Annual Report

2016

年
報
年 報

2010
2016

京都大学
福井謙一記念研究センター

ご自身の栄誉はもとより、本センター

は じ め にの名を大いに高めて頂いたことでもあ2016 年度の京都大学福井謙一記念研り、大変喜ばしいことであります。諸究センターの活動をまとめた年報をお熊先生には 2015 年からは FIFC リサー

届けします。本センターは、京都大学

チフェローとして研究ならびに若手人

本部構内の北、約１キロの高野川沿い

材育成にご尽力いただいております。

の静かな住宅街に独立して位置してお2009 年度には福井謙一記念研究部第ります。専任教員は理論研究部門と総二も設置し、名古屋大学名誉教授（前合研究部門に 1 名ずつを持っているに副学長）の大峯巖先生をリサーチリー

過ぎませんが、センター長のほか副セダーとして招聘し、研究体制を拡大しンター長とスーパーバイザーとして工ました。なお、大峯先生は 2010 年 4 月

学研究科、理学研究科、化学研究所所に分子科学研究所長に転出されました。

属の 12 名の教員にご協力頂いており、その後任として、2011 年 4 月に京都大

このメンバーが運営委員会を構成して学物質―細胞統合システム拠点（iCeMS）

います。そして優れた博士研究員に研特任教授の榊茂好先生を研究部第二の究活動の機会を与える制度を持っておリサーチリーダーとして招聘しました。

り、若手研究者が国際的な雰囲気の中榊先生は、遷移金属化合物や類縁化合で日夜研究にいそしんでいます。福井

物に関する研究で顕著な業績を挙げてセンターフェローと呼ばれる博士研究おられ、現在は d 電子複合系の理論化

員はセンターの雇用で、自分自身のア学に関する研究を推進しておられます。

イデアで一定期間、自由闊達に研究でま た、2012 年 に は シ ニ ア リ サ ー チ

きる身分を保証しています。

フェローとして永瀬茂先生（分子科学2006 年 9 月 に 福 井 謙 一 記 念 研 究 部

研究所名誉教授）を招聘しました。永

第一のリサーチリーダーとして世界的瀬先生は、望む構造、物性、機能を持な理論化学者の諸熊奎治先生（分子科

つ分子を自在に組み立てて思うよう

学研究所名誉教授）を米国エモリー大に反応させる理論と計算およびコン

学 か ら 招 聘 し、 研 究 面 で の リ ー ダ ー

ピューターシミュレーションの開発

シップを発揮して頂いております。諸において顕著な業績を挙げられまし熊 先 生 は、2012 年 に シ ニ ア リ サ ー チ

た。2015 年からは FIFC リサーチフェ

フェローに就任され、この年の 11 月にローとして高周期典型元素と遷移金属

は、複雑分子系の理論研究の発展に多元素化学種の理論化学に関する研究を大な貢献をしたとして、文化功労者の進めておられます。同じ年に、シニア顕彰を受けられました。これは、先生

リサーチフェローとして田中一義先－i－生（京都大学名誉教授）を招聘しましを 提 案 し た ご 功 績 に よ り、1981 年 にた。田中一義先生は導電性や磁性を有

わが国で最初のノーベル化学賞を受賞

する有機化合物など量子機能材料に関されました。福井先生が京都大学ご退する物理化学的研究において優れた多

官後に研究を続けられるため、京都市

くの業績を挙げておられ、現在は元素と産業界などのご支援で 1985 年に財ブロックを有する分子・高分子の理論

団法人「基礎化学研究所」が設立され化学に関する研究を展開されています。

ました。専任研究員数名の規模でした

さ ら に、2016 年 に は、 化 学 反 応 電 子

が、研究のレベルは高く、当時の研究

動力学の基礎理論研究において著名な

員は、東京大学、名古屋大学、分子科

高塚和夫先生（東京大学名誉教授）を学研究所の教授になるなど、理論化学

リサーチリーダーとして招聘しました。

分野でトップクラスの研究者として活センターでは非断熱電子動力学理論に躍しています。この基礎化学研究所はよる化学反応の解析に関する研究を推1998 年の福井先生のご逝去の後、2002

進しておられます。

年に本学に寄贈され、福井謙一記念研

私達は、センターが若手研究者の登究センターとなり、現在に至っており竜門となることを期待しています。実ます。京都大学の部局となった後、森際に、センターの博士研究員であった

島績、中辻博、榊茂好、田中功、田中

多くの方々が、現在、国内外の大学、

一義、赤木和夫の各先生にセンター長

研究機関で活躍しておられます。2016

としてご指導を頂きました。

年には、化学の将来の発展のために若本センターは、国際活動も活発で、手研究者の育成の大切さを説いておら2005 年よりチェコおよびスロバキアとれた福井博士の遺志を汲み、基礎化学・

理論化学・計算化学シンポジウムを定

理論化学の分野で顕著な研究業績を挙期的に開催しております。2011 年にはげた若手研究者を顕彰する「福井謙一国内外（主にドイツ、東欧、中国、韓奨励賞」を創設しました。第 1 回の福国）から第一線の研究者を招き、第 1

井謙一奨励賞は、「理論化学研究に立脚

回福井センター理論化学・計算化学国

した量子干渉現象の分子エレクトロニ

際シンポジウムを開催しました。こうクスへの展開」に関する成果が評価さした国際連携活動をさらに活性化するれた九州大学の辻雄太博士に授与されという観点から、2016 年 2 月に国際学ました。

術連携研究室（2016 年 12 月に国際連

当センターの歴史を簡単にご紹介し携インターディシプリナリー研究推進ます。ご承知のように故福井謙一京都室と改組）を設置し、その運営上必要

大学名誉教授はフロンティア軌道理論となるコーディネーター役として、特－ ii －

定 助 教 1 名 を 配 置 し ま し た。 本 セ ン

べき年に福井先生の業績を改めて振りターは、今後も、理論化学・計算化学

返る機会を設ける意味で、生誕百年記

分野におけるわが国の研究拠点の役割

念行事を企画しております。具体的にを果たし、国際連携活動を展開して行

は、福井先生の誕生日である 10 月 4 日

きたいと考えております。

に合わせて、シンポジウム、記念式典、

例年晩秋から初冬に福井センターシ

京大総合博物館における記念展などをンポジウムを開催しており、国内外の開催する予定で、センター内に福井謙

トップクラスの研究者による特別講演、

一生誕百年記念事業実施委員会を立ち運営委員の講演、並びに京都大学内外上げ、行事の実施に向けた準備を進めからのポスター発表を行っております。

ているところです。

研究発表のレベルは高く、特別講演に本センターは、上述のように規模は来られた講師からも毎年高い評価を得

大きくありませんが、研究活動は極めております。2016 年は、毎年実施してて活発です。今後も、京都大学あるいいる福井センターシンポジウムに加え、は国内外との共同研究を積極的に進め

複雑・複合系の理論計算科学に関するて行きたいと考えております。とくに

日・仏・スペイン合同シンポジウムを実験科学者との共同研究は重要であり、開催しました。化学、物理学、生命科

そのような連携研究をさらに活発化し学にまたがる複雑・複合系の理論計算たいと考えております。

科学に関する研究成果を三カ国の若手、

この年報により、本センターの活動

中堅研究者が互いに紹介し合い、当研に興味をお持ち頂ければ幸甚です。そ

究分野の更なる展開を議論する場となして、それが共同研究の契機となり、時りました。

間をかけて大きな成果に結実していく

さらに社会貢献活動の一環として、ことを念願しています。最後になりま2011 年が福井先生のノーベル化学賞受したが、本センターの順調な活動はひ賞 30 周年にあたるため、これを節目ととえに工学研究科、理学研究科、化学

して本センター玄関ロビーに先生ゆか研究所のご協力、ご援助の賜物であり、りの文物の展示コーナーを設置しましここに心から御礼申し上げる次第です。

た。コーナーでは先生が使用された机、椅子、ノーベル賞メダル・賞状（複製）、

2017 年 10 月

研究ノート・メモ、写真などを展示し、常設展示として一般に公開しています。

京都大学福井謙一記念研究センター長

加えて、来る 2018 年は福井謙一先生

田の生誕百年にあたります。この記念す－ 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 

20(7) リサーチリーダー 

25(8) 研究員 

26

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

27

２．共同研究員 

27

３．日本学術振興会外国人特別研究員 

27

４．博士研究員プロフィール 

28

５．共同研究員プロフィール 

44

６．日本学術振興会外国人特別研究員プロフィール 

46

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 

47

２．セミナー 

48（1）第 14 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 －

50

４．社会へのアウトリーチ活動 

50

５．福井謙一奨励賞の創設及び奨励賞の授与 

50

６．複雑・複合系の理論計算科学に関する
日・仏・スペイン合同シンポジウムを開催 
７．日本－ブラジル

Ⅳ

51

理論化学 ･ 計算化学交流会を開催 

51

８．日本化学会賞受賞（赤木和夫センター長） ��������������

51

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

52

２．FIFC リサーチフェロー����������������������

59

３．シニアリサーチフェロー 

65

４．リサーチリーダー 

77

５．研究員 

85

６．博士研究員 

88

７．共同研究員  163
８．日本学術振興会外国人特別研究員  170

Ⅴ資料
１．研究業績一覧  173
２．共同研究者受入れ状況  183
３．海外渡航一覧  184
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  185

ポスター・プログラム  191

６．複雑・複合系の理論計算科学に関する
日・仏・スペイン合同シンポジウムを開催 192
７．日本－ブラジル

理論化学･計算化学交流会を開催 ����������� 194（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/AnnualReport2016.pdf）－v－

Ⅰ 専任教員 ･ スーパーバイザー (2016)Ⅰ

専任教員・スーパーバイザー

１．教員組織職

協議

平成２８年度
名

氏

センター長

赤 木

和 夫

工学研究科高分子化学専攻

副センター長田 中勝 久

工学研究科材料化学専攻

副センター長谷 村

吉 隆

理学研究科化学専攻

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

工学研究科高分子化学専攻

理学研究科長森 脇

淳

理学研究科数学・数理解析専攻

化学研究所長時 任

宣 博

化学研究所物質創製化学研究系
物質－細胞統合システム拠点

教

授

北 川

進

教

授

佐 藤

啓 文

工学研究科分子工学専攻

教

授

佐 々

真 一

理学研究科物理学・宇宙物理学専攻

教

授

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（工学研究科合成・生物化学専攻）

総合研究部門

准 教 授

（欠員中）

理論研究部門

准 教 授

（欠員中）

国際学術連携研究室

特定助教

水 野

英 如

専

任

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

任

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－

Ⅰ 専任教員 ･ スーパーバイザー (2016)２.教員プロフィール
⑴

センター長

【氏名（ふりがな）】 赤木

和夫 （あかぎかずお）【職名】 教授【所属】 工学研究科高分子化学専攻【研究室】 赤木研究室【直通電話】 075-383-2595【FAX】 075-383-2760【電子メールアドレス】 akagi@fps.polym.kyoto-u.ac.jp【ホームページ】 http://www.fps.polym.kyoto-u.ac.jp【研究分野】 高分子化学、液晶化学、物質化学【現在の研究課題】 導電性、液晶性、発光性、階層らせん性の共役系高分子の合成と性質【研究内容キーワード】 導電性高分子、液晶性共役高分子、不斉液晶反応場、階層構造制御【最終学歴】 京都大工学研究科博士後期課程【学位】 工学博士【略歴】 福井大工助手、筑波大物質工講師、助教授、教授、同大学院数理物質科学研究科教授、学際物質科学研究センター長【在外研究歴】 カリフォルニア大サンタバーバラ校交換研究員、コーネル大客員研究員【所属学会】 日本化学会、高分子学会、日本液晶学会、アメリカ化学会【学会活動】 文部科学省科研費（特定領域研究、2005-2008）「次世代共役ポリマーの超階層制御と革新機能」領域代表、Chair of International Conference on Science andTechnology of Synthetic Metals (2010).
【主な著書、学術論文】 1. S. Matsushita, K. Akagi, “Macroscopically Aligned Graphite Films Prepared from
Iodine-Doped Stretchable Polyacetylene Films Using Morphology-Retaining（過去 5 年以内）
Carbonization”, J. Am. Chem. Soc., 137, 9077 (2015).
2. J. Bu, K. Watanabe, H. Hayasaka, K. Akagi, “Photochemically Colour-Tuneable
White Fluorescence Illuminants consisting of Conjugated Polymer Nanospheres”,
Nat. Commun. 5, 3799 (2014).
3. S. Matsushita, B. Yan, S. Yamamoto, Y. S. Jeong, K. Akagi, “Helical Carbon
and Graphite Films Prepared from Helical Poly(3,4-ethylenedioxythiophene)
Films Synthesized by Electrochemical Polymerization in Chiral Nematic Liquid
Crystals”, Angew. Chem., Int. Ed., 53, 1659 (2014).
4. B. A. San Jose, J. Yan, K. Akagi, “Dynamic Switching of the Circularly Polarized
Luminescence of Disubstituted Polyacetylene by Selective Transmission though a
Thermotropic Chiral Nematic Liquid Crystal”, Angew. Chem. Int. Ed., 53, 10641,(2014).
5. H. Hayasaka, T. Miyashita, M. Nakayama, K. Kuwada, K. Akagi, “Dynamic
Photoswitching of Helical Inversion in Liquid Crystals Containing Photoresponsive
Axially Chiral Dopants”, J. Am. Chem. Soc., 134, 3758 (2012).
【学術関係の受賞など】 日本化学会学術賞（1999 年度）、日産科学賞（2000 年度）、日本液晶学会賞論文賞（2001 年度）、つくば賞（2001 年度）、高分子学会賞（2002 年度）、文部科学大臣表彰科学技術賞（2005 年度）、筑波大学名誉教授称号授与（2009 年度）、
日本液晶学会賞業績賞（2010 年度）、日本化学会賞（2016 年度）－2－

