could not be
used for the Suzuki-Miyaura reaction of nitroarenes but BrettPhos could be, (3) why Brettphos wasused for the Suzuki-Miyaura reaction of nitroarenes but the similar tBu-BrettPhos was used for thenitration of aryl halides despite of tiny difference between these two phosphines. We theoreticallyinvestigated the oxidative addition of nitroarene to Pd0(BrettPhos) to elucidate characteristicfeatures of the oxidative addition of nitroarenes and to provide clear answers to theabove-mentioned questions.
Scheme 1. The Suzuki-Miyaura reaction of nitroarenes and nitration of aryl halides.

BrettPhos, PMe3, R-BrettPhos (R = tBu, Me, CF3, C6F5, o-tol, and 2,6-dimethylphenyl), XPhos,and BrettPhos-NMe2 were investigated as ligand. The molecular structures of these ligands are－ 128 －

Ⅳ 研究業績 (2017)shown in Scheme 2. As nitroarene, 4-nitroanisole (Rea) was employed for calculations because thiscompound was used as a typical reagent in the experiment of the Suzuki-Miyaura reaction.
Scheme 2. Molecular structures of BrettPhos and R-BrettPhos (R = tBu, Me, CF3, C6F5, o-tol, and2,6-dimethylphenyl), XPhos, and BrettPhos-NMe2.

Figure 1. Optimized geometries in oxidative addition of 4-nitroanisole to Pd0(BrettPhos) complex.

Results and Discussion
Oxidative Addition of 4-nitroanisole (Rea) and its Bromo derivative to Pd0(BrettPhos) and
Pd0(PMe3)2. The geometry and energy change of oxidative addition of Rea to Pd0(BrettPhos) 1 isshown in Figure 1. Rea approaches 1 to form stable η2-coordinated adducts, AD1a#1 and AD1a#2,
in which the C2-C3 and C1-C2 bonds coordinate with the Pd, respectively. The oxidative addition
occurs through a three-membered transition state TS1a to afford a palladium(II) complex
PdII(NO2)(C6H4-OMep)(Brettphos) (PRD1a). The Gibbs activation energy (∆Gº‡) is 30.3 kcal mol-1
and the Gibbs reaction energy (∆Gº(R)) is -2.1 kcal mol-1 relative to the most stable reactant adductAD1a#1. This oxidative addition needs rather large activation energy but it is exergonic.
Oxidative addition of 4-bromoanisole (Reb) to 1 occurs through similar η2-coordinatedadducts and transition state to afford a palladium(II) complex PdII(Br)(C6H4OMep)(Brettphos). The－ 129 －

Ⅳ 研究業績 (2017)∆Gº‡ (16.3 kcal mol-1) is much smaller and the ∆Gº(R) (-15.0 kcal mol-1) is much more negative thanthose of the oxidative addition of Rea. Therefore, the oxidative addition of nitroarene is much moredifficult than that of bromoarene kinetically and thermodynamically. To investigate the difference in∆Gº‡ between these two oxidative additions, we separated the reaction system into Pd0(BrettPhos)and substrate moieties, as shown in Scheme 3, and made deformation/interaction energy analysis.
As shown in Table 1, the potential energy barrier (Ea) is much larger for TS1a than for TS1b,
indicating that the analysis of Ea provides the reason why the oxidative addition of Rea is moredifficult than that of Reb. In TS1a, the deformation energy (EDef = 33.2 kcal mol-1) of Rea is muchlarger than that (6.2 kcal mol-1) of Reb in TS1b. Interaction energy EInt is defined as a stabilizationenergy provided by the interaction between reagent (Rea or Reb) and Pd0 complex, where bothhave deformed geometries like in TS. The EInt (-42.1 kcal mol-1) between Rea and Pd0(BrettPhos)in TS1a is much larger than that (-24.6 kcal mol-1) in TS1b by 17.5 kcal mol-1, where a negativevalue means the stabilization energy. However, this large EInt of TS1a cannot overcome the overly
large EDef of Rea at TS1a. As a result, TS1a becomes higher in energy than TS1b. These results
lead to a conclusion that the large EDef of Rea is the origin of larger Ea and larger ∆Gº‡ for Ar-NO2
bond cleavage than those for Ar-Br bond cleavage. In TS1a, the NO2 group changes its direction
toward the Pd because the sp2 orbital of NO2 must change its direction to form a bonding interaction
with the Pd, which gives rise to the large EDef value of Rea. On the other hand, Br has a sphericalvalence orbital which can start to form the bonding interaction with the Pd, keeping the Ar-Br
bonding interaction. Therefore, Reb can reach TS1b without significant distortion. This is thereason why bromoarene is more reactive for the oxidative addition than nitroarene.
Scheme 3. Definition of fragments a and b in TS1a (R=NO2), TS1b (R=Br), and TS3a.
MeO

Cy
MeO

P

a

R

Cy
Pd
iPr

OMe

a

iPr

iPr

MeO
NO2
Pd

b

b

Me3P

PMe3

TS3a

TS1a/TS1b

Table 1. Activation barrier (Ea), deformation energy (EDef) of each moiety and interaction energy(Eint) between them in transition state (in kcal mol-1).
TS1a

TS1b

TS2a

TS3a

∆E

-4.2

-14.1

-2.4

15.9

Ea

31.3

16.9

30.1

30.2

EDef-a 33.2

6.2

33.0

35.5

EDef-b

4.3

5.4

19.9

4.7

－ 130 －

Ⅳ 研究業績 (2017)

Oxidative addition of Rea to Pd0(PMe3)2 3 was investigated for making comparison between
BrettPhos and usual monodentate phosphine PMe3. This reaction occurs with ∆G°‡ of 29.1 kcal
mol-1. Though this value does not differ very much from that of the reaction with 1, its transition
state TS3a is at much higher energy than the sum of reactants, 3 + Rea, indicating that Rea moreeasily dissociates from 3 than it completes the oxidative addition via TS3a. Thus, it is concluded
that the oxidative addition of Rea to 3 does not occur.
The deformation/interaction energy analysis clearly shows that the higher energy transition
state TS3a arises from the larger EDef value (19.0 kcal mol-1) of Pd0(PMe3)2 in TS3a (Table 1). The
large EDef-a value arises from significantly small P-Pd-P angle in TS3a (Figure 1). It is ofimportance to elucidate the reason why such large distortion is needed in TS3a. In the oxidative
addition, CT from metal moiety to substrate is important. In TS1a, charge-transfer (CT) occurs
from the HOMO of Pd (φPd-HOMO) to the LUMO and LUMO+1 of Rea, as shown in Figure 2. The
0
φPd-HOMO at high energy can form large CT. As shown in Figure 3(a), the φPd-HOMO of Pd (PMe3)2 in
equilibrium geometry is calculated at much lower energy (-7.81 eV) than that (-5.82 eV) ofPd0(BrettPhos). To raise the φPd-HOMO energy, Pd0(PMe3)2 must be distorted by decreasing the P-Pd-P
angle; as shown in Figure 3(a), the φPd-HOMO energy certainly becomes higher (-5.73 eV) in the
distorted geometry of TS3a.

Figure 2. Orbital interactions in the transition state of the oxidative addition of 4-nitroanisole (a)and 4-bromoanisole (b) to Pd0(BrettPhos).
On the other hand, Pd0(BrettPhos) is distorted little at TS1a. The reason can be easily found byseeing Figure 3(b). In the case of BrettPhos, the lone pair orbital on the P atom and the π orbital on
the phenyl group overlap with the Pd dπ orbital in an antibonding way to afford the φPd-HOMO of 1. As aresult, the φPd-HOMO orbital energy is -5.82 eV in Pd0(BrettPhos) even with equilibrium geometry. It
indicates that the 2,4,6-tris-isopropylphenyl group plays crucially important role to raise the dπ
orbital energy like usual chelating diphosphine. It is concluded that the oxidative addition of
Ar-NO2 to Pd0(PR3)2 is difficult because the transition state suffers from two large deformationenergies of Ar-NO2 and Pd0(PR3)2 moieties. On the other hand, Pd0(Brettphos) is reactive for theoxidative addition of Ar-NO2 because the dπ orbital is at high energy even without distortion of－ 131 －

Ⅳ 研究業績 (2017)

Pd0(Brettphos) and the transition state suffers from only one deformation energy of the Ar-NO2
moiety. This means that the presence of 2,4,6-tris-isopropylphenyl group is crucially important in
BrettPhos because its π orbital interacts with the Pd dπ orbital to raise the φPd-HOMO energy (Figure 3b).
It is a strong point of BrettPhos-type ligand for the oxidative addition that both of phosphine lonepair and π orbital of 2,4,6-tris-isopropylpheny participate in raising the φPd-HOMO energy.

Figure 3. HOMOs of PPh3, BrettPhos, and their Pd0 complexes with deformed structure in TS.
Comparison between Pd0(BrettPhos) and Pd0(tBu-BrettPhos). Oxidative addition of Rea to
Pd0(tBu-BrettPhos) 2 occurs through similar geometry changes. The ∆Gº‡ value (28.3 kcal mol-1) ismoderately smaller than that to 1 but the ∆Gº(R) is positive (5.8 kcal mol-1), indicating that theoxidative addition of Ar-NO2 bond to 2 is endergonic. This means that 2 can be applied to the
reductive elimination of nitroarenes, which is consitent with the fact that the nitration of aryl halides
was succeeded with 2, as was reported by Fors and Buchwald. As shown in Table 2, thedeformation energy in TS2a differs little from that in TS1a but the interaction energy is moderately
less negative than in TS1a. As results, TS2a is moderately less stable than TS1a. These results
suggest that not the electronic factor but the steric factor is responsible for the positive ∆Gº(R) of theoxidative addition of Rea to Pd0(tBu-BrettPhos). In PRD2a, the P(tBu)2 moiety of tBu-BrettPhos
takes the cis-position to the C6H4OMep group to induce the steric repulsion, whereas such steric
repulsion is small in TS2a because the C6H4OMep group is distant from tBu-BrettPhos. The larger
steric repulsion of tBu-BrettPhos is supported by the longer Pd-P bond length (2.393 Å) in PRD2athan in PRD1a (2.319 Å) and the larger P-Pd-(C6H4OMep) angle (99°) in PRD2a than in PRD1a(90°). The larger cone angle of P(tBu3)3 than that of PCy3 is also one evidence that P(tBu)2 group oft
Bu-BrettPhos is more bulky than PCy2 group of BrettPhos. Because the steric effect of the tBu
group is larger than that of the Cy group, the tBu-Brettphos gives rise to the larger steric repulsion
with the C6H4OMep group to destabilize PRD2a compared to PRD1a. It should be concluded that
Pd0(tBu-BrettPhos) is advantageous for the reductive elimination of Ar-NO2 because of the large
steric repulsion of tBu-Brettphos with the C6H4OMep group.
2. Original papers(1) M. Ramu Yadav, Masahiro Nagaoka, Myuto Kashihara, Rong-Lin Zhong, Takanori Miyazaki－ 132 －

Ⅳ 研究業績 (2017)

Shigeyoshi Sakaki, and Yoshiaki Nakao, “The Suzuki–Miyaura Coupling of Nitroarenes”，J. Am.
Chem. Soc., 139 (28), 9423–9426 (2017).
(2) Feng-Wei Gao, Rong-Lin Zhong, Hong-Liang Xu, and Zhong-Min Su, “Intra- andIntermolecular Charge Transfer in a Novel Dimer: Cooperatively Enhancing Second-Order Optical
Nonlinearity”，J. Phys. Chem. C, 121 (45), 25472–25478 (2017).
3. Presentation at academic conferences(1) Rong-Lin Zhong, Masahiro Nagaoka, Yoshiaki Nakao, and Shigeyoshi Sakaki, “NewOxidative Addition of Nitrobenzene to Palladium(0) Complex: Characteristic Features in Electronic
Process”, 20th Annual Meeting of Theoretical Chemistry Society, Kyoto, May 16-18, 2017.