Ⅰ 専任教員 ･ スーパーバイザー (2016)⑵

副センター長【氏名（ふりがな）】 田中

勝久 （たなかかつひさ）【職名】 教授【所属】 工学研究科 材料化学専攻【研究室】 桂キャンパス A3 クラスター 018【直通電話】 075-383-2801【FAX】 075-383-2420【電子メールアドレス】 tanaka@dipole7.kuic.kyoto-u.ac.jp【ホームページ】 http://dipole7.kuic.kyoto-u.ac.jp/【研究分野】 無機固体化学【現在の研究課題】 新規酸化物固体の合成と磁気的・誘電的・光学的性質【研究内容キーワード】 酸化物、磁気的性質、誘電的性質、光学的性質【学歴】 1984 年 3 月 京都大学工学部工業化学科卒業
1986 年 3 月 京都大学大学院工学研究科工業化学専攻修士課程修了【学位】 1991 年 3 月 京都大学工学博士【略歴】 1986 年 4 月 三重大学工学部助手
1989 年 4 月 京都大学工学部助手
1999 年 7 月 京都工芸繊維大学工芸学部助教授
2004 年 4 月 京都大学大学院工学研究科教授【所属学会】 日本セラミックス協会、日本化学会、応用物理学会、日本物理学会、粉体
粉 末 冶 金 協 会、 日 本 材 料 学 会、 日 本 金 属 学 会、Materials Research Society、
Optical Society of America【学会活動】 日本セラミックス協会理事、粉体粉末冶金協会理事【主な著書、学術論文】 1. T. Kawamoto, K. Fujita, H. Akamatsu, T. Nakamura, T. Kinoshita, M. Mizumaki, N.
Kawamura, M. Suzuki, Y. Kususe, S. Murai, and K. Tanaka, “Eu M4,5- and L2,3（過去 5 年以内）
edge x-ray magnetic circular dichroism of ferromagnetic amorphous oxides in EuOTiO2 system”, Physical Review B 88 (2013) 024405-1-9.
2. X. Meng, A. V. Kildishev, K. Fujita, K. Tanaka, and V. M. Shalaev, “Wavelengthtunable spasing in the visible”, Nano Letters 13 (2013) 4106-4112.
3. H. Akamatsu, K. Fujita, T. Kuge, A. S. Gupta, A. Togo, S. Lei, F. Xue, G. Stone, J.
M Rondinelli, L. Chen, I. Tanaka, V. Gopalan, and K. Tanaka, “Inversion symmetry
breaking by oxygen octahedral rotations in Ruddlesden-Popper NaRETiO4 family”,
Physical Review Letters 112 (2014) 187602-1-5.
4. 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.
5. 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.
6. 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.
7. 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.

【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）－3－

Ⅰ 専任教員 ･ スーパーバイザー (2016)【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. A. Sakurai and Y. Tanimura, Self-excited current oscillations in a resonant tunneling（過去 5 年以内）
diode described by a model based on the Caldeira-Leggett Hamiltonian, New J. of
Phys. 16, 015002 [24 pages] (2014).
2. Y. Tanimura, Reduced hierarchical equations of motion in real and imaginary time:
Correlated initial states and thermodynamic quantities, J. Chem, Phys 141, 044114[13 pages](2014). [2014 JCP Editors’Choice]
3. Y. Tanimura, Real-Time and Imaginary-Time Quantum Hierarchal Fokker-Planck
Equations, J. Chem, Phys 142, 144110 [20 pages](2015).
4. 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]
5. 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]【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－4－

Ⅰ 専任教員 ･ スーパーバイザー (2016)⑶

スーパーバイザー【氏名（ふりがな）】 北川

進 （きたがわすすむ）【職名】 高等研究院副院長 / 特別教授、物質－細胞統合システム拠点拠点長【所属】 高等研究院 物質－細胞統合システム拠点【研究室】 高等研究院本館 4 階 A406

【直通電話】 075-753-9740【FAX】 075-753-9742【電子メールアドレス】 kitagawa@icems.kyoto-u.ac.jp【ホームページ】 http://www.kitagawa.icems.kyoto-u.ac.jp/【研究分野】 錯体化学、無機化学【現在の研究課題】 多孔性配位高分子の化学とその応用【研究内容キーワード】 配位空間の化学、メゾスコピック化学、多孔性配位高分子【最終学歴】 1979 年 3 月【学位】 1979 年 7 月

京都大学大学院工学研究科石油化学専攻博士課程修了
工学博士（京都大学）【略歴】 1979 年 4 月近畿大学理工学部助手、1983 年 4 月近畿大学理工学部講師、1988
年 4 月近畿大学理工学部助教授、1992 年 4 月東京都立大学理学部化学教室無機化学第一講座教授、1998 年 6 月京都大学大学院工学研究科合成・生物化学専攻教授、2007 年 10 月京都大学物質－細胞統合システム拠点・副拠点長および京都大学大学院工学研究科合成・生物化学専攻（兼任）教授、2013 年 1月京都大学物質－細胞統合システム拠点拠点長（現在に至る）および京都大学大学院工学研究科合成・生物化学専攻教授（2017 年 3 月まで）
、2016 年 6月京都大学高等研究院副院長（現在に至る）、2017 年 4 月京都大学高等研究院特別教授（現在に至る）【在外研究歴】 1986 年− 1987 年

Texas A&M 大学 Cotton 研究室博士研究員【所属学会】 日本化学会、錯体化学会、アメリカ化学会、イギリス王立化学会【主な著書、学術論文】 1.“Mesoscopic architectures of porous coordination polymers fabricated by（過去 5 年以内）
pseudomorphic replication”, J. Reboul, S. Furukawa, N. Horike, M. Tsotsalas,
K. Hirai, H. Uehara, M. Kondo, N. Louvain, O. Sakata and S. Kitagawa, Nature
Materials, 2012, 11,717-723. (Cover Picture)
2. Shape-Memory Nanopores Induced in Coordination Frameworks by Crystal
Downsizing”, Y. Sakata, S. Furukawa, M. Kondo, K. Hirai, N. Horike, Y.
Takashima, H. Uehara, N. Louvain, M. Meilikhov, T. Tsuruoka, S. Isoda, W.
Kosaka, O. Sakata, and S. Kitagawa, Science, 2013, 339, 193.
3. Self-Accelerating CO Sorption in a Soft Nanoporous Crystal”, H. Sato, W.
Kosaka, R. Matsuda, A. Hori, Y. Hijikata, R.V. Belosludov, S. Sakaki, M. Takata,and S. Kitagawa, Science, 2014, 343, 167-170.

【学術関係の受賞など】 1. 2002年 第19回日本化学会学術賞
2. 2007年 Earl L. Muetterties Memorial Lectureship (University of California,
Berkeley)、平成19年度錯体化学会賞
3. 2008年 Humboldt Research Award, Germany
4. 2009年 第61回日本化学会賞
5. 2010年 トムソン・ロイター引用栄誉賞受賞
6. 2011年 平成23年度科学技術分野の文部科学大臣表彰研究部門、The
Honorary Fellowship of the Council of the Chemical Research Society of India(CRSI)、平成23年春の紫綬褒章、京都新聞大賞文化学術賞、第22期日本学術会議会員
7. 2013年 The RSC de Gennes Prize、第10回江崎玲於奈賞、平成25年度京都大学孜孜賞、The fellow of the UK Royal Society of Chemistry (RSC)
8. 2014年 2014 Thomson Reuters Highly Cited Researcher
9. 2015年 マルコ・ポーロ イタリア科学賞
10. 2016年 平成28年度日本学士院賞
11. 2016年 2016 Thomson Reuters Highly Cited Researcher
12. 2016年 2016 Fred Basolo Medal for Outstanding Research in Inorganic Chemistry
13. 2016年 1st Air Liquide Awards on Essential Small Molecules 201614. 2017年 第58回藤原賞－5－Ⅰ 専任教員 ･ スーパーバイザー (2016)【氏名（ふりがな）】 佐藤

啓文 （さとうひろふみ）【職名】 教授【所属】 工学研究科分子工学専攻【研究室】 A4 棟 026【直通電話】 075-383-2548【FAX】 075-383-2799【電子メールアドレス】 hirofumi@moleng.kyoto-u.ac.jp【ホームページ】 http://www.riron.moleng.kyoto-u.ac.jp/【研究分野】 理論化学・量子化学・統計力学【現在の研究課題】 理論化学・物理化学【研究内容キーワード】 化学反応・自己集合・溶媒和【最終学歴】 1996 年 5 月 京都大学理学研究科化学専攻博士後期課程修了【学位】 1996 年 5 月 京都大学博士（理学）【略歴】 1996 年 8 月 岡崎国立共同研究機構分子科学研究所助手、2002 年 5 月京都大学工学研究科講師、2004 年 5 月京都大学工学研究科助教授、2010 年 7 月京都
大学工学研究科教授【在外研究歴】 2004 年 6 月− 2004 年 12 月 連合王国 Oxford 大学 PTCL 訪問研究員（Paul A.
Madden 教授）【所属学会】 日本化学会、分子科学会、理論化学研究会、溶液化学研究会、イオン液体研
究会【学会活動】 日本化学会 理論化学・情報化学・計算化学ディビジョン幹事（2011 年度−）、
副主査（2015 年度−）
理論化学研究会 第三期世話人（2009 年−）
分子科学会 幹事（2012 年度− 2013 年度）、運営委員（2012 年度−）
溶液化学研究会 運営委員（2015 年度−）
【主な著書、学術論文】 1. Yusuke Matsumi, Hiroshi Nakano, Hirofumi Sato,“Constant-potential molecular（過去 5 年以内）
dynamics simulations on an electrode-electrolyte system: calculation of staticquantities and comparison of two polarizable metal electrode models”Chem. Phys.
Lett. 681, 80-85 (2017).
2. Yuichiro Yoshida, Hirofumi Sato, John W. R. Morgan, David J. Wales,“Potential
energy landscapes of tetragonal pyramid molecules”Chem. Phys. Lett. 664, 5-9(2016).
3. Maxim Shishkin and Hirofumi Sato,“Self-consistent parametrization of DFT+U
framework using linear response approach: Application to evaluation of redox
potentials of battery cathodes”Phys. Rev. B 93(8), 085135 (2016).
4. Kento Kasahara and Hirofumi Sato,“A theory of diffusion controlled reactions inpolyatomic molecule system”J. Chem. Phys. 145(19), 194502 (2016).
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）－6－

Ⅰ 専任教員 ･ スーパーバイザー (2016)【氏名（ふりがな）】 佐々

真一 （ささしんいち）【職名】 教授【所属】 京都大学

大学院理学研究科【研究室】 理学部 5 号館

物理学宇宙物理学専攻

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

客員研究准教授【所属学会】 日本物理学会【学会活動】 2016.4-2017.3 日本物理学会領域 11 副代表【主な著書、学術論文】 1. Thermodynamic entropy as a Noether invariant, S.-I. Sasa, Yuki Yokokura, Phys.
Rev. Lett 116 140601/1-140601/6（2016）（過去 5 年以内）
2. Replica symmetry breaking in trajectories of a driven Brownian particle, Masahiko
Ueda, S.-I. Sasa, Phys. Rev. Lett 115 080605/1-080605/5（2015）
3. Derivation of Hydrodynamics from the Hamiltonian Description of Particle
Systems, S.-I. Sasa, Phys. Rev. Lett 112 100602/1-100602/5（2014）
4. Computation of large deviation statistics via iterative measurement-and-feedback
procedure, T. Nemoto, S.-I. Sasa, Phys. Rev. Lett 112 090602/1-090602/5（2014）
5. Pure glass in finite dimensions, S.-I. Sasa, Phys. Rev. Lett 109 165702/1-165702/4（2012）－7－

Ⅰ 専任教員 ･ スーパーバイザー (2016)【氏名（ふりがな）】 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. S. Bono, Y. Takanishi and J. Yamamoto, Effects of layer order on the mobility of（過去 5 年以内）
mesogenic molecules in SmA liquid-crystalline emulsions, Europhys. Lett., 113,
56004 (5P) (2016).
2. 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.
3. 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).
4. Y. Uchida, Y. Takanishi and J. Yamamoto, Controlled Fabrication and Photonic
Structure of Cholesteric Liquid Crystalline Shells, Adv. Mat., 25 (2013) 3234-3237.
5. J. Yoshioka, Y. Takanishi and J. Yamamoto, Dispersion relations of director
fluctuations along the direction perpendicular to the helical axis in cholesteric liquid
crystals, Europhys. Lett., 98 (2012) 16006(5P).
【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 (2016)【氏名（ふりがな）】 渡辺