(2) Rong-Lin Zhong, Masahiro Nagaoka, Yoshiaki Nakao, Shigeyoshi Sakaki “Oxidative
Addition of Nitrobenzene to Palladium(0) Complex: Theoretical Analysis of Unexpected Ligand
Effect”, 11th Annual Meeting of Japan Society for Molecular Science, Sendai, Sep.15-18, 2017.

－ 133 －

Ⅳ 研究業績 (2017)

Takahide Matsuoka
松岡貴英
松岡
貴英

Research Fellow
研究フェロー

元研究フェロー
1. 今年度の研究の要約
水分子の自動イオン化の背景にある非断熱電子動力学
近年の高強度レーザーの発展により，アト秒スケールの電子ダイナミックスの観測が可能となり，汎用性のある理論計算手法の確立が求められている．強光子場中の分子系はHighorder Harmonic Generation 機構と Above Threshold Ionization を考慮するために外場と電子，電子と核，電子間の動的相互作用を同等に扱ってイオン化過程を記述する必要がある．我々は，非断熱電子動力学計算手法[1]にイオン化過程を記述する方法[2]を盛り込み，
強光子場中の H2 と H2O 分子のイオン化過程における非断熱相互作用の影響を明らかにした[3]．強光子場中の高励起状態の光電子スペクトルは Auger 過程によって複雑化するが，2s を空孔とした H2O+を具体例に電子動力学を追跡し，その過程における Auger 効果を調べた．
非断熱電子動力学計算では電子基底Φ� で展開した電子波束Ψ��� � ∑� �� ���Φ� の係数についての coupled equation に従って時間発展する[1]．
����

���

���� �� � � ���� � �� ������� �

���
�� �
��
�
�� � ���� � ����� � ����� �� ���4�

Figure 1. HF 基底密度行列の対角成分（色付き太線）と自然軌道の電子占有数（黒の実線）．

－ 134 －

Ⅳ 研究業績 (2017)� ���� , �� , �� はそれぞれ電子
Hamiltonian と１次と２次の kinetic
coupling ��� � �Φ� ��� Φ� �, ��� ��Φ� ���� Φ� �である．本計算ではcomplex natural orbitals (CNO)によるイオン化過程の記述の試み[2]のため，各時刻における CNO を一電子軌道とした配置関数を基底とし，電子占有数が大きい CNO を被占軌道とした参照配置空間を用いた．H2O+の 2a1 軌道(O(2s))を空孔 Figure 2. 各時刻における電子 flux．(a1-c1) 境界面におけるとした断熱電子状態を t = 0 におけ flux. (a2-c2) 境界面のノルム方向の flux. 点線は OH 結合方向．
る電子状態とし，核は反対称伸縮
モードを初期運動とした．初期の電子状態が単一断熱電子状態であるから，核には全対称の力が働く．図 1 の各 CNO の電子占有数�� は 0.8 fs から 1.5 fs に至るまでに，2a�� (O[2s])と4a�� が上昇し，1b�� (O[2px])と3a�� (O[2pz])が減少している．ここで，各時刻における HF 軌

道は初期の HF 軌道との連続性を考慮した上でその既約表現にチルダを付している．反対
称伸縮方向の核の運動によって1b�� → 2a�� への失活と3a�� → 4a�� への励起が誘起される(Process A)．1.5 fs から 2.0 fs においては， 全対称の核の運動によって3a�� → 1b�� への失活と4a�� → 2b�� への励起が誘起される(Process B)．2.0 fs から 2.4 fs では，1b�� → 2a�� の失活と3a�� → 2b�� の励起が全対称の核の運動によって誘起される(Process C)．初期の電子状態の主配置から Process B が起こり難いことから，Process A と B は連続して誘起され，Process Aが生じなかった重ね合わせ状態に Process C が誘起されると言える．Process B と C は全対
称の核の運動によって誘起され，この時刻において電子 flux は OH 結合方向へ強く見られることが分かった（図 2）．H2O の 2 電子イオン化過程のうち直接イオン化と自動イオン化の 2 段階過程では自動イオン化電子は OH 結合方向に分布する[4]．本計算結果は，2 段
階イオン化過程における自動イオン化電子の分布と一致し，その自動イオン化過程は反対
称伸縮振動モードによって誘起されることを示す．
[1] K. Takatsuka, T. Yonehara, K. Hanasaki and Y. Arasaki, “Chemical Theory Beyond
the Born-Oppenheimer Paradigm: Nonadiabatic Electronic and Nuclear Dynamics in Chemical
Reactions.” (World Scientific, 2014).
[2] K. Takatsuka, J. Phys. B: At. Mol. Opt. Phys. 47, 124038 (2014).
[3] T. Matsuoka and K. Takatsuka, J. Chem. Phys. 146, 134114 (2017).
[4] H. Sann, et al., Phys. Rev. Lett. 106, 133001 (2011).

高強度レーザー中の非断熱電子波束の対称性の破れ
断熱状態が密集する高励起状態において核と外場の非断熱相互作用が電子波束の対称性－ 135 －

Ⅳ 研究業績 (2017)へ及ぼす影響に着目し，電子波束の対称性の破れがいかに観測されるかに着目した.
Semiclassical Ehrenfest theory では核は force matrix の期待値の，path-branching 法ではforce matrix の固有値の運動方程式に従う.
����

��

���� � ��� ��� � �
� ��

�

����

����

���

�
�
����
��� � ��� ���� � �� ���� ��� �� � �
�
�
�

���

�

�
�
��� ��� ���� �� ���
���� ��� �� �� � �� �� �� �� ��� .

第 3 項の Lorentz-like force が核の速度と垂直に見かけ上の力として働き，対称性の破れを誘起する[2].特に path へ分岐する際には結合方程式と運動方向の force matrix∑� ���� ���の交差項がゼロであることが要請され，結合方程式の固有状態個々の force 期待値からLorentz-like force の働き方を調べることができる．特に縮重している状態は断熱状態の円錐
交差と同様に� − �平面を定義できる．
��
��
1
���∗
���
���∗
���
�� � �� �� ���� �� � � �� ���� �� �,��������� � �1,��� �,2������ � �

�������∗ � ������ �� ,�������� � �1,��� �.

��

核が seam に沿って運動している場合に�と�は任意に入れ替えることが可能で対称性が破れる方向を�に選ぶことが可能である.
基底状態の H2O に波長� = 800 nm 強度� = 225 TW/cm2 の 3-cycle パルスを照射した系を計算した．レーザーの分極
方向は C2 軸に，核の初期運動は対称
伸縮振動モード方向に設定した．外場によって電子波束は多くの状態へ広く分布し，レーザーのピーク (� = 5 fs)に
Figure 3. (a)結合方程式の固有値．各固有状態の(b)変角振動
おいて 550 eV 程度離れた状態へも分布
モードと(c)対象伸縮振動モードと(d)反対称伸縮振動モードを示す(図 3a). これは電子と親イオン方向の加速度．濃淡は各固有状態と電子波束の重なりの大の再衝突による内殻空孔状態への励起
きさを表す．
を示している.図 4 の HF 軌道基底の一電子密度行列の 1a1 軌道対角成分はレー
ザーピークにおいて減少する.各状態に働く力は変角振動モード成分(図 3b)と対
称伸縮振動(図 3c)モード成分が主である
が，レーザーピーク近傍以降は，反対称伸縮振動モード成分が非ゼロである状態が出現する(図 3d). Lorentz-like force によFigure 4. HF 軌道基底の密度行列成分．
－ 136 －

Ⅳ 研究業績 (2017)

る見かけ上の力は相殺するように対称性が破れる方向に働くことがわかる．これは密集す
る多くの状態に波束が分布し，それらの状態の Lorentz-like force が反対称伸縮振動モード
方向の力としてあらわれていることによる．
[1] T. Matsuoka and K. Takatsuka, J. Chem. Phys. 146, 134114 (2017).
[2] K. Takatsuka, J. Chem. Phys. 146, 084312 (2017).

2. Original papers(1) Takahide Matsuoka, and Kazuo Takatsuka,“Nonadiabatic electron wavepacket dynamics behind molecular autoionization”
J. Chem. Phys. 148, 014106 (2018).
3. Presentation at academic conferences(1) 松岡貴英・高塚和夫「水分子のイオン化の背景にある非断熱電子動力学：Auger 電子と高強度レーザーによる光電子について」
第 20 回理論化学討論会 新宿 2017/5/17 2L14
(2) Takahide Matsuoka, and Kazuo Takatsuka,“Auger Decay Process in Water Molecule: A Nonadiabatic Electron Dynamics Treatment”
2nd International Symposium on Attosecond Science (P4), Wako, Aug. 26, 2017(3) 松岡貴英・高塚和夫「高強度レーザー中の非断熱電子波束の対称性の破れについて」
第 11 回分子科学討論会 2017 仙台 2017/9/17 3A05

－ 137 －

Ⅳ 研究業績 (2017)

山本憲太郎
山本 憲太郎
研究フェロー（高塚グループ）
研究フェロー（高塚グループ）

１．今年度の研究の要約
今年度は，Mn を含む触媒系における非断熱動力学的な電荷分離の基底状態の機構の理論的研究を行った．
【序】生化学的にはしばしば，生物系における電子伝
達はいくつかの分子を基底状態で逐次的に経由すると理解されている．たとえば天然光合成系のphotosystem II (PSII) における水分解では，P680←tyrosine Z←Mn cluster←水の順に電子が移動するとされている．しかしながら，量子力学的には，このような逐次的な電子移動の機構は自明ではない．そこで本研究では，生物系から着想を得た単純な系に対する非断熱の電子波束動力学の解析から，このような逐次的な電子移動の機構を提案した．

Fig. 1. Bio-inspired model system.