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

理学博士

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

博士研究員【所属学会】 日 本 レ オ ロ ジ ー 学 会 ; The Society of Rheology (USA); The Korean Society ofRheology; The American Chemical Society; The American Physical Society【学会活動】 2015.5-2017.5: 日本レオロジー学会 会長
2016.8-2020.8: President, The International Committee on Rheology
2011.3- 現在 : Associate Editor of Macromolecules (ACS)【主な著書、学術論文】 1. Y. Doi, A. Matsumoto, T. Inoue, T. Iwamoto, A. Takano, Y. Matsushita, Y.
（過去 5 年以内）
Takahashi, and H. Watanabe, "Re-examination of terminal relaxation behavior ofhigh-molecular-weight ring polystyrene melts", Rheol. Acta, 56:567-581 (2017).
2. 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)
3. Y. Matsumiya, H. Watanabe, O. Urakawa, and T. Inoue, "Experimental Test for
Viscoelastic Relaxation of Polyisoprene Undergoing Monofunctional Head-to-Head
Association and Dissociation", Macromolecules, 49, 7088-7095 (2016).
4. 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)
5. 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).
－9－

Ⅰ 専任教員 ･ スーパーバイザー (2016)

6. 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).
7. 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).
8. 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).
9. 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).
10. 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
11. 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).
12. 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).
13. 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).
14. 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).
15. 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).
16. H. Watanabe, Y. Matsumiya, and E. van Ruymbeke, "Component relaxation times
in entangled binary blends of linear chains: Reptation/CLF along partially or fully
dilated tube", Macromolecules, 46, 9296-9312 (2013).
17. Q. Huang, N. J. Alvarez, Y. Matsumiya, H. K. Rasmussen, H. Watanabe, and O.
Hassager, "Extensional Rheology of Entangled Polystyrene Solutions Suggests
Importance of Nematic Interactions", ACS Macro Letters, 2, 741-744 (2013).
18. Y. Matsumiya, K. Kumazawa, M. Nagao, O. Urakawa, and H. Watanabe,"Dielectric Relaxation of Monodisperse Linear Polyisoprene: Contribution ofConstraint Release", Macromolecules, 46, 6067-6080 (2013).
19. S. Suzuki, T. Uneyama, and H. Watanabe, "Concentration Dependence ofNonlinear Rheological Properties of Hydrophobically Modified Ethoxylated
Urethane (HEUR) Aqueous Solutions ", Macromolecules, 46, 3497-3504 (2013).
20. Y. Matsumiya, H. Watanabe, A. Takano, and Y. Takahashi, "Uniaxial Extensional
Behavior of (SIS)p-type Multiblock Copolymer Systems: Structural Origin of High
Extensibility", Macromolecules, 46, 2681-2695 (2013).
【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 (2016)【氏名（ふりがな）】 田中

功 （たなかいさお）【職名】 教授【所属】 工学研究科

材料工学専攻【研究室】 吉田キャンパス

工学部物理系校舎

量子材料学研究室【直通電話】 075-753-5465【FAX】 075-753-5447【電子メールアドレス】 tanaka@cms.MTL.kyoto-u.ac.jp【ホームページ】 http://cms.mtl.kyoto-u.ac.jp/tanaka.html【研究分野】 材料科学
【現在の研究課題】 計算材料科学，構造材料科学，材料情報学，エネルギー材料学【研究内容キーワード】 量子材料設計，第一原理計算，材料ｲﾝﾌｫﾏﾃｨｸｽ，ｾﾗﾐｯｸｽ科学，電子分光【最終学歴】 1987 年 3 月 大阪大学大学院基礎工学研究科物理系専攻博士後期課程修了【学位】 1987 年 3 月 大阪大学工学博士【略歴】 1987 年 4 月 日本学術振興会特別研究員 (PD)、1987 年 6 月 大阪大学産業科学研究所・助手、1993 年 4 月 京都大学工学部・助手、1996 年 5 月 京都大学大
学院エネルギー科学研究科・助教授、2001 年 7 月 京都大学大学院工学研究科・助教授、2003 年 12 月 京都大学大学院工学研究科・教授【在外研究歴】 1992 年 4 月− 1993 年 3 月 ドイツ マックスプランク金属研究所・客員研究員（アレキサンダー・フォン・フンボルト財団奨学研究員）【所属学会】 日 本 金 属 学 会、 日 本 セ ラ ミ ッ ク ス 協 会、 日 本 鉄 鋼 協 会， 応 用 物 理 学 会、American Ceramic Society、Materials Research Society【学会活動】 Journal of American Ceramics Society フ ェ ロ ー・ 編 集 委 員、World Academy of
Ceramics 会員【主な著書、学術論文】 1. G. Kobayashi, Y. Hinuma, S. Matsuoka, A. Watanabe, M. Iqbal, M. Hirayama,
M. Yonemura, T. Kamiyama, I. Tanaka & R. Kanno. Pure H- conduction in（過去 5 年以内）
oxyhydrides. Science 351, 1314-1317, (2016).
2. Y. Ikeda & I. Tanaka. Stability of the omega structure of transition elements.
Physical Review B 93, 094108 (2016).
3. A. Togo & I. Tanaka. First principles phonon calculations in materials science.
Scripta Mater 108, 1-5, (2015).
4. A. Togo, L. Chaput & I. Tanaka. Distributions of phonon lifetimes in Brillouinzones. Physical Review B 91, 094306 (2015).
5. A. Seko, A. Togo, H. Hayashi, K. Tsuda, L. Chaput & I. Tanaka. Prediction of
Low-Thermal-Conductivity Compounds with First-Principles Anharmonic LatticeDynamics Calculations and Bayesian Optimization. Physical Review Letters 115,
205901 (2015).
6. A. Seko & I. Tanaka. Special quasirandom structure in heterovalent ionic systems.
Physical Review B 91, 024106 (2015).
7. A. Seko, A. Takahashi & I. Tanaka. First-principles interatomic potentials for ten
elemental metals via compressed sensing. Physical Review B 92, 054113 (2015).
8. M. Nishijima, T. Ootani, Y. Kamimura, T. Sueki, S. Esaki, S. Murai, K. Fujita,
K. Tanaka, K. Ohira, Y. Koyama & I. Tanaka. Accelerated discovery of cathodematerials with prolonged cycle life for lithium-ion battery. Nature Communications
5, 4553 (2014).
【学術関係の受賞など】 ドイツ政府
ﾌｨﾘｯﾌﾟ ･ ﾌﾗﾝﾂ ･ ﾌｫﾝ ･ ｼﾞｰﾎﾞﾙﾄ賞（2008 年）
ﾙｰﾏﾆｱ科学ｱｶﾃﾞﾐｰ ﾄﾞﾗｺﾞﾐｰﾙ・ﾌﾙﾑｾﾞｽｺ賞（2006 年）
米国ｾﾗﾐｯｸｽ学会 ﾘﾁｬｰﾄﾞ・ﾌﾙﾗｰｽ賞（2004 年）－ 11 －

Ⅰ 専任教員 ･ スーパーバイザー (2016)【氏名（ふりがな）】 田中

庸裕 （たなかつねひろ）【職名】 教授【所属】 工学研究科

分子工学専攻【研究室】 桂キャンパス A4 棟 126 号室【直通電話】 075-383-2558【FAX】 075-383-2561【電子メールアドレス】 tanakat@moleng.kyoto-u.ac.jp【ホームページ】 http://www.moleng.kyoto-u.ac.jp/~moleng_04/【研究分野】 触媒化学・固体物理化学【現在の研究課題】 固体と接触したナノ粒子・光触媒による人工光合成【研究内容キーワード】 元素戦略・ナノ粒子・X 線分光法
【学歴】 1987 年 3 月 京都大学工学研究科博士後期課程修了【学位】 1987 年 7 月 京都大学工学博士【略歴】 1987 年 10 月 北海道大学理学部助手，1990 年 4 月 京都大学工学部助手，1997
年 7 月 京都大学工学研究科助教授，2004 年 同教授【所属学会】 触媒学会，日本化学会，石油学会，アメリカ化学会，日本 XAFS 研究会，英国王立化学会【主な著書、学術論文】 1. Visible Light-Induced Water Splitting in an Aqueous Suspension of a Plasmonic（過去 5 年以内）
Au/TiO 2 Photocatalyst with Metal Co-Catalysts, A. Tanaka, K. Teramura, S.
Hosokawa, H.Kominami, T. Tanaka, Chemical Science, 2017, 8, 2574-2580.
2. 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.
3. 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.
4. 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.
5. Oxygen Storage Capacity of Sr3Fe2O7-δ Having High Structural Stability, K. Beppu,
S. Hosokawa, K. Teramura, T. Tanaka, J. Mater. Chem. A, 2015, 3, 13540-13545.
6. Highly Efficient Photocatalytic Conversion of CO2 into Solid CO Using H2O asa Reductant over Ag-Modified ZnGa2O4, Z. Wang, K. Teramura, S. Hosokawa, T.
Tanaka, J. Mater. Chem. A, 2015, 3(21), 11313-11319.
7. A Theoretical Approach to La L1-edge XANES Spectra of La Complex Oxides andTheir Local Configuration, H. Asakura, T. Shishido, K. Teramura, T. Tanaka,
J. Chem. Phys., 2015, 142(16):164507 (8 pages)

8. Noble-Metal-Free NOx Storage over Ba-Modified TiO2 Photocatalysts under UVLight Irradiation at Low Temperatures, A. Yamamoto, Y. Mizuno, K. Teramura, S.
Hosokawa, T. Shishido, T. Tanaka, ACS Catalysis, 2015, 5, 2939-2943.
9. The Support Effect on the Size and Catalytic Activity of Thiolated Au 25
Nanoclusters as Precatalyst, J. Fang, J. Li, B. Zhang, X. Yuan, H. Asakura, T.
Tanaka, K. Teramura, J. Xie, N. Yan, Nanoscale, 2015, 7, 6325-6333.
－ 12 －

Ⅰ 専任教員 ･ スーパーバイザー (2016)【氏名（ふりがな）】 山本

量一 （やまもと

りょういち）【職名】 教授【所属】 工学研究科【研究室】 桂キャンパス

化学工学専攻A 棟 118 号室【直通電話】 075-383-2661【FAX】 075-383-2651【電子メールアドレス】 ryoichi@cheme.kyoto-u.ac.jp【ホームページ】 http://www-tph.cheme.kyoto-u.ac.jp/【研究分野】 ソフトマター／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【主な著書、学術論文】 1. Simon K. Schnyder, Yuki Tanaka, John J. Molina, and Ryoichi Yamamoto,（過去 5 年以内）
Collective motion of cells crawling on a substrate: roles of cell shape and contact
inhibition, Scientific Reports, in print.
2. N. Oyama, J. J. Molina, R. Yamamoto, Purely hydrodynamic origin for swarmingof swimming particles, Phys. Rev. E 93, 043114 (2016).
3. 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).
4. A. J. Dunleavy, K. Wiesner, R. Yamamoto, and C. P. Royall, Mutual information
reveals multiple structural relaxation mechanisms in a model glassformer, Nature
Communications 6, 6089 (2015).
5. 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).
6. J. J. Molina and R. Yamamoto, Direct numerical simulations of rigid bodydispersions. I. Mobility/Friction tensors of assemblies of spheres, J. Chem. Phys.
139, 234105 (2013).
7. H. Mizuno and R. Yamamoto, General constitutive model for supercooled liquids:
Anomalous transverse wave propagation, Phys. Rev. Lett. 110, 095901 (2013).
【学術関係の受賞など】 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 (2016)【氏名（ふりがな）】 高田

彰二 （たかだ

しょうじ）【職名】 教授【所属】 理学研究科

生物科学専攻生物物理学教室【研究室】 理学部 1 号館 205 号室【直通電話】 075-753-4220【FAX】 075-753-4222【電子メールアドレス】 takada@biophys.kyoto-u.ac.jp【ホームページ】 http://theory.biophys.kyoto-u.ac.jp【研究分野】 理論生物物理学【現在の研究課題】 生体分子の構造機能についての理論およびコンピュータシミュレーション研
究【研究内容キーワード】 タンパク質フォールディング、分子モーター、遺伝子動態、生体分子モデリ
ング【最終学歴】 1991 年 9 月 総合研究大学院大学数物科学研究科機能分子科学専攻博士後期課
程退学【学位】 1994 年 3 月 理学博士（総合研究大学院大学）【略歴】 1991 年～ 1995 年 岡崎国立共同研究機構技官（分子科学研究所）、1995 年～
1998 年 日本学術振興会研究員（イリノイ大学化学科）、1998 年～ 2001 年 神戸大学理学部化学科講師、2001 年～ 2007 年 同助教授、2007 年～ 2013 年 京都大学理学研究科生物科学専攻生物物理教室准教授、2013 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 (2016)【氏名（ふりがな）】 林