【方法】 Fig. 1 に示すような，PSII の tyrosine Z (YZ) から着想を得た単純な model
system を考える．EA1 = electron acceptor 1 (semiquinone cation), EA2 = electron
acceptor 2 (4-methylphenol), PA = proton acceptor (imidazole), W = water (OH),そして EPD = electron–proton donor (Mn(OH)OH2) からなる. System 全体としてcation であり, 初期状態では, charge は EA1 上に局在する．PSII の YZ 周辺における逐次的な電子移動 (P680 ← YZ ← Mn cluster) は, 本研究の system では EA1 ←EA2 ← EPD のそれに相当する．動力学計算は，path-branching representation に基づく.[1] この理論では，量子的な電子波束が，原子核の経路に沿って時間発展する．
この方法では，原子核と電子の動的なカップリングを，あらわに考慮する．事前の静的な解析に基づいて，EA1←EA2 の electron transfer が起こる直前を初期構造とする．

Fig. 2. Selected snapshots of the unpaired electron density along the path of electron-wavepacket dynamics.
－ 138 －

Ⅳ 研究業績 (2017)

その後，EA1 が離脱しつつ，EPD が EA2 および W に衝突するように初期運動量を与える．
初期の電子波束は，断熱基底状態とする．
【結論】Fig. 2 に示すある典型的な path に沿った unpaired electron density の空間分布の時間変化のスナップショットを用いて，proton と electron の dynamics を概観
する. 最初の約 10 fs の間に, PA ← EA2 の proton transfer に伴って，EA1 ← EA2の electron transfer が起こる. これに伴って，EA1 と EA2 上に，biradical state が生じる. このとき, EA1 ← EPD の proton および electron transfer は, ほとんど見られない. これは単純に, EA1 と EPD の距離が離れているためだと考えられる. その後,
EPD が W および EA2 に接近する. このとき, EA1 は徐々に離脱する. この間, 電子状態に重要な変化はない. そして t = 50 fs 付近で, EA2←EPD の electron transfer だけが起こり, 同じ donor-acceptor 間での proton transfer は起こらない. ただし，ほぼ同じタイミングで EA2←PA の proton transfer が起こっており, これが electrontransfer と couple しているように見える．最後に, t = 125 fs 付近の HT1–H T2–H T3 が関 与 す る PA←EA2←W←EPD の proton relay-transfer が 起 こ る . 以 上 の proton–
electron coupled dynamics の結果として, 実効的に, PA←EPD の proton transfer,
EA1←EPD の electron transfer がなされる．Electron-wavepacket は全体を通して，
ground state が支配的である．これは生化学的な描像と一致する. しかしながら，主に proton の運動と couple して，電子状態の性質が変化する．したがって，この場合の逐次的な電子移動は，proton transfer に伴って非断熱領域を断熱的に通過することに対応する．よって，分子構造の変化に伴う複数の電子状態の変化をあらわに考慮しなけ
れば，この電子移動の機構は理解できない．
本研究は，生物学的な電子移動のさらなる理解のためには，静的な情報だけではなく，それぞれの donor-acceptor pair の運動と，それに伴う複数の電子状態の変化をあらわに追跡する必要があることを示唆する．今年度は，このような dynamics の詳細に加えて，複数の電子状態が反応経路に沿ってどのように絡み合うか，そして励起状態で見出されていた類似の電荷分離の機構[2, 3]との関係などについて議論した．
【参考文献】[1] T. Yonehara, K. Hanaksaki, and K. Takatsuka, Chem. Rev. 112, 499 (2012).
[2] K. Yamamoto and K. Takatsuka, Chem. Phys. 475, 39 (2016) (perspective).
[3] K. Yamamoto and K. Takatsuka, ChemPhysChem 18, 537 (2017).
2. 論文(1) Kentaro YAMAMOTO and Kazuo TAKATSUKA,“"On the photocatalytic cycle of water splitting with small manganese oxides and the rolesof water clusters as direct sources of oxygen molecules”
Phys. Chem. Chem. Phys. 20, 12229-12240 (2018)3. 学会発表－ 139 －

Ⅳ 研究業績 (2017)(1) 山本憲太郎，高塚和夫「電子波束動力学的な電荷分離の機構によって駆動される Mn 酸化物中の水の光分解サイクル」第 20 回理論化学討論会, 京都 2017/5/16-18 2L16.
(2) 山本憲太郎，高塚和夫「生物系から着想を得た単純な系における衝突誘起の逐次的な電子移動; 非断熱の電子波束による研究」第 11 回分子科学討論会, 仙台 2017/9/15-18 2D03.
(3) Kentaro Yamamoto and Kazuo Takatsuka“Photocatalytic cycle of water splitting with small
manganese oxides and water clusters as source of oxygen molecules”, 第 15 回京都大学福井謙一記念研究センターシンポジウム, Kyoto, Japan 2018/2/2 P17.
(4) Kentaro Yamamoto and Kazuo Takatsuka“Photocatalytic cycle of water splitting with small
manganese oxides and the roles of water cluster as a direct resource of oxygen molecules”,
The 58th Sanibel Symposium, St. Simons Island, Georgia, 2018/2/18-23 5P13.

－ 140 －

Ⅳ 研究業績 (2017)

新崎
新崎

康樹
康樹

研究フェロー（高塚グループ）

研究フェロー（高塚グループ）
1. 今年度の研究の要約
今年度はホウ素クラスター系における、個々の断熱状態が意味をなくすほど強く非断熱相互作用する電子状態およびそれを反応場ととらえた場合の動力学の理論研究を行った。
【序】

これまで電子状態の断熱描像、その描像における非断熱相互作用は化学反応の解釈に重要な役割を果たしてきた。一方で分子に内在する非断熱相互作用や外場によるその制御の研究が進むにつれて、従来の断熱電子状態という描像ではとらえきれないような状態を考える可能性が出てきた。
そのような電子状態を反応場として利用する新規な化学反応の開発に繋げたい。
【方法論】

原子核の時間発展と同時に、多くの断熱電子状態が強く相互作用する電子状態が時間発展する系を理論計算により取り扱いたい。まずはそのような扱いを最も簡単に実現できる半古典エーレンフェスト理論による動力学計算を行う。ここでは断熱電子状態ではなく、電子の配置状態関数（CSF）を基底として電子状態を展開し、その展開係数

を時間発展させることで非断熱相互作用の強い系を必ずしも断熱状態で記述することなく扱う。
(1)

原子核座標

はその電子状態の平均場フォースに駆動されるとする。
(2)

平均場フォースは(3)によって計算される（最後の項は CSF 基底ハミルトニアンの空間微分）。このとき電子、原子核の時間発展はともに CSF 間の相互作用行列要素(4)の影響を受ける。電子状態、核座標の時間発展は影響を強く受ける。

－ 141 －、

非対角項による CSF 間の混合のⅣ 研究業績 (2017)【ホウ素クラスターによる電子混合状態の検討】 ホウ素原子は電子が 5 つであり、2p 軌道に電子が１つの基底配置をとる。そのためホウ素クラスターでは多数の安定な励起状態が密に存在し、電子励起状態では原子核の運動にともない非断熱相互作用により電子状態が強く混合される。そのような励起状態での動力学は少数の断熱状態とその間の相互作用と解釈するよりは、個々の断熱状態が区別できない混合状態と解釈することが妥当であることが先行研究で示唆されている[1,2]。本研究ではまずこの新規な状態の特徴を動力学計算から探った。B6、B12 クラスターで非断熱相互作用を含
む時間発展と仮想的な断熱時間発展との比較により、非断熱相互作用がなければ解離する条件の軌跡であっても、頻繁に強く非断熱相互作用することによって解離が阻害される場合のあることが確認できた（図１）。これは実効的には強い非断熱相互作用が存在する場合にのみ、原子核運動によって維持される「結合状態」ととらえることができる。

図１

B12 クラスターで断熱時間発展では解離する（左）が非断熱相互作用により束縛される（右）例。

【反応場としての電子混合状態】 さらに、上記のような非断熱相互作用によって維持される励起状態
クラスターを反応場とした場合の特徴を検討するために、B12 クラスターに N2、Be2、Mg2 を添加した場合の動力学を調べた。B12 クラスターの自由度の高い電子状態が N2 の強い結合を弱め、あるいは Be2、Mg2 の弱い結合を強める場合があることが見られる。このような働きを含め、電子混合状態における反応を特徴づける指標やその法則性の検討を現在進めている（図２）。

図２

Mg2B12 クラスターの初期断熱状態（#1、#97、#528）別の電子エネルギーと総原子価の時間発展。

－ 142 －

Ⅳ 研究業績 (2017)【参考文献】[1] T. Yonehara and K. Takatsuka, J. Chem. Phys. 137, 22A520 (2012).
[2] T. Yonehara and K. Takatsuka, J. Chem. Phys. 144, 164304 (2016).

2. 論文(1) Yasuki ARASAKI and Kazuo TAKATSUKA,“Time-resolved photoelectron signals from bifurcating electron wavepackets
propagated across conical intersection in path-branching dynamics”
Chem. Phys. 493, 42-48(2017).

－ 143 －

Ⅳ 研究業績 (2017)

６．日本学術振興会外国人特別研究員
Xue-Feng Ren

Xue-Feng Ren
JSPS Fellow
Research
Fellow
1. Summary of the research of the year
Computational Insights into the Non-radiative Deactivation Pathways of phosphorescentPt(�) EmitterFor emitters, a large radiative rate constant (kr) and a small non-radiative rate constant (knr) arehighly pursued to achieve high quantum yield. With the development of phosphorescent materials,
great success has been achieved on revealing radiative process by the discussions of the absorption
spectra, spin-orbit coupling (SOC) matrix elements in the Tm→Sn transition, and energy gaps
between E(Tm) and E(Sn). However, revealing the non-radiative decay is intrinsically more difficult,since it involves possibilities of the internal conversion (IC) and intersystem crossing (ISC). The
non-radiative decay efficiently takes place between two nearly degenerate electronic states.
Regarding phosphorescence quantum yield, the intensive competition between the emission from thelocal minimum of T1 state and non-radiative pathway to the singlet ground electronic state S0 through
MESX point. Therefore, the geometry and energy of MESX between the lowest triplet excited state(T1) and the ground state (S0) should play a key role in intersystem crossing.
Recently, a new type of Pt emitting materials with high color purity and improved quantum
yields (Φ) by replacing the ppy ligand of complex 1 with tpy moiety (ppy=2-phenylpyridine,
dmpt=4,5-dimethyl-3-phenylthiazol, as shown in Fig. 1). The Φ of complex 2 has been greatly
improved by 0.57, while it is only 0.01 of complex 1. Though the analyses by Escudero andco-workers, the kr (Tem→S0) of complex 1 is 2.730×103(s-1), thus the non-radiative decay is
crucially responsible for explaining the low Φ. Therefore, to effectively and accurately estimate theemission behavior, a deep understanding of the mechanism of non-radiative decay is a great demand.
In this work, we will investigate the geometry and energy of MESX between the lowest lying triplet
excited state (T1) and the ground state (S0). After that, the mechanism of non-radiative decay ofcomplex 1 and complex 2 will be analyzed to reveal how the dmpt
(dmpt=4,5-dimethyl-3-phenylthiazole) ligand influences the decay process. Based on the above
analyzes, some valuable information for promising emitters with difficulty in non-radiative decay
will be provided.
S
N