重彦 （はやししげひこ）【職名】 教授【所属】 理学研究科

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

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

博士（理学）（京都大学）【略歴】 1998 年 4 月 日本学術振興会特別研究員（名古屋大学）、2000 年 4 月 米国イリノイ大学ベックマン研究所博士研究員、2003 年 6 月 京都大学福井謙一記念
研究センター博士研究員、2003 年 10 月 科学技術振興機構さきがけ研究員、2005 年 5 月 京都大学大学院理学研究科准教授、2013 年 7 月 同教授【所属学会】 分子科学会、生物物理学会、蛋白質科学会、日本化学会【主な著書、学術論文】 1. Photoactivation intermediates of a G-protein coupled receptor rhodopsin（過去 5 年以内）
investigated by a hybrid molecular simulation. Motoshi Kamiya and ShigehikoHayashi*, J. Phys. Chem. B, 121, 3842-3852 (2017).
2. 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)
3. Linear response path following: a molecular dynamics method to simulate global
conformational changes of protein upon ligand binding. Koichi Tamura andShigehiko Hayashi*, J. Chem. Theory Comput., 11, 2900-2917 (2015)
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 (2016)

⑷

専任教員

【氏名（ふりがな）】 水野

英如 （みずのひでゆき）【職名】 助教【所属】 東京大学大学院総合文化研究科広域科学専攻相関基礎科学系【直通電話】 03-5454-4376【電子メールアドレス】 hideyuki.mizuno@phys.c.u-tokyo.ac.jp【研究分野】 ソフトマター物理学【現在の研究課題】 ガラス・粉体系の振動・熱物性【研究内容キーワード】 ガラス、粉体、振動モード、熱容量、熱伝導率【学歴】 2012 年 3 月 京都大学大学院工学研究科化学工学専攻博士後期課程修了【学位】 2012 年 3 月 京都大学博士（工学）【略歴】 2012 年 4 月 Universite Grenoble 1 and CNRS, France, Postdoctoral fellow
2014 年 4 月 German Aerospace Center, Germany, Postdoctoral fellow
2016 年 2 月 京都大学福井謙一記念研究センター 研究員
2016 年 3 月 京都大学福井謙一記念研究センター 特定助教
2016 年 6 月 東京大学大学院総合文化研究科 助教【所属学会】 日本物理学会、分子シミュレーション研究会【主な著書、学術論文】 1. H. Mizuno and R. Yamamoto, “General Constitutive Model for Supercooled
Liquids: Anomalous Transverse Wave Propagation”, Physical Review Letters,（過去 5 年以内）
Vol.110, p.095901 (5pages), 2013.
2 H. Mizuno, S. Mossa, and J.-L. Barrat, “Elastic heterogeneity, vibrational states,
and thermal conductivity across an amorphisation transition”, Europhysics Letters(EPL), Vol.104, p.56001 (6pages), 2013.
3. H. Mizuno, S. Mossa, and J.-L. Barrat, “Acoustic excitations and elastic
heterogeneities in disordered solids”, Proceedings of the National Academy of
Sciences of the United States of America, Vol.111, p.11949-11954 (6pages), 2014.
4. H. Mizuno, S. Mossa, and J.-L. Barrat, “Beating the amorphous limit in thermal
conductivity by superlattices design”, Scientific Reports, Vol.5, p.14116 (15pages),2015.
5. H. Mizuno, L.E. Silbert, and M. Sperl, “Spatial Distributions of Local Elastic
Moduli Near the Jamming Transition”, Physical Review Letters, Vol.116, p.068302(5pages), 2016.
【学術関係の受賞など】 日本物理学会第 11 回若手奨励賞（2017 年 3 月）

－ 16 －

Ⅰ 専任教員 ･ スーパーバイザー (2016)【氏名（ふりがな）】 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. “Analytic Hyperpolarizability and Polarizability Derivative with
Fractional Occupation Numbers for Large Extended Systems”, J. Chem. Phys.
（過去 5 年以内）
2017, 146. 084101.
2. 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.
3. Nishimoto, Y.; Irle, S. “Quantum Chemical Prediction of Vibrational Spectra ofLarge Molecular Systems with Radial or Metallic Electronic Structure”, Chem.
Phys. Lett. 2017, 667, 317-321.
4. Nakata, H.; Nishimoto, Y.; Fedorov, D. G. “Analytic second derivative of theenergy for density-functional tight-binding combined with the fragment molecularorbital method”, J. Chem. Phys. 2016, 145, 044113.
5. Nishimoto, Y.; Fedorov, D. G. “The fragment molecular orbital method combinedwith density-functional tight-binding and the polarizable continuum model”, Phys.
Chem. Chem. Phys. 2016, 18, 22047-22061. Selected as a front cover picture.
【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 (2016)⑸

FIFC リサーチフェロー【氏名（ふりがな）】 諸熊

奎治 （もろくまけいじ）【職名】 FIFC リサーチフェロー【所属】 福井謙一記念研究センター 福井謙一記念研究部門第一【研究室】 福井謙一記念研究センター 202【直通電話】 075-711-7843【FAX】 075-781-4757【電子メールアドレス】 morokuma@fukui.kyoto-u.ac.jp【ホームページ】 http://www.fukui.kyoto-u.ac.jp/~morokuma; http://kmweb.fukui.kyoto-u.ac.jp/【研究分野】 理論化学・計算化学【現在の研究課題】 複雑分子系の分子理論によるシミュレーション【研究内容キーワード】 分子理論。複雑分子系、シミュレーション、ナノ構造、酵素反応【最終学歴】 1962 年 3 月 京都大学大学院工学研究科博士課程単位修得退学【学位】 1963 年 3 月 工学博士（京都大学）【略歴】 1962 年 4 月 京 都 大 学 工 学 部 助 手、1964 年 9 月 Columbia 大 学 客 員 助 教 授、1966 年 9 月 Harvard 大 学 博 士 研 究 員、1967 年 9 月 Rochester 大 学 助 教 授、1971 年 9 月 同 教 授、1976 年 12 月分子科学研究所教授、1993 年 1 月 Emory
大 学 教 授、2006 年 9 月 Emory 大 学 名 誉 教 授、2006 年 9 月 京 都 大 学 福 井 謙
一記念研究センターリサーチリーダー、2012 年同シニアリサーチフェロー【所属学会】 日本化学会、American Chemical Society、分子科学会【主な著書、学術論文】 過去 5 年間に約 130 報（過去 5 年以内） 1. R. I. Kaiser, L. G. Muzangwa, T. Yang, D. S. N. Parker, A. M. Mebel, A. Jamal, and
K. Morokuma, A Crossed Molecular Beam and Ab Initio Study on the Formation of
5- and 6-Methyl-1,4-Dihydronaphthalene (C11H12) via the Reaction of Meta-Tolyl(C7H7) with 1,3-Butadiene (C4H6). Phys. Chem. Chem. Phys. 17, 7699-7706 (2015).
2. B. Liu, J. Liu, H.-B. Li, R. Bhola, E. A. Jackson, L. T. Scott, A. J. Page, S.
Irle, K. Morokuma and C. Zhou, Nearly Exclusive Growth of Small Diameter
Semiconducting Single-Wall Carbon Nanotubes from Organic Chemistry Synthetic
End-Cap Molecules, Nano Lett. 15, 586-595 (2015).
3. M. Hatanaka and K. Morokuma, Exploring the reaction coordinates for f-f emission
and quenching of lanthanide complexes – thermo-sensitivity of terbium(III)luminescence. J. Chem. Theo. Comp. 10, 4184-4188 (2014).
4. M. Isegawa, F. Liu, S. Maeda and K. Morokuma, Complete active space second
order perturbation theory (CASPT2) study of N(2D) + H2O reaction paths on D1
and D0 potential energy surfaces: direct and roaming pathways, J. Chem. Phys. 141,154303/1-9 (2014).
5. S. Maeda, Y. Harabuchi, T. Taketsugu, and K.Morokuma, Systematic Exploration of
Minimum Energy Conical Intersection Structures near the Franck-Condon Region, J.
Phys. Chem. A 118, 12050-12058 (2014).
6. S. Maeda, Y. Harabuchi, Y. Ono, T. Taketsugu, and K. Morokuma, Intrinsic
Reaction Coordinate: Calculation, Bifurcation, and Automated Search, Int. J.
Quant. Chem. 115, 258-269 (2015).
7. X. Li, L. W. Chung, K. Morokuma and G. Li, A Theoretical Study on the
UVR8 Photoreceptor: Sensing Ultraviolet-B by Tryptophan and Dissociation of
Homodimer, J. Chem. Theo. Comp. 10, 3319–3330 (2014).
8. M. Isegawa, F. Liu, S. Maeda, and K. Morokuma, Ab initio reaction pathways
for photodissociation and isomerization of nitromethane on four singlet potential
energy surfaces with three roaming paths J. Chem. Phys. 140, 244310/1-11 (2014).
9. G. P. Petrova, H.-B. Li, K. Maruoka and K. Morokuma, Asymmetric phase-transfer
catalysis with homo- and heterochiral quaternary ammonium salts: a theoretical
study, J. Phys. Chem. B, 118, 5154–5167 (2014). doi:10.1021/jp501520g【学術関係の受賞など】 International Academy of Quantum Molecular Science Medal, 1978; 日本化学会賞,
1992; Schrödinger Medal, World Association of Theoretical Organic Chemists, 1993;
Fukui Medal, Asian Pacific Association of Theoretical & Computational Chemists,
2005; 恩賜賞、日本学士院賞, 2008; 瑞宝中綬章, 2010; 文化功労者, 2012－ 18 －

Ⅰ 専任教員 ･ スーパーバイザー (2016)【氏名（ふりがな）】 永瀬

茂 （ながせしげる）【職名】 FIFC リサーチフェロー【所属】 福井謙一記念研究センター【研究室】 104 室【直通電話】 075-711-7792【FAX】 075-711-4757【電子メールアドレス】 nagase@fukui.kyoto-u.ac.jp, nagase@ims.ac.jp【ホームページ】 http://www.fukui.kyoto-u.ac.jp/【研究分野】 理論化学・計算化学【現在の研究課題】 元素の特性とナノ構造を利用した分子開発の理論と計算【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

－ 19 －

Ⅰ 専任教員 ･ スーパーバイザー (2016)⑹

シニアリサーチフェロー【氏名（ふりがな）】 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. Absorption of CO2 and CS2 into the Hofmann-Type Porous Coordination Polymer:（過去 5 年以内）
Electrostatic versus Dispersion Interactions, M. M. Deshmukh, M. Ohba, S.
Kitagawa, and S. Sakaki, J. Am. Chem. Soc., 135, 4840-4849 (2013).
2. Theoretical Study of One-Electron Oxidized Mn(III) − and Ni(II) − Salen
Complexes: Localized vs Delocalized Ground and Excited States in Solution
S. Aono, M. Nakagaki, T. Kurahashi, H. Fujii, and S. Sakaki, J. Chem. Theory
Comput., 10, 1062-1073 (2014).
3. Reasons Two Nonstrained C-C σ-Bonds Can Be Easily Cleaved in Decyanative[4 + 2] Cycloaddition Catalyzed by Nickel(0)/Lewis Acid Systems. Theoretical
Insight, W. Guan, S. Sakaki, T. Kurahashi, S. Matsubara, ACS Catalysis, 5, 1-10
(2015).
4. 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).
5. 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).
6. 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).
7. 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).
8. Hetero-dinuclear complexes of 3d metals with a bridging dinitrogen ligand:theoretical prediction of the characteristic features of geometry and spin
multiplicity, M. Nakagaki, S. Sakaki, Phys. Chem. Chem. Phys., 18, 26365-26375(2016).
9. 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)【学術関係の受賞など】 第１回分子科学会賞（2009 年 9 月） 第 66 回日本化学会賞（2014 年 3 月）
Fukui Medal (2015; from APATCC)－ 20 －

Ⅰ 専任教員 ･ スーパーバイザー (2016)【氏名（ふりがな）】 田中

一義 （たなかかずよし）【職名】 シニアリサーチフェロー【所属】 福井謙一記念研究センター【研究室】 福井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

京都大学工学研究科石油化学専攻博士課程修了【学位】 1978 年 3 月

工学博士（京都大学）【略歴】 1979 年 6 月 米国エナージー・コンバージョン・デバイシズ社リサーチケミスト、
1981 年 12 月 京都大学工学部助手、1988 年 12 月 同 助教授、1996 年 11 月
京都大学大学院工学研究科教授、2012 年 4 月 京都大学福井謙一記念研究セン
ター長併任、2015 年 4 月 京都大学名誉教授ならびに京都大学福井謙一記念研究センターシニアリサーチフェロー【所属学会】 日本化学会・日本物理学会・高分子学会【主な著書、学術論文】 1. 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,
21-26 (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).
（以上和文総説）－ 21 －

Ⅰ 専任教員 ･ スーパーバイザー (2016)

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).
－ 22 －

Ⅰ 専任教員 ･ スーパーバイザー (2016)

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).
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).
－ 23 －

Ⅰ 専任教員 ･ スーパーバイザー (2016)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).
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).
（以上学術論文）【学術関係の受賞など】 2002-2007 年 科学技術振興機構（JST）の戦略的創造研究推進事業（CREST）「精密分子設計に基づくナノ電子デバイス構築」研究代表者
2004-2005 年 文部科学省知的クラスター創成事業「京都ナノテククラスター」のナノテク共同研究テーマ「mRNA の数理学的特異性抽出ソフトの開発と解析サービスの事業化展開」研究代表者－ 24 －

Ⅰ 専任教員 ･ スーパーバイザー (2016)⑺

リサーチリーダー【氏名（ふりがな）】 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】 分子科学会運営委員，計算分子科学研究拠点長（2016 年 3 月まで）
【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“Dynamical mechanism of charge
separation by photoexcited generation of proton-electron pairs in organic molecularsystems. A nonadiabatic electron wavepacket dynamics study.”Chem. Phys.
(Perspective article) 475, 39-53 (2016).
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. Takahide Matsuoka and Kazuo Takatsuka“Dynamics of photoionization frommolecular electronic wavepacket states in intense pulse laser fields: A nonadiabatic
electron wavepacket study.”J. Chem. Phys. 146, 134114 (14 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）－ 25 －

Ⅰ 専任教員 ･ スーパーバイザー (2016)⑻

研究員【氏名（ふりがな）】 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).

－ 26 －

Ⅱ 博士研究員 (2016)

Ⅱ

博士研究員等１．博士研究員組織職

平成２８年度
名

氏

名

齋藤

拓也

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
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

諸熊グループ研究フェロー

Pedro Javier Castro Pelaez
Puripat, Maneeporn

福井センターフェロー

青野

信治

中垣

雅之

Zheng, Hong

榊グループ

研究フェロー

Nishamol Kuriakose
Lu, Jing
Zhong, Ronglin

福井センターフェロー
高塚グループ研究フェロー

市川

雄一

松岡

貴英

山 本 憲太郎
長谷川 太 祐２．共同研究員
職

名

氏

名

Sameera W.M.C.
諸熊グループ共同研究員

Yanying Zhao
Ming. Chung Yang

３．日本学術振興会外国人特別研究員
職
諸熊グループ

名氏

外国人特別研究員－ 27 －

名Ren, Xuefeng

Ⅱ 博士研究員 (2016)４.博士研究員プロフィール【氏名】 Takuya Saito【研究分野】 Polymer Physics and Biophysics【現在の研究課題】 Dynamics of Single Polymeric Chain【研究内容キーワード】 Polymer dynamics, Fluctuation of driven polymer【学歴】 March 2004, Master of Sci., Graduate School of Science, Kyoto University
March 2007, Doctor of Sci., Graduate School of Science, Kyoto University【学位】 Doctor of Science from Kyoto University【略歴】 May 2007, The University of Tokyo
Apr. 2010, Kyushu University【所属学会】 The Physical Society of Japan【主な著書、学術論文】 1. Takahiro Sakaue and Takuya Saito, “Active diffusion of model chromosomal locidriven by athermal noise”, Soft Matter, 13, 81(7 pages total) (2017).
（過去 5 年以内）
2. Takuya Saito, and Takahiro Sakaue, “Driven anomalous diffusion: An example
from polymer stretching”, Phys. Rev. E, 92, 012601 (13 pages total) (2015).
3. Takuya Saito, “Rate in template-directed polymer synthesis”, Phys. Rev. E, 89,
062716 (8 pages total) (2014).
4. Takuya Saito, Takahiro Sakaue, “Cis-trans dynamical asymmetry in driven polymertranslocation”, Phys. Rev. E, 88, 042606 (5 pages total) (2013).
5. Takuya Saito, Takahiro Sakaue, “Process time distribution of driven polymertransport”, Phys. Rev. E, 85, 061803 (7 pages total) (2012).
6. Takahiro Sakaue, Takuya Saito, Hirofumi Wada, “Dragging a polymer in a viscous
fluid: steady state and transient”, Phys. Rev. E, 86, 011804 (8 pages total) (2012).
7. 坂上貴洋、齋藤拓也, 日本物理學會誌 67(10), 705-709, 2012-10-05.「紐状分子の非平衡ダイナミクス：細孔通過現象を中心に」【学術関係の受賞など】 JSPS Research Fellowships for Young Scientists(DC2) 2005.4-2007.3－ 28 －

Ⅱ 博士研究員 (2016)【氏名（ふりがな）】 多羅間

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

京都大学理学研究科
京都大学理学研究科【学位】 博士（理学）【略歴】 福井センターフェロー（2015/4/1 より）【所属学会】 日本物理学会【学会活動】 アクティブマター研究会 2016（2016 年 1 月 22-23 日）の世話人をしました。
アクティブマター研究会 2017（2017 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).
【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)－ 29 －

Ⅱ 博士研究員 (2016)【氏名（ふりがな）】 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】 非線形ランジュバン方程式の導出・熱流に誘起された非平衡力【研究内容キーワード】 大偏差理論・経路積分・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).

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Ⅱ 博士研究員 (2016)【氏名（ふりがな）】 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（過去 5 年以内）
and Natsuhiko Yoshinaga, Journal of Fluid Mechanics, November 2016, Pages
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. “Hydrodynamics in bridging and aggregation of two colloidal particles in a nearcritical binary mixture”, Shunsuke Yabunaka, Ryuichi Okamoto and Akira Onuki,
Soft Matter, 2015, 11, 5738
5. “Geometric pumping induced by shear flow in dilute liquid crystalline polymer
solutions”, Shunsuke Yabunaka and Hisao Hayakawa, J. Chem. Phys. 142, 054903(2015)【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

－ 31 －

Ⅱ 博士研究員 (2016)【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, 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【所属学会】 German Physical Society (DPG)【主な著書、学術論文】 1. S. K. Schnyder, T. O. E. Skinner, A. Thorneywork, D. G. A. L. Aarts, J. Horbach,（過去 5 年以内）
R. P. A. Dullens, “Dynamic heterogeneities and non-Gaussian behaviour in 2D
randomly confined colloidal fluids”, Physical Review E (2017).
2. M. Heinen, S. K. Schnyder, J. F. Brady, H. Löwen, “Classical liquids in fractal
dimension”, Physical Review Letters 115, 097801 (2015).
3. S. K. Schnyder, M. Spanner, F. Höfling, T. Franosch, J. Horbach, “Rounding of thelocalization transition in model porous media”, Soft Matter 11, 701 (2015).
4. T. O. E. Skinner, S. K. Schnyder, D. G. A. L. Aarts, J. Horbach, R. P. A. Dullens,“Localization Dynamics of Fluids in Random Confinement”, Physical Review
Letters 111, 128301 (2013).
5. M. Spanner, S. K. Schnyder, F. Höfling, Th. Voigtmann, T. Franosch, “Dynamic
arrest in model porous media—intermediate scattering functions”, Soft Matter 9,1604-1611 (2013).

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Ⅱ 博士研究員 (2016)【氏名（ふりがな）】 伊勢川

美穂 （いせがわみほ）【職名】 Postdoctoral Fellow【所属】 FIFC, Kyoto University【研究室】 Morokuma Group【直通電話】 075-711-7708【電子メールアドレス】 isegawa.miho.5s@kyoto-u.ac.jp【研究分野】 計算化学
【現在の研究課題】 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
2013 年 3 月
2014 年 6 月
2016 年 1 月

米国ミネソタ大学博士研究員
京都大学福井謙一記念研究センター研究員
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
京都大学福井謙一記念研究センター研究員【主な著書、学術論文】 1. Copper-catalyzed Enantioselective Boron Conjugate Addition: DFT and AFIR
（過去 5 年以内）
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, (2017).
2. 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).
3. 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).
4. 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).
5. 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).
6. Electrostatically Embedded Molecular Tailoring Approach and Validation for
Peptides, M. Isegawa, B. Wang, D. G. Truhlar, J. Chem. Theory Comput. 9, 1381
(2013).

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Ⅱ 博士研究員 (2016)【氏名（ふりがな）】 鈴木

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

計算化学

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

九州大学理学府【学位】 2014 年 3 月

博士（理学） 九州大学

【略歴】 2014 年 4 月

福井謙一記念研究センター

化学専攻修了【所属学会】 分子科学会、理論化学研究会【主な著書、学術論文】 1. T. Tsuneda, J.-W. Song,S. Suzuki, and K. Hirao ”On Koopmans'theorem in density
functional theory” J. Chem. Phys. 133, 174101 (2010).
（過去 5 年以内）
2. S.Suzuki, S. Maeda, K. Morokuma, Exploration of Quenching Pathways ofMultiluminescent Acenes Using the GRRM Method with the SF-TDDFT Method, J.
Phys. Chem. A, 119 pp 11479-11487 (2015)
3. S.Sasaki, S.Suzuki, W.M.C. Sameera, K. Igawa, K. Morokuma, G. Konishi,
Highly twisted N,N-dialkylamines as a design strategy to tune simple aromatichydrocarbons as steric environment-sensitive fluorophores, J. Am. Chem. Phys.,138, 8194-8206 (2016)【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－ 34 －

Ⅱ 博士研究員 (2016)【氏名】 Akhilesh Kumar Sharma【職名】 Postdoctoral Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room No. 203【直通電話】 075-711-7831【FAX】 075-781-4757【電子メールアドレス】 sharma@fukui.kyoto-u.ac.jp【研究分野】 Computational Chemistry【現在の研究課題】 Mechanistic study of organic and 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. Akhilesh K. Sharma, Raghavan B. Sunoj, “Refined Transition-State Models for
Proline-Catalyzed Asymmetric Michael Reactions under Basic and Base-Free（過去 5 年以内）
Conditions” J. Org. Chem. 77 (23), 10516-10524 (2012).
2. Dmitry Katayev, Yi-Xia Jia, Akhilesh K. Sharma, Dipshikha Banerjee, Celine
Besnard, Raghavan B. Sunoj, and E. Peter Kundig, “Synthesis of 3,3-Disubstituted
Oxindoles by Palladium-Catalyzed Asymmetric Intramolecular α-Arylation ofAmides: Reaction Development and Mechanistic Studies” Chem. Eur. J. 19, 1191611927 (2013).
3. Akhilesh K. Sharma, Dipankar Roy and Raghavan B. Sunoj, “Mechanism of
Catalytic Methylation of 2-Phenylpyridine Using di-tert-Butyl Peroxide” Dalton
Trans. 43, 10183-10201 (2014).
4. W. M. C. Sameera, Akhilesh K. Sharma, Satoshi Maeda, Keiji Morokuma, “Artificial
Force Induced Reaction Method for Systematic Determination of Complex
Reaction Mechanisms” Chemical Record, 16 (5), 2349-2363 (2016).
5. 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).
6. 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. DOI: 10.1021/acscatal.7b01152.
【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.

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Ⅱ 博士研究員 (2016)【氏名】 Maneeporn Puripat【職名】 Research Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 213【直通電話】 075-711-7834【電子メールアドレス】 puripat@fukui.kyoto-u.ac.jp【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【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 urea（過去 5 年以内）
catalyzed organocatalytic multicomponent reaction” J. Org. Chem. 80 (14), 69596967 (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).

【学術関係の受賞など】 The Development and Promotion of Science and Technology Talents Project (DPST)(Royal Government of Thailand scholarship) of Thailand (2004-2016)－ 36 －

Ⅱ 博士研究員 (2016)【氏名（ふりがな）】 青野

信治 （あおのしんじ）【職名】 特定研究員【所属】 京都大学 福井謙一記念研究センター【研究室】 福井記念研究センター 303 号室【直通電話】 075-711-7907【電子メールアドレス】 saono@fukui.kyoto-u.ac.jp【研究分野】 溶液化学・計算化学・理論化学【現在の研究課題】 溶液中の遷移金属錯体の化学反応の理論的解析【研究内容キーワード】 3D-RISM-SCF 法、平均場 QM/MM 法、自由エネルギー解析、溶媒和構造解析、
周期的分子結晶解析【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, 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（過去 5 年以内）
(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).
2. 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).
3. 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).
4. Aono S., Hosoya T., and Sakaki S., “A 3D-RISM-SCF method with dual solvent
boxes for a highly polarized system: application to 1,6-anhydrosugar formation
reaction of phenyl alpha- and beta-D-glucosides under basic conditions” Phys.
Chem. Chem. Phys. 17, 6368, (2013)
5. Aono S. and Sakaki S., “Evaluation Procedure of Electrostatic Potential in
3D-RISM-SCF Method and Its Application to Hydrolyses of Cis- and Transplatin
Complexes” J. Phys. Chem. B 116, 13045, (2012)
6. Aono S. and Sakaki S., “Proposal of new QM/MM approach for geometry
optimization of periodic molecular crystal: Self-consistent point charge
representation for crystalline effect on target QM molecule” Chem. Phys. Lett. 544,
77, (2012).
－ 37 －