Pt

O

N

O

Pt

O
O

complex 1: (ppy)Pt(dbm)Φ<0.01complex 2: (dmpt)Pt(dbm)Φ=0.57

Fig. 1. Structures of studied complexes: 1: (ppy)Pt(dbm) and complex 2: (dmpt)Pt(dbm),
together with the quantum yield.
Computational details－ 144 －

Ⅳ 研究業績 (2017)

The ground-state equilibrium geometries (S0) of studied complexes were fully optimized
utilizing by M06L functional. Unrestricted Kohn-Sham DFT (UKS) was applied to optimize thelocal minimum geometries of T1 state. The minimum energy seams of crossings (MESXs) between
T1 and S0 were explored by single-component artificial force induced reaction (SC-AFIR) method
associated with the seam model function (SMF). After SC-AFIR search on SMF surfaces, MESXs
were fully optimized by UM06L method without artificial force. To study the mechanism of thermal
deactivations, the TS geometries between T1-M1 and MESX were optimized by UM06L functional.
After verification of vibrational frequency, the connection between the T1-M1 and MESX througheach TSs were confirmed by the intrinsic reaction coordinate (IRC) calculations. All the
calculations were performed with the development version of the GRRM program combined with
the Gaussian 09 electronic structure calculation program.
Results:
The non-radiative decay process of complex 1

The non-radiative decay process of complex 2-165.54271.43269.80(3MLCT/3LCdbm)(3MLCT/3LCdbm)h
3(3MLCT/3LCdbm)

T1-M1

160.05147.433( MLCT/ LCdbm)
N(3MLCT/3LCdbm)

151.23-174.38Pt
O2 O1

Φ2=Pt-O2-C3-C4 C

3

C4

C1
C5

110.78TS1S

Φ1=Pt-O1-C1-C2
C2

Φ3=C1-C5-C3-C4

134.33

157.31-98.0
TS2

The results revealed that the MESX of complex 1 had out-of-plane bending of phenyl moiety,which low energy was compared with the T1 state at Frank-Condon (FC). While for complex 2, the
MESX had two phenyl rings bent out of plane, which was higher than T1 at FC by 20.6kJ/mol. Theenergy barrier of most favorable deactivation process from 3MLCT/3LCdbm state to triplet
metal-centered (3MC) character of complex 1 was 29.46 kJ/mol, while the energy barrier of decay
process of complex 2 was 42.76 kJ/mol. Clearly, the non-radiative decay process of complex 2cannot easily take place, which can explain the great improvement of the observed quantum yields－ 145 －

Ⅳ 研究業績 (2017)(Φ=0.57) relative to complex 1 (Φ<0.01).
The ways to improve emission quantum yield
The kinetics of quenching is determined by the energies of MESXs and TSs connecting the
FC and the MESXs. We tried to modify ligands to improve emission quantum yield. To improve theemissive behavior, one successful approach is to import the -CN at the dbm ligand. The MESX ofdesigned complex (239.73 kJ/mol) is higher than the T1 state at FC (224.3 kJ/mol). Furthermore, alarge energy barrier is necessary (47.29 kJ/mol) from the T1 state to go over the MESX. Therefore,
the non-radiative decay is difficult for designed complex, which means that the phosphorescentprocess might be dominant.
Original papers
Xue Feng Ren, Satoshi Suzuki, Pedro J. Castro Pelaez, Satoshi Maeda, Keiji Morokuma,“Computational Insights into the Non-radiative Deactivation Pathways of phosphorescent Pt(�)Emitter”, In preparation.
2. Presentation at academic conferences(1) Xue Feng Ren and Keiji Morokumma“The potential energy surface of non-radiative process: a type of Pt emitters”, The 11th
Annual Meeting of Japan Society for Molecular Science, 2017,9,15-18, Tohoku university,
Poster－ 146 －

Ⅳ 研究業績 (2017)７．日本学術振興会特別研究員

Rei Matsuzaki
Matsuzaki
Rei
JSPS Fellow
FIFC Fellow
1. Summary of the research of the year
Flux analysis of nonadiabatic electron transfer reaction in LiF
Nonadiabatic transition is one of the key notions with which to comprehend sudden transition ofmolecular states on the way of chemical reactions such as radiation less decay from an electronic excitedstate, and so on. Among many nonadiabatic dynamics, intra- and intermolecular electron transfers throughthe so-called avoided crossing are particularly interesting, in which potential surfaces of ionic and covalentcharacter mutually avoid-cross at a relatively long interatomic distance such as LiF ↔ Li� F � or NaI ↔

Na� I � . Since the nonadiabatic transitions are ultrafast process, direct experimental observation of theinstance of the passing of quantum wavepackets across the crossing regions still face technical difficulties
and limitations. Therefore, theoretical studies can play a vital role to explore the hidden features of

nonadiabatic dynamics, which may in turn give a guiding principle of experimental studies. We have
performed a flux analysis of full quantum mechanical dynamics of a nonadiabatic electron transfer process inthe system of LiF ↔ Li� F � and interesting features of electron flow have observed. We also have surveyed

a flux-flux correlation between nuclear and electronic motion, which clearly exposes the deviation from theBorn-Oppenheimer dynamics in a quantitative manner.

Here, we calculated the electronic and nuclear wave function of LiF by using the Born-Huang
expansion within the two states model. We set the initial state as well localized gauss type wave packet on
the first excited state (the covalent state). Then, we evaluated the electronic flux ���, �, �� and nuclear flux
���, �, �� from the wave function. � is electron coordinate in the molecular frame and � is internuclear

distance. In our coordinate F atom is located at � � �0,0,0� and Li atom is located at � � �0,0, ��. To

extract sufficient characteristic features of the electron flux, we introduce the reduced quantity�� ��, �� � � �� � ���, �, �����

Figures 1 shows the reduced quantity �� ��, ��. Starting at � � 0 fs and up to about � � �0 fs, theelectron flux represented in �� have almost zero values, since the nonadiabatic interaction is very weak inthis region. At � � �0 fs, the nuclear wavepacket enters the crossing region (the potential crossing at� � �����) and the electronic flux a large there. This nonadiabatic reaction can be expressed as LiF →Li� F � thereby representing the electron transfer from Li to F. Passing across the nonadiabatic transition at� � �0 fs, �� oscillates as a function of Q. We will discuss these oscillations later. At � � ��0 fs, thenuclear wave packet turns back because of attractive ionic potential and the electron flux occurs again with
the inverse reaction (Li� F � → LiF).

－ 147 －

Ⅳ 研究業績 (2017)

Figure 1. The reduced electron flux �� ��, ��.

We analyze this spatiotemporal oscillation of Figure 1 and its physical implication. In terms of the

Born-Huang expansion, the electron flux can be rewritten as���, �, �� ���� ��� �� � ��� ��� ��Im ���∗ ��, ���� ��, ���,�� ��

where ��� is matrix element of electron flux between two electronic states. In this expression, the diagonalterm vanishes. Recall that the nuclear wave packets χ� and χ� run on the different potential curves (theionic and covalent potential curves) and the product χ�∗ �� may show a complicated phase and amplitude

variations in space time as long as the interfere coherently. Figure 1 is seen to reflect such an interference
pattern between the two wavefunctions with weighting factor of ����� . Here, we want to emphasize thatthe electron transfer dynamics is far from a simple and uniform flow.

Finally, we studied the correlation of the electronic and nuclear fluxes. The adiabatic approximation

assumes that electrons in a molecule instantaneously follow and adjust the nuclear dynamics. It is widely
known through that this is not actually the case, since electrons can only move with finite speed, which gives
the physical foundation of nonadiabatic transition. Our task here is to quantify the deviation of the actualdynamics from the Born-Oppenheimer limit. To figure out the extent of this deviation from the view point offlux analysis, we consider the following flux-flux correlation function between electronic and nuclear
dynamics
��t� � � ���� ��� ������ ���� � ��� ��� �����,�,where the operators ��� ���� � and ��� ��� � are defined as the operator form of the reduced flux �� ��, �� and�� ��, ��, respectively. In Figure 2 (a) ���� are shown for the current LiF dynamics along with thetime-variation of the state populations as plotted in panel (b). These two panels share the same time
coordinate (horizontal one). Figure 2(a) shows that during the time-interval from � � � fs and � � �� fs,���� takes only values close to zero, because the dynamics is nearly adiabatic in this region. Then the firstlarge negative peak is observed around � � �� fs. After all a total of four major groups of significant peaks

are seen in the correlation function in Figure 2(a); (A) negative peak around � � �� fs, (B) negative one

around � � ��� fs－ 148 －

Ⅳ 研究業績 (2017), (C) transition from negative to positive one around ‫ ݐ‬ൌ ͵ͷͲ fs, and (D) negative peak around ‫ ݐ‬ൌ ͶͺͲ fs.
The peaks (A), (B) and (D) are all associated with the nonadiabatic crossings, as identified in the panel (b).

The origin of the peak (C) is obviously different from the others. In the current calculation, the nonadiabatic
electron transfer has been induced in the vicinity of the inner turning point and this is origin of the peak (C).
Aside from the precise interpretation as above for deeper understanding of the flux-flux correlation function,
we have seen that the flux-flux correlation function can well quantify the extent of the breakdown of the
Born-Oppenheimer approximation not only by the absolute magnitude but also in the local directions ofmoving electrons and nuclei.
The present flux analysis for both electronic and nuclear wave packets in LiF has revealed novel
features in the electron transfer driven by nonadiabatic dynamics. In particular, the spatiotemporal oscillatory
pattern observed in Figure 2 in terms of our defined reduced electronic flux is found not only interesting but
instructive in the deeper understanding of electronic and nuclear coupled dynamics. We also havedemonstrated that the flux-flux correlation between electrons and nuclei describe the deviation from theBorn-Oppenheimer approximation.

Figure 2. (a) Flux-Flux correlation function ‫ܥ‬ሺ‫ݐ‬ሻ between electrons and nuclei. (b) The time

variation of the state populations. Blue and orange lines are for the covalent and ionic states inthe diabatic representation.