Ⅱ 博士研究員 (2016)【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)－ 38 －

Ⅱ 博士研究員 (2016)【氏名】 Hong Zheng【職名】 SPR Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 303【直通電話】 075-711-7907【FAX】 075-711-7838【電子メールアドレス】 zhenghong@fukui.kyoto-u.ac.jp【研究分野】 Computational chemistry【現在の研究課題】 Theoretical Study of C-O activation by Rh-(PAlP) complex【研究内容キーワード】 Transition state and electronic property of C-O activation【学歴】 December 2012, School of Science, Xi’an Jiaotong University【学位】 Doctor of Materials Physics and Chemistry, Xi’an Jiaotong University【略歴】 July 2014, Postdoctoral Fellow, Kyoto University【主な著書、学術論文】 1. H. Zheng, X. Zhao, T. Ren, W. W. Wang, C 74 Endohedral metallofullerenes
violating the isolated pentagon rule: A density functional theory study, Nanoscale, 4,（過去 5 年以内）
4530-4536 (2012)
2. H. Zheng, X. Zhao, W. W. Wang, T. Yang, S. Nagase, Sc2@C70 rather than Sc2C2@
C68: Density functional theory characterization of metallofullerene Sc2C70, J. Chem.
Phys., 137, 014308 (2012)
3. H. Zheng, J. Li, X. Zhao, Regioselective Chlorine-Addition Reaction toward C54Cl8
and Role of Chlorine Atoms in Stone-Wales Rearrangement, Dalton Trans, 41,
14281-14287 (2012)
4. H. Zheng, X. Zhao, W. W. Wang, J. S. Dang, S. Nagase, Quantum Chemical Insight
into Metallofullerenes M2C98: M2C2@C96 or M2@C98, Which Will Survive? J. Phys.
Chem. C, 117, 25195-25204 (2013)
5. H. Zheng, J. Zheng, L. He, X. Zhao, Unique Configuration of A Nitrogen-doped
Graphene Nanoribbon: Potential Applications to Semiconductor and Hydrogen Fuel
Cell, J. Phys. Chem. C, 118, 24723-24729 (2014)
6. H. Zheng, X. Zhao, L. He, W. W. Wang, S. Nagase, Quantum Chemical
Determination of Novel C82 Monometallofullerenes Involving a HeterogeneousGroup, Inorg. Chem., 53, 12911-12917 (2014)
7. K. Semba, K. Ariyama, H. Zheng, R. Kameyama, S. Sakaki, Y. Nakao, “Reductive
Cross-Coupling of Conjugated Arylalkenes and Aryl Bromides with Hydrosilanes
by Cooperative Palladium/Copper Catalysis”, Angew. Chem. Int. Ed. 55, 6275
-6279 (2016)
8. H. Zheng, X. Zhao, S. Sakaki, “[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”, Inorg. Chem. 56, 67466754 (2017)－ 39 －

Ⅱ 博士研究員 (2016)【氏名】 Lu Jing
【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【学歴】 June 2016, Doctor of Sci., Polymer chemistry and physics, Northeast Normal
University, P.R. China【学位】 Doctor of Science from Northeast Normal University【略歴】 Oct. 2016, Postdoctoral Fellow, FIFC, Kyoto University【主な著書、学術論文】 1. J. Lu, Y. Zheng, J., Zhang, Tuning the color of thermally activated delayed
fluorescent properties for spiro-acridine derivatives by structural modification of the（過去 5 年以内）
acceptor fragment: a DFT study, RSC Adv., 5, 18588-18592 (2015).
2. J. Lu, Y. Yao, P. M. Shenai, L. Chen, Y. Zhao, 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).
3. J. Lu, Y. Zheng, J., Zhang, Rational design of phenoxazine-based donor-acceptordonor thermally activated delayed fluorescent molecules with high performance.
Phys. Chem. Chem. Phys., 17, 20014-20020 (2015).
4. J. Lu, Y. Zheng, J., Zhang, Computational design of benzo [1,2-b:4,5-b']
dithiophene based thermally activated delayed fluorescent materials, Dyes andpigments, 127, 189-196 (2016).

－ 40 －

Ⅱ 博士研究員 (2016)【氏名】 Rong-Lin Zhong【職名】 SPR Fellow【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 303【直通電話】 075-711-7907【FAX】 075-711-7907【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/piccon.php?id=89&SortID=9【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. Rong-Lin Zhong, Hong-Liang Xu,* Zhi-Ru Li* and Zhong-Min Su*. Role of
Excess Electrons in Nonlinear Optical Response. J. Phys. Chem. Lett. 2015, 6, 612（過去 5 年以内）
619
2. Rong-Lin Zhong, Hong-Liang Xu,* Shi-Ling Sun, Yong-Qing Qiu, and Zhong-Min
Su*. The Excess Electron in a Boron Nitride Nanotube: Pyramidal NBO Charge
Distribution and Remarkable First Hyperpolarizability. Chem. Eur. J. 2012, 18,11350-11355.
3. Rong-Lin Zhong, Ji Zhang, Shabbir Muhammad, Yang-Yang Hu, Hong-Liang Xu,*
and Zhong-Min Su*. Boron/Nitrogen Substitution of the Central Carbon Atomsof the Biphenalenyl Diradical pi-Dimer: A Novel 2e–12c Bond and Large NLO
Responses. Chem. Eur. J. 2011, 17, 11773-11779
4. Rong-Lin Zhong, Hong-Liang Xu,* Shabbir Muhammad, Ji Zhang and ZhongMin Su*. The stability and nonlinear optical properties: Encapsulation of an excess
electron compound LiCN/Li within boron nitride nanotubes. J. Mater. Chem., 2012,
22, 2196-2202.
5. Rong-Lin Zhong, Shi-Ling Sun, Hong-Liang Xu,* Yong-Qing Qiu, and ZhongMin Su*. BN Segment Doped Effect on the First Hyperpolarizibility ofHeteronanotubes: Focused on an Effective Connecting Pattern. J. Phys. Chem. C
2013, 117, 10039-10044.

－ 41 －

Ⅱ 博士研究員 (2016)【氏名（ふりがな）】 松岡

貴英 （まつおかたかひで）【職名】 研究フェロー【所属】 福井謙一記念研究センター【研究室】 303
【電子メールアドレス】 matsuoka@fukui.kyoto-u.ac.jp【研究分野】 計算化学

【現在の研究課題】 非断熱電子動力学理論による化学反応【研究内容キーワード】 電子動力学，非断熱相互作用，高強度レーザー【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

慶應義塾大学准訪問研究員、2015 年 7 月 東京大学特定研究員【所属学会】 日本化学会，分子科学会，理論化学研究会【主な著書、学術論文】 1. 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).

－ 42 －

Ⅱ 博士研究員 (2016)【氏名（ふりがな）】 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【研究室】 福井謙一記念研究センター

高塚グループ305【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. J. Manz and K. Yamamoto, Mol. Phys. 110, 517 (2012).
（過去 5 年以内）
2. K. Yamamoto and K. Takatsuka, J. Chem. Phys. 140, 124111 (2014).
3. K. Yamamoto and K. Takatsuka, ChemPhysChem 16, 2534 (2015).
4. K. Yamamoto and K. Takatsuka, Chem. Phys. 475, 39 (2016).
5. K. Yamamoto and K. Takatsuka, ChemPhysChem 18, 537 (2017)－ 43 －

Ⅱ 博士研究員 (2016)５.共同研究員プロフィール【氏名】 Yanying Zhao
【職名】 Visiting Scholar【所属】 Fukui Institute for Fundamental Chemistry【研究室】 Room 203【直通電話】 075-711-7834【FAX】 075-711-7834【電子メールアドレス】 zhaoyying2008@hotmail.com【研究分野】 Molecular Spectroscopy and Computational Chemistry【現在の研究課題】 Reaction of photo-functional molecules, metal catalysis reaction【研究内容キーワード】 Transition metal catalyzed synthetic reaction by GRRM
【学歴】 Sept. 2000, Master of Sci., Department of Chemistry, Hebei Normal University, China
Sept. 2004, Doctor of Sci., Department of Chemistry, Fudan University, China【学位】 Doctor of Science from Fudan University, China【略歴】 October. 2007, Assistant Professor, Associate Professor, Zhejiang Sci-Tech University,
China【所属学会】 Chemical Society of China【主な著書、学術論文】 1. Pang, Sumei, Zhao Yanying*, Xue Jiadan, Zheng Xuming. "Solvent-dependent
dynamics of hydrogen bonding structure 5-(methylthio)-1, 3, 4-thiadiazole-2（過去 5 年以内）(3H)-thione as determined by Raman spectroscopy and theoretical calculation."Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 171 (2017):
470-477.
2. Liu, Xin, and Yanying Zhao*. "Adsorption Kinetics of Methylene Blue on
Synthesized DMF-MIL-101 (Cr), a DMF-functionalized Metal-organic
Framework." Key Engineering Materials 671 (2016).
3. Chen Xiao, Zhao Yanying*, Zhang Haibo, Xue jiadan, Zheng Xuming* Excitedstate proton transfer dynamics of thioacetamide in S2(π-π*) state: resonance Raman
spectroscopic and quantum mechanical calculations study. J. Phys. Chem. A 119,
832-842(2015)
4. Zhao Yanying, Xu Qiang* Chapter 15, Metal-organic frameworks as platforms
for hydrogen generation from chemical hydrides in Organometallics and Related
Molecules for Energy Conversion, Green Chemistry and Sustainable Technology.
Springer-Verlag Berlin Heidelberg 421-467(2015). W.-Y. Wong (ed.), DOI
10.1007/978-3-662-46054-2_15.
5. Li Dan, Zhao Yanying*, Xue Jia-Dan, Zheng Xuming Structural dynamics of
4-formaldehyde imidazole and imidazole in light absorbing S2(π-π*) state Journalof Raman Sepctroscopy 46(3), 293-301 (2015).
6. Zhao Yanying*, Zhang Yuchen, Liu Xin, Zheng Xuming Formation,
characterization, structure and bonding analysis of the metal-carbon bond OM-(ŋ6C6H6) (M = Sc, Ti) complexes in solid matrix: Infrared spectroscopic and theoretical
study. J. Orgmet. Chem. 777, 25-30 (2015)
7. Zhao Yanying*, Fan Kexue, Huang Yongfei, Zheng Xuming Matrix isolation
infrared spectra, assignment and DFT investigation on reactions of iron andmanganese monoxides with CH3C1. Spectrochimica Acta Part A-Molecular andBiomolecular Spectroscopy 116, 96-101 (2013)
8. Zhao Yanying* C-Cl Activation by Group IV Metal Oxides in Solid Argon
Matrixes: Matrix Isolation Infrared Spectroscopy and Theoretical Investigations of
the Reactions of MOx (M = Ti, Zr; x=1, 2) with CH3Cl. J. Phys. Chem. A 117(27),5664-5674 (2013)【学術関係の受賞など】 Project Grants 521 521 Talents Cultivation, Zhejiang Sci-Tech University, Zhejiang,
Zhejiang, 2012~Present－ 44 －

Ⅱ 博士研究員 (2016)【氏名】 Ming-Chung Yang
【職名】 Postdoctoral research fellow【所属】 National Chiayi University, Department of Applied chemistry【研究室】 Room 407【直通電話】 886 5 2717899【FAX】 00886 5 2717901【電子メールアドレス】 mingchungmc@gmail.com【研究分野】 Computational Chemistry【現在の研究課題】 Reaction of Transition metal complexes【研究内容キーワード】 Endohedral metallofullerenes, Triply-bonded molecules【学歴】 September 2006 - January 2012 National Tsing Hua University, Chemistry Department【学位】 Doctor of Philosophy【略歴】 Auguest 2013 – up to date Postdoctoral research fellow【主な著書、学術論文】 1. 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) and（過去 5 年以内）
L2M(M = Pd, Pt) to Li+@C60. The Journal of Physical Chemistry A, 2017, 121,2665-2673.
2. Jia-Syun Lu, Ming-Chung Yang and Ming-Der Su Triply-bonded indium
phosphorus molecules: theoretical designs and characterization. RSC Advances,
2017, 7, 20597-20603.
3. Jia-Syun Lu, Ming-Chung Yang, and Ming-Der Su Indium–Arsenic Molecules withan In≡As Triple Bond: A Theoretical Approach. ACS Omega, 2017, 2, 1172-1179.
4. Jia-Syun Lu, Ming-Chung Yang and Ming-Der Su. The effect of substituents on
triply bonded boron≡antimony molecules: a theoretical approach. Phys. Chem.
Chem. Phys., 2017, 19, 8026-8033.
5. Jia-Syun Lu, Ming-Chung Yang and Ming-Der Su. The Effect of Substituents on
the Stability of Triply Bonded Gallium≡Antimony Molecules: A New Target for
Synthesis. Dalton Transactions, 2017, 46,1848-1856.

－ 45 －

Ⅱ 博士研究員 (2016)６.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－ 46 －

Ⅲ 研究広報活動 (2016)

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 14 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2017 年 1 月 27 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
高塚

和夫 （京都大学 福井謙一記念研究センター リサーチリーダー）「化学反応における電子動力学 －電子の運動が観える時代の基礎化学－」
11:25 – 12:25
八島栄次 （名古屋大学 大学院工学研究科）「らせん構造を基本骨格とする超分子・高分子の創成、構造と機能」

12:35 – 13:35
高田彰二 （京都大学 大学院理学研究科）「複雑生体分子系のマルチスケールシミュレーション」

―

休

憩

―

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）－ 47 －

Ⅲ 研究広報活動 (2016)

２．セミナー（1）第 14 回 福井センターセミナー
日時2016 年（平成 28 年）4 月 13 日（水） 13:30 − 17:00

場

所

京都大学福井謙一記念研究センター（１階 106 室）
13:30 − 14:20
Takahiro Sasamori (Kyoto Univ.)“What is the Difference of Multiple Bonds between Carbon and heavier
Group 14 Elements?”
14:20 − 15:10
Atsushi Wakamiya (Kyoto Univ.)“Materials Design for Highly Efficient Perovskite Solar Cells”
15:25 − 16:15
Hideki Yorimitsu (Kyoto Univ.)“Journey from Discovery of New Pummerer Chemistry to Catalytic C-S
Bond Cleavage”
16:15 − 17:00
Shigeyoshi Sakaki (Kyoto Univ.)“The Present and Future of Molecular Theory and Calculations inTransition Metal Chemistry”（2）その他のセミナー
Contact

Speaker

Shigeyoshi
Sakaki

GernotFrenking

Title
Dative bonding in maingroup compounds－ 48 －

Affiliation

Date

PhilippsUniversität
Marburg

April 26
(Tue),
2016

Ⅲ 研究広報活動 (2016)

Contact

Affiliation

Date

HannesJonssonMechanism and rateof hydrocarbon andalcohol formation in CO2electroreduction obtained
from detailed atomic scalemodeling

University of
IcelandJune 10(Fri),
2016

Jörn Manz

Intramolecular ﬂuxes:
form tunnelling to charge
migration, or fromkiloseconds to attoseconds

Freie
Universität
Berlin andShanxiUniversity

July 14(Thu),
2016

Bun ChanDouble-Hybrid Density
Functional Theory:
Development and Application
to Fullerene Chemistry

Nagasaki
University

August25 (Thu),
2016

Shigeyoshi
Sakaki

Naoki
Nakatani

Density Matrix
Renormalization Group in
Practice: A Guide to Large
Active-Space Multi-Reference
Computations

Tokyo
Metropolitan
University

February
15 (Wed),
2017

Keiji
Morokuma

Rajeev
Prabhakar

Computational Modeling ofReaction Mechanisms, Drugs
and Biomaterials

University of
Miami

February
16 (Thu),
2017

Shigeyoshi
Sakaki

Ashutosh
Gupta

Role of Noble Gas in Binding
Ability of Metal Cyanides,
Halides and Oxides (Metal =Cu, Ag, Au): A Computational
Investigation

Udai Pratap
CollegeMarch
3 (Fri),2017

Shigeyoshi
SakakiTsuyoshi
Kato

Some interesting perspectivesof stable silylenes

Université deToulouseMarch
9 (Thu),2017

Ingo Barth

Quantum Hydrodynamice
Approach for Calculations ofElectronic Current Densities

Max Planck
InstituteJörn Manz

Electronic ﬂuxes during
intramolecular adiabatic
attosecond charge migration

Berlin Free
University

Wolfgang
DomckeBurning water withsunlight: guidelines fromcomputational chemistry

Technical
University of
MunichShigeyoshi
Sakaki

Kazuo
Takatsuka

Shigeyoshi
Sakaki

Kazuo
Takatsuka

Speaker

Title－ 49 －March
9 (Thu),
2017

March
10 (Fri),
2017

Ⅲ 研究広報活動 (2016)

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

4．社会へのアウトリーチ活動＜研究紹介＞
2016年（平成28年）9月18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：分子内の電子のダイナミクスを観る・操る

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：自動車触媒とコンピュータ計算化学

場

所：京都大学百周年時計台記念館＜学術講演＞
2016年（平成28年）11月15日（２）田中 一義 シニアリサーチフェロー
演

題：元素ブロック設計のための計算化学とその実例

行事名：日本化学会秋季事業第６回 CSJ 化学フェスタ 2016 特別企画
場

所：江戸川区タワーホール船堀
2016年（平成28年）12月6日（３）田中 一義 シニアリサーチフェロー
演

題：企業研究者のための計算化学

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－ 50 －

Ⅲ 研究広報活動 (2016)

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 28 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 29 年 1 月 27 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：辻 雄太（九州大学 分子システムデバイス国際リーダー教育センター 助教）
受賞題目：理論化学研究に立脚した量子干渉現象の分子エレクトロニクスへの展開

6．複雑・複合系の理論計算科学に関する
日・仏・スペイン合同シンポジウムを開催
本学は、福井謙一博士の存在により、特に化学および生命科学分野で計算科学研究が歴史的に盛んであり、わが国はもとより世界レベルで先導的な研究を進めてきた。本シンポ
ジウムは、わが国の窓口となり、わが国の若手、中堅研究者に、フランス、スペインからの若手、中堅研究者を加え、複雑・複合系に関する理論計算科学に関する研究成果を互いに紹介しあい、理論計算科学を機軸とする融合研究の更なる展開を目指し、このシンポジウムが開催された。（平成 28 年 10 月 26 日～ 28 日）

7．日本－ブラジル

理論化学 ･ 計算化学交流会を開催

国 際 シ ン ポ ジ ウ ム“Multi-scale Simulation of Condensed-phase Reacting Systems
2016”へのブラジルからの参加者とセンター関係者との交流会を開催。（平成 28 年 10 月
13 日）

8．日本化学会賞受賞（赤木和夫センター長）
赤木和夫センター長は、日本化学会賞を受賞した。受賞の対象となった業績は「液晶と共役ポリマーとの融合化学の開拓と展開」であった。（平成 29 年 3 月 17 日の日本化学会
第 97 回春季年会）－ 51 －

Ⅳ 研究業績 (2016)

Ⅳ

研究業績

１．専任教員

Hideyuki Mizuno
Hideyuki Mizuno
Assistant Professor
Assistant Professor

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

1. Summary of the research of the year (2016)
Vibrational properties of amorphous solids in the continuum limit
Why low-ω-vibrational and low-T-thermal properties of amorphous solids are markedly different
from the crystalline counterparts is a long-standing mystery in condensed matter physics. Crystals
follow the universal laws which are controlled by phonon [1]. Experimental observations of thevibrational density of states g(ω) ~ ω2, heat capacity C ~ T3, and the thermal conductivity κ ~ T3 arerationalized by the Debye theory and the phonon-gas theory based on the phonon. Amorphoussolids are characterized as well by the universal laws that are, however, anomalous with respect tothe crystalline counterparts [2]. Much attention has been paid to the boson peak (BP): The heat
capacity C is larger than the crystalline value at T ≈ 10[K], which directly reflects the excess
vibrational modes around ωBP ≈ 1[THz].
Here, we would remark that even at much lower T ≤ 1[K], thermal properties are alreadyanomalous, e.g., the thermal conductivity increases as κ ~ T2, instead of κ ~ T3 [3]. This indicatesthat the vibrational modes are not rationalized by the phonon even at very low ω ≈ 0.1[THz], oneorder of magnitude lower than ωBP. This behavior is highly counter-intuitive because any solid
matter, not only crystalline but also amorphous, is expected to behave as a homogeneous elastic
medium in the continuum limit, and its vibrational modes are expected to converge to the phonons
in the low-ω regime.
To resolve this issue, we report the first numerical evidence that these anomalous properties ofamorphous solids can be described in terms of the coexistence of phonons and “soft localized
modes”. In our study [4], we performed extremely large-scale molecular-dynamics simulations on
amorphous solids and directly observed very-low-frequency vibrational modes. Here we wouldemphasize that direct observation of such the low-frequency modes is technically challenging sothat it has never been achieved before. We found that phonons and soft localized modes coexist in
the low-frequency regime, which should control the low-temperature thermal properties ofamorphous solids. Importantly, we discovered that the phonons follow the Debye law, whereas thesoft localized modes follow another universal, non-Debye law. These findings provide the first firm
theoretical ground to explain the experimentally established anomalous properties of amorphoussolids.

－ 52 －

Ⅳ 研究業績 (2016)

References[1] C. Kittel, Introduction to Solid State Physics, 7th ed. (John Wiley and Sons, New York, 1996).
[2] W. A. Phillips, Amorphous Solids: Low Temperature Properties, 3rd ed. (Springer, Berlin, 1981).
[3] R. C. Zeller and R. O. Pohl, Phys. Rev. B 4, 2029 (1971).
[4] H. Mizuno, H.Shiba, A.Ikeda, arXiv:1703.10004 (2017).

2. Original papers[1]

H. Mizuno, S. Mossa, and J.-L. Barrat, “Relation of vibrational excitations and thermal
conductivity to elastic heterogeneities in disordered solids”, Physical Review B, Vol.94,
p.144303 (22pages), 2016.

[2]

H. Mizuno, K. Saitoh, and L. E. Silbert, “Elastic moduli and vibrational modes in jammed
particulate packings”, Physical Review E, Vol.93, p.062905 (21pages), 2016.

[3]

H. Mizuno, L. E. Silbert, M. Sperl, S. Mossa, and J.-L. Barrat, “Cutoff nonlinearities in the
low-temperature vibrations of glasses and crystals”, Physical Review E, Vol.93, p.043314(18pages), 2016.

[4]

H. Mizuno, L. E. Silbert, and M. Sperl, “Spatial Distributions of Local Elastic Moduli Near the
Jamming Transition”, Physical Review Letters, Vol.116, p.068302 (5pages), 2016.

[5]

K. Saitoh and H. Mizuno, “Enstrophy cascades in two-dimensional dense granular flows”,
Physical Review E, Vol.94, p.022908 (11pages), 2016.

[6]

K. Saitoh and H. Mizuno, “Anomalous energy cascades in dense granular materials yielding
under simple shear deformations”, Soft Matter, Vol.12, p.1360-1367 (8pages), 2016.

3. Presentation at academic conferences (invited talk)[1]

水野英如, “ジャミング転移点近傍における粉体の弾性応答”, 粉体工学会「計算粉体力学研究会」, 同志社 大学, 京都, 2016.7.4.

[2]

水野英如, “ガラスとナノ構造化物質の力学・熱物性の理論的研究”,日本物理学会第 11 回若手奨
励賞(領域 12) 受賞記念講演, 大阪大学, 大阪, 2017.3.17.

4. Others[1]池田昌司, 水野英如, 尾澤岬, 宮崎州正, “ガラス転移とアモルファス固体：最近の理論研究から”, ニューガラス, Vol.31, p.3-6 (4pages), 2016.（依頼解説）－ 53 －

Ⅳ 研究業績 (2016)

Yoshio Nishimoto
Program-Specific Assistant Professor
1. Summary of the research of the year
Theoretical Developments of FMO-DFTB
I’m developing a large-scale quantum-mechanical method, FMO-DFTB [1], these days.
FMO-DFTB is a combined method between the fragment molecular orbital (FMO) approach and thedensity-functional tight-binding (DFTB) method. A previous study revealed the efficiency of FMO-DFTB,
and a geometry optimization of a one-million-atom system could be successfully completed.
The first development is referred to as FMO-DFTB/PCM [2], which is the combination of
FMO-DFTB and the polarizable continuum model (PCM). Application of FMO-DFTB to some proteins
which usually have a lot of charged residues has been prohibited, because SCF convergence of dimers (andtrimers) has been poor without solvent effects. In this study, I developed the energy and its analytic gradientof FMO-DFTB/PCM. The energy and its derivative can be implemented by following previous studies. Since
FMO is not a fully variational method, one has to compute the response of molecular orbitals (MOs) incomputing the analytic gradient. The response can be efficiently computed by solving the Z-vector equationfor each monomer self-consistently with respect to the auxiliary density on each monomer.
By comparing the MO diagrams
obtained with and without PCM, I found that
there is a large difference between the levels of
the HOMO and the LUMO. In the computationin vacuum without PCM, the level of the
HOMO of a monomer with a negative charge
tends to be high. In this case, the level of the
HOMO may be higher than that of the LUMO.
If one performs a dimer SCF calculation by
combining these monomers (Fig. 1(A)), the
HOMO of a fragment is higher than the LUMO

Fig. 1 A possible initial electronic configuration of a dimer
without PCM.

of another fragment. Here, Ith and Jth fragments roughly corresponds to positively and negatively charged
fragments, respectively. In this case, electron transfer may occur between the two fragments, if electrons
occupy orbitals according to the building principle, and the electronic state may break down as aconsequence. If such a breakdown occurs, the accuracy may be extremely poor or the SCF cycle may notconverge. On the other hand, if PCM is employed, the reversal of the energy level does not occur, so there
are no such problems in the computation. Eventually, a geometry optimization for the bovine
chymotrypsinogen A (PDB ID: 2CGA) consisting of 3578 atoms could be completed.
Another development is the inclusion of the three-body effect, referred to as FMO3-DFTB [3]. The－ 54 －

Ⅳ 研究業績 (2016)previous developments were limited to the two-body case (FMO2), and the inclusion of the three-body effectshould be beneficial in improving the accuracy of FMO-DFTB. I could indeed verify this; for instance, there
was an error of 25.88 kcal/mol for the 2CGA protein with the conventional FMO2-DFTB/PCM<1>, while
the error was decreased to 7.71 kcal/mol with FMO3-DFTB/PCM<1>. However, the computational cost isapproximately four times more expensive.
I also performed molecular dynamics (MD)simulations for Na+(H2O)473 and predicted the hydration
number of the sodium cation. Because the positive
charge should delocalize around Na+, FMO2-DFTB
which is not sufficiently take into account many bodyeffects may not describe the coordination structurearound Na+ correctly. FMO2-DFTB predicted ahydration number of 8.6, while FMO3-DFTB which
was developed in this study did that of 6.5. The value
obtained with 6.5 reasonably agrees with the hydration
number predicted with other methodologies (5–6), andFig. 2 Radial distribution function between

Na+–O.
in addition, it is also found that FMO2-DFTB highly overestimates the hydration number. Indeed,

FMO2-DFTB (the black line in Fig. 2) overestimates the first peek at around a Na+–O distance of 2.5 Å,compared with FMO3-DFTB (the red line in Fig. 2). In another comparison using a smaller system also revealed
that FMO3-DFTB reproduced the radial distribution function predicted by full DFTB (without fragmentation)
fairly well.
A collaboration study made it possible to calculate the second-order geometrical derivative of the totalenergy within FMO-DFTB approximately [4]. A computation of the second-order geometrical derivative for asystem consisting of 1125 atoms ((H2O)375) with FMO-DFTB was 3465 times faster than the corresponding
computation without fragmentation. Eventually, it was possible to calculate the derivative for a system consistingof 10,041 atoms. The evaluation itself took only 17.2 minutes using six CPU cores, but the normal mode analysis(diagonalization of Hessian) took 262.4 minutes, and it is the bottleneck. Calculations for even larger systems issomewhat challenging at the moment, because of large memory requirement; the computation for 10,041 atoms
required a total memory of 10.2 GB per core.