－ 149 －

Ⅳ 研究業績 (2017)

2. Original papers(1) Rei Matsuzaki, Satoshi Yabushita, “Calculation of Photoionization differential crosssections using complex Gauss-type orbitals”, J. Comput. Chem. 38, 2030 (2017).
(2) Rei Matsuzaki, Kazuo Takatsuka, “Electronic and Nuclear Flux Analysis on Nonadiabatic
Electron Transfer Reaction”, J. Comput. Chem. (投稿中)

3. Presentation at academic conferences(1) 松崎黎、薮下聡,“複素基底関数法による光イオン化微分断面積の計算”, 第２０回理論化学論会,京都,2017 年 5 月(2) 松崎黎、高塚和夫,“非断熱過程における電子と原子核フラックス” , 第２１回理論化学討論会,岡崎,2018 年５月
4. Others(1) Rei Matsuzaki, Kazuo Takatsuka, “Flux analysis on nonadiabatic chemical dynamics”, 学
第６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 2018年2月－ 150 －

Ⅴ 資料 (2017)

Ⅴ資料

１．研究業績一覧（平成 29 年度）№

西本Authors

Title

JournalVolume (Number),first page tolast page

year

佳央

1

Yoshio Nishimoto, Hiroki
Kondo, Kazuya Yamaguchi,
Daisuke Yokogawa, Junichiro
Yamaguchi, Kenichiro Itami,
and Stephan Irle

Theoretical Elucidation of Potential
Enantioselectivity in a Pd-Catalyzed
Aromatic C—H Coupling Reaction

J. Org. Chem.

82(9), 49004906

2017

2

Hirotaka Kitoh-Nishioka, Kai
Welke, Yoshio Nishimoto,
Dmitri G. Fedorov, andStephan Irle

Multiscale Simulations on Charge
Transport in Covalent Organic
Frameworks Including Dynamics ofTransfer Integrals from the FMO-DFTB/LCMO ApproachJ. Phys. Chem. C

121(33), 1771217726

2017

3

Yoshio Nishimoto and Dmitri
G. Fedorov

Adaptive frozen orbital treatment for
the fragment molecular orbital method
combined with density-functional tightbinding

J. Chem. Phys.

148(6), 064115

2018

4

Y. Maeda, Y. Takehana, J.
–S. Dang, M. Suzuki, M.
Yamada, and S. Nagase

Effect of Substituents and Initial Degreeof Functionalization of Alkylated SingleWalled Carbon Nanotubes on Their
Thermal Stability and Photoluminescence
Properties

Chem. Eur. J.

23, 1789-1794

2017

5

K. Yuan, R. –S. Zhao, J. –J.
Zheng, H. Zheng, S. Nagase,
S. –D. Zhao, Y. –Z. Liu, and
X. Zhao

Van der Waals Heterogeneous Layer-Layer
Carbon Nanostructures Involving
π H-C-C-H π H-C-C-H Stacking Based on
Graphene and Graphane Sheets

J. Comput.
Chem.

38, 730-739

2017

6

M. Yamada, T. Abe, C.
Saito, T. Yamazaki, S. Sato,N. Mizorogi, Z. Slanina,
F. Uhlík, M. Suzuki, Y.
Maeda, Y. Lian, X. Lu, M.
M. Olmstead, A. L. Balch, S.
Nagase, and T. Akasaka

Adamantylidene Addition to M3N@IhC80 (M = Sc, Lu) and Sc3N@D5h-C80:
Synthesis and Crystallographic
Characterization of the [5,6]-Open and[6,6]-Open Adducts

Chem. Eur. J.

23, 6552-6561

2017

7

M. Kako, K. Minami, T.
Kuroiwa, S. Fukazawa, Y.
Arikawa, M. Yamada, Y.
Maeda, Q. –Z. Li, S. Nagase,and T. Akasaka

Photoreactions of Endohedral
Metallofullerene with Siliranes:
Electronic Properties of Carbosilylated
Lu3N@Ih-C80

Molecules

22, 850 (10pages)

20178

Y. Morinaka, R. Zhang, S.
Sato, H. Nikawa, T. Kato,
K. Furukawa, M. Yamada,Y. Maeda, M. Murata, A.
Wakamiya, S. Nagase, T.
Akasaka and Y. Murata

Fullerene C70 as a Nanoflask that Reveals
the Chemical Reactivity of Atomic
NitrogenAngew. Chem.
Int. Ed.

56, 6488-6491

2017

9

M. Yamada, S. Sato, W. Choi,
S. Seki, T. Abe, M. Suzuki,
Y. Maeda, S. Nagase, and T.
AkasakaTemperature Dependence of Anisotropic
Transient Conductivity of a La@C2vC82(Ad) Crystal

Chem. Lett.

46, 973-975

2017

永瀬

茂

－ 151 －

Ⅴ 資料 (2017)№

Authors

Title

JournalVolume (Number),first page tolast page

year

10

M. Kako, T. Sugiura, K.
Miyabe, M. Yasui, M.
Yamada, Y. Maeda, J. –D. Guo, S, Nagase, and T.
Akasaka

Preparation, Structural Determination,
and Characterization ofElectronic Properties of [5,6]- and[6,6]-Carbosilylated Sc3N@Ih-C80

Chem. Asian. J.

12, 1391-1399

2017

11

J. –S. Dang, W. –W. Wang,
J. –J. Zheng, X. Zhao, and S.
NagaseFused-Pentagon-ConfigurationDependent Electron Transfer ofMonotitanium-Encapsulated Fullerenes

Inorg. Chem.

56, 6890-6896

2017

12

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

Synthesis, Electronic Structure, andReactivities of Two-Sulfur Stabilized
Carbones Exhibiting Four-Electron Donor
Ability

Chem. Eur. J.

23, 8694-8702

2017

13

Z. Slanina, F. Uhlík, S.
Nagase, T. Akasaka, L.
Adamowicz, and X. Lu

Eu@C72: Computed Comparable
Populations of Two Non-IPR Isomers

Molecules

22, 1053 (8pages)

2017

14

Q. –Z. Li, J. –J. Zheng, X.
Zhao, and S. Nagase

Epoxy and Oxidoannulene Oxidation
Mechanisms of Fused-Pentagon
Chlorofullerenes: Oxides Linked by a
Pirouette-Type Transition State

J. Org. Chem.

82, 6541-6549

2017

15

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

Functionalization of Endohedral
Metallofullerenes with Reactive Silicon
and Germanium Compounds

Molecules(Review)

22, 1179 (17pages)2017

16

T. Akasaka, A. Nakata,
M. Rudolf, W. –W. Wang,
M. Yamada, M. Suzuki,
Y. Maeda, R. Aoyama, T.
Tsuchiya, S. Nagase, and D.
M. Guldi

Synthesis and Photoinduced ElectronTransfer Reactions in a La2@Ih-C80Phenoxazine Conjugate

ChemPlusChem

82, 1067-1072

2017

17

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

Concave Binding of Cationic Li to
Quadrannulene

Phys. Chem.
Chem. Phys.

19, 2077320777

2017

18

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

Formation of Stone-Wales Edge:
Multistep Reconstruction and Growth
Mechanisms of Zigzag Nanographene

J. Comput.
Chem.

38, 2241-2247

2017

19

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

A Mechanistic Study on Cationic Li
Prompted Diels-Alder Cycloaddition of
Cycloparaphenylene

Org. Chem.
Front.

4, 1757-1761

2017

20

R. Zhao, K.Yuan, S. Zhao,
M. Ehara, S. Nagase, J. M.
Poblet, and X. Zhao

Deciphering the Role of LongRange Interaction in Endohedral
Metallofullenes: A Revisit to Sc2C70

J. Phys. Chem. C

121, 2048120488

2017

21

Z. Slanina, F. Uhlík, L.
Adamowicz, T. Akasaka, S.
Nagase, and X. Lu

Stability Issues in Computational
Screening of Carbon Nanostructures:
Illustrations on La Endohedrals

Mol. Simul.

43, 1472-1479

2017

22

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

Revisit of the Saito-DresselhauseDresselhaus C2 Ingestion Model: On
the Mechanism of Atomic-CarbonParticipated Fullerene Growth

Nanoscale9, 16742-16748

2017－ 152 －

Ⅴ 資料 (2017)№

Authors

Title

JournalVolume (Number),first page tolast page

year

23

Z. Slanina, F. Uhlík, S.
Nagase, T. Akasaka, L.
Adamowicz, and X. Lu

Computational Comparison of the WaterDimer Encapsulation into D2(22)-C84 andD2d(23)-C84

ECS, J. Solid
State Sci. and
Tech.

6,
M3113-M3115

2017

24

Z. Slanina, F. Uhlík, S.
Nagase, T. Akasaka, L.
Adamowicz, and X. Lu

A Computational Characterization of
CO@C60tubes, Carbon
Nanostruct.

25, 624-629

2017

榊

茂好

25

Ryoichi Fukuda, Nozomi
Takagi, Shigeyoshi Sakaki,
and Masahiro Ehara

On the Structures of Bimetallic CopperRuthenium Nanoparticles: Incoherent
Interface and Surface Active Sites for
Catalytic Nitric Oxide Dissociation

J. Chem. Theory
Comput.

121, 300-307

2017

26

Vijay Singh, Yoshiaki Nakao,
Shigeyoshi Sakaki, andMilind M. Deshmukh

Theoretical Study of Nickel-Catalyzed
Selective Alkenylation of Pyridine:
Reaction Mecha- nism and Crucial
Roles of Lewis Acid and Ligands in
Determining the Selectivity

J. Org. Chem.

82, 289-301

2017

27

Tao Yang, Ryoichi Fukuda,
Saburo Hosokawa, Tsunehiro
Tanaka, Shigeyoshi Sakaki,
and Masahiro Ehara

A Theoretical Investigation on CO
Oxidation by Single-Atom Catalysts M1/
γ-Al2O3 (M = Pd, Fe, Co, and Ni)

ChemCatChem,

9, 1222-1229

2017

28

Takako Muraoka, Haruhiko
Kimura, Gama Trigagema,
Masayuki Nakagaki,
Shigeyoshi Sakaki, and Keiji
Ueno

Reactions of Silanone(silyl)tungsten
and -molybdenum Complexes with
MesCNO, (Me2SiO)3, MeOH, and H2O:
Experimental and Theoretical Studies

Organometallics

36, 1009-1018

2017

29

Yue Chen and Shigeyoshi
SakakiMo−Mo Quintuple Bond is Highly
Reactive in H−H, C−H, and O−H σ‑Bond
Cleavages Be-cause of the PolarizedElectronic Structure in Transition State

Inorg. Chem.

56, 4011-4020

2017

30

Hong Zheng, Xiang Zhao,
Shigeyoshi Sakaki[2+2]-type Reaction of Metal-Metal
sigma-Bond with Fullerene Formingan η1-C60 Metal Complex: Mechanistic
Details of Formation Reaction andPrediction of a New η1-C60 Metal Complex

Inorg. Chem.

56, 6746-6754

2017

31

Hajime Kameo, Yuki
Baba, Shigeyoshi Sakaki,
Didier Bourissou, Hiroshi
Nakazawa, Hiroyuki
Matsuzaka

Iridium Hydride Mediated StannaneFluorine and -Chlorine sigma-Bond
Activation: Re-versible Switching
between X-Type Stannyl and Z-Type
Stannane Ligands

Organometallics

36, 2096-2106

2017

32

Yue Chen, Jyun-ya
Hasegawa, Kazuya
Yamaguchi, Shigeyoshi
SakakiA coordination strategy to realize a
sextuply-bonded complex

Phys. Chem.
Chem. Phys.

19, 1494714954

2017

33

Kenji Hirano, Hiroshi
Nakano, Yoshihide Nakao,
Hirofumi Sato, Shigeyoshi
Sakai

Photo Absorption of p-Coumaric Acid
in Aqueous Solution: RISM-SCF-SEDD
Theory Approach

J. Comp. Chem.

38, 1567-1573

2017－ 153 －

Ⅴ 資料 (2017)

JournalVolume (Number),first page tolast pageyear

Shinji Aono, Masayuki
Nakagaki, Shigeyoshi Sakaki

Theoretical study of one-electronoxidized salen complexes of group 7(Mn(III), Tc(III), and Re( III)) and group10 metals (Ni(II), Pd(II), and Pt(II)) withthe 3D-RISM-GMC-QDPT method:
localized vs. delocalized ground andexcited states in solution

Phys. Chem.
Chem. Phys.

19, 16831-16849

2017

35

M. Ramu Yadav, Masahiro
Nagaoka, Myuto Kashihara,Rong-Lin Zhong, Takanori
Miyazaki, Shigeyoshi Sakaki,
Yoshiaki Nakao

The Suzuki–Miyaura Coupling of
Nitroarenes

J. Am. Chem.
Soc.

139, 9423-9426

2017

36

Shuwei Tang, Odile
Eisenstein, Yoshiaki Nakao,
and Shigeyoshi Sakaki

Aromatic C-H σ-Bond Activation by
Ni0, Pd0, and Pt0 Alkene Complexes:
Concerted Oxida-tive Addition to
Metal vs Ligand-to-Ligand H Transfer
Mechanism

Organonetallics

36, 2761-2771

2017

37

Nozomi Takagi, Kazuya
Ishimura, Masafuyu Matsui,
Ryoichi Fukuda, Masahiro
Ehara, and Shigeyoshi SakakiCore−Shell versus Other Structures in
Binary Cu38−nMn Nanoclusters (M =Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au; n= 1, 2, and 6): Theoretical Insight into
Determining Factors

J. Phys. Chem. C

121, 1051410528

2017

38

Jingui Duan, Masakazu
Higuchi, Jiajia Zheng, Shinichiro Noro, I-Ya Chang,
Hyeon-Deuk Kim, Simon
Mathew, Shinpei Kusaka,
Easan Sivaniah, Ryotaro
Matsuda, Shigeyoshi Sakaki,
SusumuKitagawa

Density Gradation of Open Metal Sites
in the Mesospace of Porous Coordination
Polymers

J. Am. Chem.
Soc.,

139, 1157611583

2017

39

Jiajia Zheng, Shinpei Kusaka,
Ryotaro Matsuda, Susumu
Kitagawa, and Shigeyoshi
Sakaki

Characteristic Features of CO2 and CO
Adsorptions to Paddle-Wheel-Type
Porous Coordination Polymer

J. Phys. Chem. C

121, 1912919139

2017

40

Masafuyu Matsui and
Shigeyoshi Sakaki

Embedded Cluster Model for Al2O3 and
AlPO4 Surfaces Using Point Charges andPeriodic Electrostatic Potential

J. Phys. Chem. C

121, 2024220253

2017

41

Longfei Li, Ming Lei, andShigeyoshi Sakaki

DFT Mechanistic Study on Alkene
Hydrogenation Catalysis of Iron
Metallaboratorene: Characteristic
Features of Iron Species

Organometallics

36, 3530-3538

2017

42

Hong Zheng, Kazuhiko
Semba, Yoshiaki Nakao, andShigeyoshi Sakaki

How to Control Inversion vs. Retention
Transmetallation between PdII-Phenyl andCuI-Alkyl Complexes: Theoretical Insight

J. Am. Chem.
Soc.

139, 1406514076

2017

№

Authors

Title

34－ 154 －

Ⅴ 資料 (2017)

Volume (Number),first page tolast page

year

Heterocycles

94(5), 923-937

2017

Studies of Spherically Distributed LUMO
and Electron-Accepting Properties ofCaged Hexakis(germasesquioxanes)

Organometallics

36(14), 25362540

2017

45

Toshiaki Ikeda, Hiroaki
Adachi, Hiroyuki Fueno,
Kazuyoshi Tanaka, andTakeharu Haino

Induced-Dipole-Directed, Cooperative
Self-Assembly of a Benzotrithiophene

J. Org. Chem.

82(19), 1006210069

2017

46

Katsunori Suzuki, Yasuyuki
Numata, Naoko Fujita,
Naoki Hayakawa, Tomoharu
Tanikawa, Daisuke
Hashizume, Kohei Tamao,
Hiroyuki Fueno, Kazuyoshi
Tanaka, and Tsukasa Matsuo

A Stable Free Tetragermacyclobutadiene
Incorporating Fused-ring Bulky EMind
GroupsChem. Commun.

54(18), 22002203

2018

J. Chem. Phys.

146, 084312 (10pages)

2017№

Authors

Title

43

Kensuke Naka, Takuji
Kato, Koushi Abe, Makoto
Ishidoshiro, Shintaro
Nishiyama, Susumu Tanaka,
Hiroaki Imoto, Seiji Watase,
Kimihiro Matsukawa,
Hiroyuki Fueno, andKazuyoshi Tanaka

Stereoisomerization of 1,4-Dihydroarsinet
etracarboxylic Acid Diimides under Nonacidic Condition from cis- to trans-Forms

44

Joji Ohshita, Toshiyuki
Tsuchida, Kenji Komaguchi,
Kazuki Yamamoto, Yohei
Adachi, Yousuke Ooyama,
Yutaka Harima, andKazuyoshi Tanaka

田中

高塚

Journal

一義

和夫

47

Kazuo Takatsuka

Lorentz-like force emerging fromkinematic interactions between electrons
and nuclei in molecules. A quantum
mechanical origin of symmetry breaking
that can trigger molecular chirality

48

Takahide Matsuoka, Kazuo
Takatsuka,

Dynamics of photoionization frommolecular electronic wavepacket states inintense pulse laser fields: A nonadiabatic
electron wavepacket study

J. Chem. Phys.

146,134114 (14pages)

2017

49

Yasuki Arasaki and Kazuo
Takatsuka

Time-resolved photoelectron signals
from bifurcating electron wavepackets
propagated across conical intersection inpath-branching dynamics

Chem. Phys.

493, 42-48(2017)

2017

50

Kazuo Takatsuka

Theory of molecular nonadiabatic
electron dynamics in condensed phases

J. Chem. Phys.

147, 174102 (13pages)

2017

51

Takahide Matsuoka andKazuo Takatsuka

Nonadiabatic electron wavepacket
dynamics behind molecularautoionization

J. Chem. Phys.

148, 014106 (15pages)

2018－ 155 －

Ⅴ 資料 (2017)№

Authors

Title

JournalVolume (Number),first page tolast page

year

Mol. Phys.

DOI:10.1080/00
268976.2018.14
30389

2018

52

Kazuo Takatsuka

Adiabatic and nonadiabatic dynamics inclassical mechanics for coupled fast andslow modes: sudden transition causedby the fast mode against the slaving
principle.

53

Kentaro Yamamoto andKazuo Takatsuka,

On photocatalytic cycle of water splittingwith small manganese oxides and theroles of water cluster as a direct resourceof oxygen molecules

PhysChemChem
Phys20, 6708-6725

2018

54

Kentaro Yamamoto andKazuo Takatsuka,

Collision induced charge separation in
ground-state water splitting dynamics

PhysChemChem
Phys

20, 1222912240

2018

多羅間

充輔

55

M. Tarama

Swinging motion of active deformableparticles in Poiseuille flow

Phys. Rev. E

96, 022602

2017

56

M. Tarama

Dynamics of Deformable Active Particles
under External Flow Field

J. Phys. Soc. Jpn.

86, 101011

2017

57

M. Tarama and R. Yamamoto

Mechanics of cell crawling by means offorce-free cyclic motion

J. Phys. Soc. Jpn.

87, 044803

2018

藪中

俊介

58

Shunsuke Yabunaka andBertrand Delamotte

Surprises in O (N) Models:Nonperturbative Fixed Points, Large N
Limits, and Multicriticality

Physical review
letters

19, 191602 1-5

2017

59

Shunsuke Yabunaka andAkira Onuki

Critical adsorption profiles arounda sphere and a cylinder in a fluid at
criticality: Local functional theory

Physical review
E96, 3, 032127
1-7

2017

60

Shunsuke Yabunaka andAkira Onuki

Electric double layer composed of anantagonistic salt in an aqueous mixture:
Local charge separation and surface
phase transition

Physical review
letters

19, 118001 1-5

2017

61

Shunsuke Yabunaka andMarcq Philippe

Cell growth, division, and death incohesive tissues: A thermodynamic
approachPhysical review
E96, 2, 022406
1-9

2017

62

Shunsuke Yabunaka andMarcq Philippe

Emergence of epithelial cell density
waves

Softmatter

13, 39, 70467052

2017

Simon K. Schnyder
63

S. K. Schnyder, J. J Molina,
Y. Tanaka, R. Yamamoto

Collective motion of cells crawling on asubstrate: roles of cell shape and contact
inhibition

Scientific
Reports

7, 5163

2017

64

J. Horbach, N. H. Siboni, & S.
K. Schnyder

Anomalous transport in heterogeneousmedia

The European
Physical Journal
Special Topics

226(14), 31133128

2017－ 156 －

Ⅴ 資料 (2017)

Authors

Title

JournalVolume (Number),first page tolast pageyear

S. K. Schnyder, & J. Horbach

Crowding of interacting fluid particles
in porous media through molecular
dynamics: breakdown of universality forsoft interactions

Physical Review
Letters120(7), 78001

2018

66

Miho Isegawa, W. M. C.
Sameera, Akhilesh K.
Sharma, Taku Kitanosono,
Masako Kato, Shū Kobayashi,
Keiji Morokuma

Copper-catalyzed Enantioselective Boron
Conjugate Addition: DFT and AFIR
Study on Different Selectivities of Cu(I)and Cu(II) Catalysts

ACS Catalysis

7, 5370-5380

2017

67

Miho Isegawa,, Akhilesh
K. Sharma, Seiji Ogo, Keiji
MorokumaDFT Study on Fe(IV)-Peroxo Formationand H Atom Transfer Triggered O2
Activation by NiFe Complex

Organometallics

37, 1534-1545

2018

The K-Region in Pyrenes as a Key
Position to Activate Aggregation-Induced
Emission: Effects of Introducing Highly
Twisted N,N-Dimethylamines

J. Org. Chem.

82, 6865-6873

2017

69

Akhilesh K. Sharma, W. M.
C. Sameera, Masayoshi Jin,
Laksmikanta Adak, Chiemi
Okuzono, Takahiro Iwamoto,
Masako Kato, Masaharu
Nakamura, and Keiji
Morokuma

DFT and AFIR Study on the Mechanism
and the Origin of Enantioselectivity in
Iron-Catalyzed Cross-Coupling Reactions

J. Am. Chem.
Soc.

139(45), 1611716125

2017

70

Miho Isegawa, Akhilesh K.
Sharma, Seiji Ogo, and Keiji
MorokumaDFT Study on Fe(IV)-Peroxo Formationand H Atom Transfer Triggered
O2 Activation by NiFe Complex

Organometallics

37(10), 15341545

2018

Promotional effect of CH3I onhydroxycarbonylation of cycloalkene
using homogeneous rhodium catalysts
with PPh3 ligand

J. Co2. Util.

25, 1-5

2018

Theoretical Study of One-ElectronOxidized Salen Complexes of Group 7(Mn(III), Tc(III), and Re(III)) and Group
10 Metals (Ni(II), Pd(II), and Pt(II))
with 3D-RISM-GMC-QDPT Method:
Localized vs. Delocalized Ground andExcited States in Solution

Phys. Chem.
Chem. Phys.

19, 16831-16849

2017

№

65

伊勢川

鈴木

68

美穂

聡
S.Sasaki, S.Suzuki, K.
Igawa, K. Morokuma, G.
Konishi,Akhilesh Kumar Sharma

Maneeporn Puripat

71

青野

72

Tomoharu Oku, Masaki
Okada, Maneeporn
Puripat, Miho Hatanaka,
Keiji Morokuma, and JunChulChoi

信治

Shinji Aono, Nakagaki
Masayuki, and Shigeyoshi
Sakaki－ 157 －

Ⅴ 資料 (2017)

Authors

Title

JournalVolume (Number),first page tolast pageyear

Takako Muraoka, Haruhiko
Kimura, Gama Trigagema,
Masayuki Nakagaki,
Shigeyoshi Sakaki, and Keiji
Ueno

Reactions of Silanone(silyl)tungsten
and -molybdenum Complexes with
MesCNO, (Me2SiO)3, MeOH, and H2O:
Experimental and Theoretical Studies

Organometallics

36, 1009-1018

2017

Theoretical Insight into Core–Shell
Preference for Bimetallic Pt-M (M = Ru,
Rh, Os, and Ir) Cluster and Its Electronic
Structure

J. Phys. Chem. C

122 (16), 90819090

2018

75

M. Ramu Yadav, Masahiro
Nagaoka, Myuto Kashihara,Rong-Lin Zhong, Takanori
Miyazaki Shigeyoshi Sakaki,
and Yoshiaki Nakao

The Suzuki–Miyaura Coupling of
Nitroarenes

J. Am. Chem.
Soc.

139(28), 94239426

2017

76

Feng-Wei Gao, Rong-Lin
Zhong , Hong-Liang Xu,
and Zhong-Min Su

Intra- and Intermolecular Charge
Transfer in a Novel Dimer: Cooperatively
Enhancing Second-Order Optical
Nonlinearity

J. Phys. Chem. C

121(45), 2547225478

2017

Nonadiabatic electron wavepacket
dynamics behind molecularautoionization

J. Chem. Phys.

148(1), 014106

2018

On the photocatalytic cycle of water
splitting with small manganese oxides
and the roles of water clusters as directsources of oxygen molecules

Phys. Chem.
Chem. Phys.

20(9), 67086725

2017Time-resolved photoelectron signals
from bifurcating electron wavepackets
propagated across conical intersection
path-branching dynamics

Chem. Phys.

493, 42-48

2017

Calculation of photoionization differential
cross sections using complex Gauss-type
Orbitals

J. Comput.
Chem.

38(23), 20302040

2017

№

中垣

74

雅之

Jing Lu73

Jing Lu, Kazuya Ishimura,and Shigeyoshi SakakiRong-Lin Zhong

松岡
77

山本

78

新崎

79

松崎
80

貴英
Takahide Matsuoka, andKazuo Takatsuka

憲太郎
Kentaro Yamamoto andKazuo Takatsuka

康樹
Yasuki Arasaki and Kazuo
Takatsuka

黎Rei Matsuzaki, and Satoshi
Yabushita－ 158 －

Ⅴ 資料 (2017)

２．共同研究者受入れ状況（平成 29 年度）

受入れ教員

共同研究者名

受入れ身分

受入れ期間

諸熊奎治
榊 茂好

REN, Xuefeng

招へい
外国人学者

平成 28 年 6 月 18 日～
平成 30 年 6 月 17 日

中国鉱山技術大学（中国）・准教授

光機能性分子の発行阻害機構の理論化学
的研究

諸熊奎治
榊 茂好

畑中

共同研究者

平成 28 年 8 月 1 日～
平成 29 年 7 月 31 日

奈良先端科学技術
大学院大学（日本）・
特任准教授

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

招へい
外国人学者

平成 30 年 1 月 13 日～
平成 30 年 3 月 3 日

蘇州大学（中国）・
教授

均一触媒反応の反応機構に関する理論化
学・計算化学研究榊美穂

BAO, Xiaoguang

茂好

所属機関・職研究内容

３．海外渡航一覧（平成 29 年度）

職

氏

名

期間（自）

期間（至）

田中

一義

2017/6/3

2017/6/11

アメリカ合衆国

特定研究員

多羅間 充輔2017/6/13

2017/6/28

ドイツ、スペイン

特定研究員

多羅間 充輔2017/7/12

2017/7/27

ドイツ、スロベニア

特定研究員

SCHNYDER, Simon Kaspar

2017/7/16

2017/7/28

スロベニア、ドイツ

研

名

究

員

目

的

地

特定研究員

薮中

俊介

2017/8/1

2017/9/20

フランス

特 定 助 教西本佳央

2017/8/27

2017/9/2

ドイツ

特定研究員

伊丹

將人

2017/9/3

2017/9/10

ポーランド

研

員

高塚

和夫

2017/12/13

2017/12/19

インド

特定研究員

薮中

俊介

2018/1/1

2018/3/15

フランス

研

高塚

和夫

2018/1/29

2018/2/9

インド

特定研究員

山本 憲太郎2018/2/17

2018/2/25

アメリカ合衆国研

高塚2018/3/9

2018/3/17

イスラエル

究

究

究

員

員

和夫

－ 159 －

Ⅴ 資料 (2017)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－ 160 －

Ⅴ 資料 (2017)

第 15 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

2018 年 2 月 2 日（金） 10:00~19:00

場所

京都大学 福井謙一記念研究センター

開会式 (Opening)： 3 階大会議室[開会の辞]

田中 勝久（京都大学 福井謙一記念研究センター長）

10:00 – 10:05[ご 挨 拶]北村 隆行（京都大学 工学研究科長）

10:05 – 10:15

講演会 (Lecture Session) ： 3 階大会議室


10:15 – 11:15

佐々 真一（京都大学 大学院理学研究科）「気液転移と熱伝導が出会うとき：１９世紀科学から２１世紀科学への展開」
座長：古賀 毅（京大院工）

北浦 和夫（京都大学 福井謙一記念研究センター）

11:30 – 12:30「The Group Molecular Orbital Method For Large Molecular Systems」
座長：永瀬 茂（福井センター）— 昼食 —


13:50 – 14:50

幾原 雄一（東京大学 大学院工学系研究科）「原子直視 STEM 法の新展開と材料科学への応用」
座長：田中 功（京大院工）「福井謙一奨励賞」表彰式 (Ceremony of Kenichi Fukui Encouragement Award)：
3 階大会議室

15:00 – 15:30

受賞者：越智 正之 （大阪大学 大学院理学研究科）「第一原理波動関数理論の固体への展開：量子化学と固体電子論の融合」

ポスターセッション (Poster Session) ： 3 階大会議室

15:30 – 17:20

懇親会 (Banquet) ： 1 階多目的ルーム

17:30 – 19:00－ 161 －

Ⅴ 資料 (2017)

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 the first half (15:30–16:25)

and the second half (16:25–17:30) of the session, respectively.
1.

遷移金属錯体の内殻イオン化・内殻励起スペクトルに関する理論的研究〇中谷 直輝（首都大院理工）2.

Random matrix theory in proteogenesis〇山中 雅則（日大理工）

3.

Stereoselective

isomerizationofeugenoltotrans-isoeugenol

catalyzed

by Ni(0)phosphines: experimental and theoretical studies(Chemistry Department, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung[1],ITbM[2]) Yessi Permana[1], 〇Arifin[2], Leo Saputra[1], Nunik Gustini[1], Stephan Irle[2], Aep Patah[1],and Muhamad A. Martoprawiro[1]4.

高次三重項状態からの逆系間交差を利用した新規有機 EL 素子の設計指針〇佐藤 徹[1,2]、林 里香[3]、春田 直毅[1]、夫 勇進[4,5]（京大院工[1]、京大 ESICB[2]、京大工[3]、山形大院理工[4]、JST さきがけ[5]）5.

福井謙一生誕百年記念事業のご紹介とフロンティア軌道に関連した展示物の準備〇西本 佳央（京大福井セ）

6.

Deformable swimmers in Poiseuille flow
〇Mitsusuke Tarama (FIFC)

7.

The difference between the heat-induced forces of the Soret effect and the adiabatic piston
problem〇Masato Itami[1] and Shin-ichi Sasa[2] (FIFC[1], Dept. of Phys. Kyoto Univ.[2])8.

Cell Colony Growth〇Simon K. Schnyder[1], John J. Molina[2], and Ryoichi Yamamoto[2] (FIFC[1], Grad. School of Eng.,
Kyoto Univ.[2])－ 162 －

Ⅴ 資料 (2017)9.

理論的観点から見た凝集誘起発光〇鈴木 聡、諸熊 奎治（京大福井セ）

10. 結晶・溶媒中における五配位四角錐型コバルトサレン錯体の混合原子価電子状態と吸収スペクト
ル〇青野 信治、中垣 雅之、榊 茂好（京大福井セ）
11. Theoretical Study on the Mechanism of Phoshoranide-Trihydroborate Reaction with Methyl
Iodide〇Akhilesh Kumar Sharma[1], Miho Isegawa[1,2], Keiji Morokuma[1], N. J. O'Brien[3], and Naokazu
Kano[3] (FIFC[1], Kyushu Univ.[2], Univ. of Tokyo[3])12. The potential energy surfaces of emission decay of a type of platinum(II) cyclometalated
complexes〇Xuefeng Ren and Keiji Morokuma (FIFC)
13. ルイス塩基安定化シリレン分子を用いた Si-H 結合の可逆的酸化的付加/還元的脱離反応の機構

解明と制御〇中垣 雅之[1]、Antoine Baceiredo[2]、加藤 剛[2]、榊 茂好[1]（京大福井セ[1]、トゥールーズ大ヘテロ化研[2]）14. Theoretical Understanding of Segregation Behavior and Electronic Structure of 55 and147-atom PtTc and PtRe Nanoclusters〇Jing Lu[1], Kazuya Ishimura[2], and Shigeyoshi Sakaki[1] (FIFC[1], IMS[2])15. How to control Ar-NO2 bond activation and Ar-NO2 bond formation〇Rong-Lin Zhong[1], Masahiro Nagaoka[2], Myuto Kashihara[2], Yoshiaki Nakao[2], and Shigeyoshi
Sakaki[1] (FIFC[1], Grad. School. of Eng. Kyoto Univ.[2])16. Theoretical Study on C4-Hydrocarbon Adsorption and Separation by a Soft Porous
Coordination Polymer〇 Jia-Jia Zheng[1,2], Shinpei Kusaka[2], Ryotaro Matsuda[2], Susumu Kitagawa[2], and Shigeyoshi
Sakaki[1] (FIFC[1], KUIAS-iCeMS, Kyoto Univ.[2])17. Photocatalytic cycle of water splitting with small manganese oxides and water clusters assource of oxygen molecules〇Kentaro Yamamoto and Kazuo Takatsuka (FIFC)－ 163 －

Ⅴ 資料 (2017)18. Flux analysis on nonadiabatic chemical dynamics〇Rei Matsuzaki and Kazuo Takatsuka (FIFC)
19. CaO-SiO2 融液におけるソレー効果解明への分子動力学計算によるアプローチ〇清水 雅弘、下間 靖彦、三浦 清貴（京大院工）20. メチル化ポリロタキサン水溶液の熱誘起ゲル化に関する理論的研究〇小島 広之、古賀 毅（京大院工）21. 円盤状粒子/高分子混合ネットワークの構造と力学物性に関する分子シミュレーション〇古谷 勉、古賀 毅（京大院工）22. 会合性高分子のゲル化の分子シミュレーション：分子内会合と分子間会合の競合〇柴田 基樹、古谷 勉、古賀 毅（京大院工）23. D-B-A 型分子の電子カップリングに対する架橋部分の影響の評価〇由本 美香[1]、中農 浩史[2,3]、佐藤 啓文[2,3]（京大工[1]、京大院工[2]、京大 ESICB[3]）24. 電極－電解液界面における酸化還元反応を扱うための新規方法論開発〇松三 勇介[1]、中農 浩史[1,2]、佐藤 啓文[1,2]（京大院工[1]、京大 ESICB[2]）25. 分子センシングに向けた酸化インジウムスズと金粒子アレイにおける表面増強赤外吸収〇鎌倉 涼介[1]、村井 俊介[1,2]、藤田 晃司[1]、田中 勝久[1]（京大院工[1]、JST さきがけ[2]）26. 層状ペロブスカイト酸化物における間接型強誘電性〇吉田 傑[1]、藤田 晃司[1]、赤松 寛文[2]、Olivier Hernandez[3]、Arnab Sen Gupta[4]、Alexandra S.
Gibbs[5]、辻 涼介[1]、Venkatraman Gopalan[4]、田中 勝久[1] （京大院工[1]、九大院工[2]、レンヌ第一大[3]、ペンシルバニア州立大[4]、ラザフォード・アップルトン研[5]）27. Theoretical Study on Substrate and Inhibitor of HIV-1 protease〇Masahiko Taguchi, Masahiro Kaneso, and Shigehiko Hayashi (Grad. Sch. of Sci. Kyoto Univ.)
28. 光誘起チャネルロドプシンに関する理論研究〇成 せい[1]、神谷 基司[1]、吉田 紀生[2]、林 重彦[1]（京大院理[1]、九大院理[2]）29. アルキルπピレン液体発光特性の理論的研究〇山本 裕生[1]、中西 尚志[2]、林 重彦[1]（京大院理[1]、NIMS[2]）－ 164 －

Ⅴ 資料 (2017)30. コアシェル型混合金属微粒子 Cu32Ru6 による NO-CO 反応の理論研究～Cu38 との比較
〇高木 望[1]、石村 和也[2]、福田 良一[1]、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]）31. 遷移金属担体の埋め込みクラスターモデルの構築〇松井 正冬[1]、榊 茂好[1,2]（京大 ESICB[1]、京大福井セ[2]）32. 溶媒和自由エネルギーの新しい表式とタンパク質の構造安定性への適用〇丸山 豊[1]、光武 亜代理[2]（理研 AICS[1]、慶應大理工[2]）33. Optimizing conical intersections by particle-particle random phase and Tamm-Dancoff
approximations〇嶺澤 範行（理研 AICS）
34. シクロオクタテトラエンを導入した一次元共役縮環系の構造と電子状態の理論研究〇西垣 佑亮、高椋 章太、山根 将暉、當波 孝凱、岸 亮平、中野 雅由（阪大院基礎工）
35. ペンタセン二量体における三次非線形光学特性のスピン状態及び分子配向依存性についての理論研究〇當波 孝凱、永海 貴識、山根 正暉、岸 亮平、中野 雅由（阪大院基礎工）
36. Push-pull-biphenyl (PPB) の開殻性及び電荷移動性のねじれ角依存性に関する理論研究〇北野 奨実[1]、山根 正暉[1]、當波 孝凱[1]、岸 亮平[1]、平尾 泰一[2]、久保 孝史[2]、中野 雅由[1]（阪大院基礎工[1]、阪大院理[2]）37. スマネン縮合アセンのシングレットフィッションについての理論研究〇渡邊 健一郎[1]、永海 貴識[1]、當波 孝凱[1]、伊藤 聡一[2]、中野 雅由[1]（阪大院基礎工[1]、分子研[2]）
38. 螺旋骨格を有する開殻分子の非線形光学物性および分子アクチュエーター機能〇高椋 章太、中野 雅由（阪大院基礎工）39. Pyridinium N-phenoxide betaine とその誘導体の開殻性と非線形光学特性の理論研究〇渡部 晃希[1]、北野 奨実[1]、山根 正暉[1]、當波 孝凱[1]、清水 章弘[1]、吉田 潤一[2]、岸 亮平[1]、中野 雅由[1]（阪大院基礎工[1]、京大院工[2]）－ 165 －

Ⅴ 資料 (2017)40. テリレンのシングレットフィッションにおける分子間相互作用に関する理論研究〇永海 貴識[1]、伊藤 聡一[2]、久保 孝史[3]、中野 雅由[1,4]（阪大院基礎工[1]、分子研[2]、阪大院
理[3]、阪大 CSRN[4]）41. Mn(III)ダイマー錯体の分子内磁気的相互作用に関する理論研究〇北河 康隆[1]、加知 千裕[2]、宮坂 等[3]、中野 雅由[1]（阪大院基礎工[1]、東邦大理[2]、東北大
金研[3]）
42. ナノベルト系の一重項開殻性と第二超分極率の理論研究○山根 正暉、岸 亮平、中野 雅由（阪大院基礎工）
43. Ab initio free-energy calculations on reactions of carbon dioxide with aqueous aminecompounds〇Yoshiyuki Kubota[1] and Tomáš Bučko[2,3] (Kansai Electric Power Co.[1], Comenius Univ. Bratislava[2],Slovak Acad. Sci.[3])44. 不斉希土類 N,N’－ジオキシド誘導体を触媒とするマイケル付加反応の立体選択性発現機構の解明〇宮崎 文[1]、畑中 美穂[1,2,3]（奈良先端大物質創成[1]、奈良先端大研究推進・データセンター[2]、JST さきがけ[3]）45. 不斉トリアゾリウム塩を触媒とする開環アルキル化における立体選択性発現機構の解明〇鎌田 安奈[1]、畑中 美穂[1,2,3]（奈良先端大物質創成[1]、奈良先端大研究推進・データセンター[2]、JST さきがけ[3]）46. Theoretical study on palladium(0)-catalyzed intramolecular cyclization: formation of
δ-lactam〇Takayoshi Yoshimura[1], Yohei Ogiwara[2], Norio Sakai[2], and Miho Hatanaka[1,3] (NAIST[1], Tokyo
Univ. of Science[2], JST Presto[3])47. 2Fe–2S ferredoxin 活性中心の電子状態と水素結合に関する理論研究〇江良 伊織、名取 圭紀、寺本 玲奈、青木 笙悟、多田 隼人、北河 康隆、中野 雅由（阪大基礎工）
48. クロムおよびモリブデン二核錯体の単分子電気伝導性に関する理論研究〇多田 隼人、名取 圭紀、寺本 玲奈、青木 笙悟、江良 伊織、北河 康隆、中野 雅由（阪大基礎工）
49. ビス(ジピリナト)錯体における中心金属イオン種がフロンティア軌道に与える影響についての理論研究〇青木 笙悟、名取 圭紀、北河 康隆、中野 雅由（阪大基礎工）－ 166 －

Ⅴ 資料 (2017)

５．福井センターセミナー

ポスター・プログラム

第１５回
福井センターセミナー
The 15th Fukui Center Seminar
2017年5月25日(木) 15:00–17:20

京都大学福井謙一記念研究センター1F 多目的室㻌 (Room: 1F 106)
http://www.fukui.kyoto-u.ac.jp/〒606-8103㻌 京都市左京区高野西開町34-4（℡075-711-7708)(at FIFC, Kyoto Univ. on May, 25 (Thur.), 2017)

15:00–15:40

Yoshio Nishimoto (FIFC)㻌

“Analytic Derivatives with Fractional Occupation
Number”
15:40–16:20

Mitsusuke Tarama (FIFC)㻌 㻌“Nonlinear Dynamics of Active Deformable Particles:
From Liquid Droplets to Biological Cells”
Break (10 min.)16:30–17:20 Dmitri G. Fedorov (AIST)㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌㻌“Large Scale Quantum-Mechanical Calculations with
the Fragment Molecular Orbital Method”
多数の方のご来場を歓迎いたします
We welcome all of you to join.

－ 167 －

京都大学福井謙一記念研究センター

年報

2017

2019 年 2 月発行
発行人

田 中 勝 久編

田 中 勝 久者

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）