Development of Analytic Derivatives with Fractional Occupation Number
I also developed analytic derivatives with the fractional occupation number (FON). One problem inthe calculation for large extended systems is the steep increase of computational cost, but another problem isthe difficulty of SCF convergence because of a small HOMO–LUMO gap. The problem may be attributed to
the fact that the orbital occupation number is integer and may be avoided by employing the FON withreasonable computational cost.
In computing second- and higher-order derivatives, coupled-perturbed (CP) equations are usually
solved. In the conventional CP equation, an explicit computation of dependent pairs (rotation within the fully－ 55 －

Ⅳ 研究業績 (2016)

occupied or unoccupied region) can be avoided, because the total energy is invariant to a rotation of MOs
within the diagonal blocks. It is thus possible to avoid the division by the difference of the orbital energies.
The difference between the orbital energy of two MOs in the off-diagonal blocks are usually large, so theexistence of degenerated orbitals are not problematic in solving CP equations. However, with FON, one
additionally has to consider the response term in partially occupied MOs. Since the denominator of the
response term is the difference between two orbital energies, the response term may be extremely large when
degenerated orbitals are partially occupied, and the convergence of CP equations may be challenging. In oneof the two studies [5], I solved the problem in the first-order CP equation and made it possible to computesecond-order geometrical derivatives analytically.
In the other study [6], I derived and implemented analytic third-order derivatives(hyperpolarizability and polarizability derivative) with FON. With integer occupation, it is well know thatthe analytic third-order derivative can be computed using first-order response terms by exploiting Wigner’s
2n+1 rule. Here, I derived that one with FON. I used the fact that the Lagrangian is stationary with respect tothe change of the MO coefficient and the occupation number. The expression obtained here can employ limit
values for small difference of orbital energies, so it is possible to compute third-order derivatives even withdegenerated orbitals. The derived equations for the density-functional tight-binding (DFTB) method were
implemented into GAMESS-US. By modifying the expression for the terms relevant to the two-electron
integral and exchange–correlation terms, it can be applicable to Hartree–Fock and DFT.
The developed method was applied to a series of zigzag-type graphene nanoribbon (ZGNR).
Non-resonance Raman spectra may be simulated by computing the polarizability derivative semi-numerically,
but spectra obtained in this way is very sensitive to the choice of electric field for a system with a small
HOMO–LUMO gap such as ZGNR. Moreover, we do not know an optimum electric field beforehand. By
computing the derivative analytically, I verified that it is possible to obtain non-resonance Raman spectrathat do not include numerical error.
Eventually, by exploiting the efficiency of DFTB, I performed a calculation with a ZGNR
consisting of 1012 atoms. By performing a parallel calculation using four E5-1650 v3 calculation node (24CPU cores in total), a computation of energy, gradient, Hessian, dipole derivative, hyperpolarizability, andFig. 3 Non-resonance Raman activity spectra of ZGNRs－ 56 －

Ⅳ 研究業績 (2016)

polarizability derivative of the ZGNR finished in 7.55 hours. The scaling of the computation was 3.98 withrespect to the number of atoms. Eventually, the evolution of the non-resonance Raman activity spectrum for
the ZGNRs consisting of less than 1012 atoms can be simulated (Fig. 3). The evolution of the spectrum issystematic. I expect that the developed method is useful in simulating infrared and non-resonance Raman
spectra of large extended systems.
References[1] Nishimoto, Y.; Fedorov, D. G.; Irle, S. J. Chem. Theory Comput. 2014, 10, 4801–4812.
[2] Nishimoto, Y.; Fedorov, D. G. Phys. Chem. Chem. Phys. 2016, 18, 22047–22061.
[3] Nishimoto, Y.; Fedorov, D. G. J. Comput. Chem. 2017, 38, 406–418.
[4] Nakata, H.; Nishimoto, Y.; Fedorov, D. G. J. Chem. Phys. 2016, 145, 044113.
[4] Nishimoto, Y.; Irle, S. Chem. Phys. Lett. 2017, 667, 317–321.
[5] Nishimoto, Y. J. Chem. Phys. 2017, 146, 084101.

2. Original papers(1) Yoshio Nishimoto and Dmitri G. Fedorov“The fragment molecular orbital method combined with density-functional tight-binding
and the polarizable continuum model”
Phys. Chem. Chem. Phys. 18(32), 21997–22734 (2016).
(2) Hiroya Nakata, Yoshio Nishimoto, and Dmitri G. Fedorov"Analytic second derivative of the energy for density-functional tight-binding combinedwith the fragment molecular orbital method”
J. Chem. Phys. 145(4), 044113 (2016).
(3) Yoshio Nishimoto and Stephan Irle
“Quantum Chemical Prediction of Vibrational Spectra of Large Molecular Systems with
Radial or Metallic Electronic Structure”
Chem. Phys. Lett. 667, 317–321 (2017).
(4) Yoshio Nishimoto and Dmitri G. Fedorov“Three-body expansion of the fragment molecular orbital method combined withdensity-functional tight-binding”
J. Comput. Chem. 38(7), 406–418 (2017).
(5) Yoshio Nishimoto“Analytic Hyperpolarizability and Polarizability Derivative with Fractional Occupation
Numbers for Large Extended Systems”
J. Chem. Phys. 146(8), 084101 (2017).
3. Presentation at academic conferences－ 57 －

Ⅳ 研究業績 (2016)(1) 西本 佳央、フェドロフ ドミトリ
「FMO 法と DFTB 法と PCM 法の組み合わせ（FMO-DFTB/PCM）」
第 10 回分子科学討論会（3G14）、兵庫県、2016 年 9 月 15 日
(2) 西本 佳央、イレ ステファン「小数軌道占有数を用いた二次微分計算」
日本化学会第 97 春季年会（1A7-01）、神奈川県、2017 年 3 月 16 日
4. Others(1) 西本 佳央「小数軌道占有数を用いた解析的微分法の開発」
第14回福井謙一記念研究センターシンポジウム、京都府、2017年1月27日－ 58 －

Ⅳ 研究業績 (2016)

２．FIFC リサーチフェロー

Shigeru
Shigeru Nagase
NagaseFIFCResearch
ResearchFellow
Fellow
FIFC
1. Summary of the Research of the Year(a) Formation Mechanisms of Graphitic-N: Oxygen Reduction and Nitrogen Doping ofGraphene Oxides
Deoxygenation and nitrogen-doping mechanisms of graphene oxides with participation of foreign
NH3 molecules were investigated by density functional theory calculations. First, it was proved that
reduction on perfect graphene oxide without any structural defect is facilitated at high temperature, but thefollowing doping process is impracticable because of the huge energy requirement for C−C cleavage. To
elucidate the formation of hexagonal graphitic-N, we explored oxygen reduction and subsequent
nitrogen-doping processes on defective graphene oxides with single vacancies for the first time. All possible
reaction pathways were taken into account, and the results demonstrate that the formation of graphitic-N
from NH3 and defective graphene oxides with one carbonyl or two hydroxyl groups is feasible in energy.
The dominant reaction route is found to be exothermic with a practical reaction rate of 2.26 × 106 s−1 at
900 °C, which is in good agreement with experimental observations.

(b) D2d(23)-C84 versus Sc2C2@D2d(23)-C84: Impact of Endohedral Sc2C2 Doping on Chemical
Reactivity in the Photolysis of Diazirine
We compared the chemical reactivity of D2d(23)-C84 and that of Sc2C2@D2d(23)-C84, both having thesame carbon cage geometry, in the photolysis of 2-adamantane-2,3′-[3H]-diazirine, to clarify metal-atom
doping effects on the chemical reactivity of the carbon cage. Experimental and computational studies haverevealed that the chemical reactivity of the D2d(23)-C84 carbon cage is altered drastically by endohedral
Sc2C2 doping. The reaction of empty D2d(23)-C84 with the diazirine under photoirradiation yields two
adamantylidene (Ad) adducts. NMR spectroscopic studies revealed that the major Ad monoadduct(C84(Ad)-A) has a fulleroid structure and that the minor Ad monoadduct (C84(Ad)-B) has amethanofullerene structure. The latter was also characterized using X-ray crystallography. C84(Ad)-A isstable under photoirradiation, but it interconverted to C84(Ad)-B by heating at 80 °C. In contrast, thereaction of endohedral Sc2C2@D2d(23)-C84 with diazirine under photoirradiation affords four Ad
monoadducts (Sc2C2@C84(Ad)-A, Sc2C2@C84(Ad)-B, Sc2C2@C84(Ad)-C, and Sc2C2@C84(Ad)-D). The
structure of Sc2C2@C84(Ad)-C was characterized using X-ray crystallography. Thermal interconversion of
Sc2C2@C84(Ad)-A and Sc2C2@C84(Ad)-B to Sc2C2@C84(Ad)-C was also observed. The reaction
mechanisms of the Ad addition and thermal interconversion were elucidated from theoretical calculations.
Calculation results suggest that C84(Ad)-B and Sc2C2@C84(Ad)-C are thermodynamically favorable
products. Their different chemical reactivities derive from Sc2C2 doping, which raises the HOMO andLUMO levels of the D2d(23)-C84 carbon cage.

－ 59 －

Ⅳ 研究業績 (2016)(c) Molecular Location Sensing Approach by Anisotropic Magnetism of an Endohedral

Metallofullerene
Location recognition at the molecular scale provides valuable information about the nature offunctional molecular materials. This study presents a novel location sensing approach based on an
endohedral metallofullerene, Ce@C82, using its anisotropic magnetic properties, which lead totemperature-dependent

paramagnetic

shifts

in

1

H

NMR

spectra.

Fivesite-isomers

of

Ce@C82CH2-3,5-C6H3Me2 were synthesized to demonstrate the spatial sensing ability of Ce@C82.
Single-crystal structures, absorption spectra, and density functional theory calculations were used to selectthe plausible addition positions in the radical coupling reaction, which preferentially happens on the carbon
atoms with high electron density of the singly occupied molecular orbital (SOMO) and positive charge.
Temperature dependent NMR measurements demonstrated unique paramagnetic shifts of the 1H peaks,
which were derived from the anisotropic magnetism of the f-electron in the Ce atom of the isomers. It was
found that the magnetic anisotropy axes can be easily predicted by theoretical calculations. Further analysis
revealed that the temperature-dependent trend in the shifts is clearly predictable from the distance andrelative position of the proton from the Ce atom. Hence, the Ce-encapsulated metallofullerene Ce@C82 canprovide spatial location information about nearby atoms through the temperature-dependent paramagnetic
shifts of its NMR signals. It can act as a molecular probe for location sensing by utilizing the anisotropic
magnetism of the encapsulated Ce atom. The potentially low toxicity and stability of the endohedral
fullerene would make Ce@C82 suitable for applications in biology and material science.
(d) Stabilization of a Chlorinated#4348

C66:C2v Cage by Encapsulating Monometal Species:

Coordination between Metal and Double Hexagon-Condensed Pentalene
Carbon cages in endohedral and exohedral fullerene derivatives are usually different. A recent reportsuggested that chlorofullerene C66Cl10:Cs and endohedral metallofullerene (EMF) Sc2@C66 shared the same
cage #4348C66:C2v, while it was denied by the definitive characterization of Sc2@C66, which actuallypossesses the #4059C66:C2v isomer. Here, we show that a #4348C66:C2v cage with a double hexagon-condensed
pentalene (DHCP) moiety, which was captured by exohedral chlorination, is also capable of beingstabilized by encapsulating tri- or divalent monometal (M) species. On the basis of density functional
theory calculations combined with statistical#4348

mechanics analyses, it was demonstrated that

C66:C2v-based mono-EMFs M@C2v(4348)-C66 (M = Tb, La, Y, and Yb) are the most stable andpredominant isomers at the fullerene formation temperature region, while another chlorinated cage
#4169

C66:Cs, featured with triple sequentially fused pentagon (TSFP) moiety, is less favorably obtained in theform of EMFs, although these two cages can be interconverted by a simple Stone−Wales transformation.
The superiority of M@C2v(4348)-C66 over M@Cs(4169)-C66 comes from the stronger interaction of M−
DHCP over that of M−TSFP in both ionic and covalent bonding aspects. In addition, size-selective
complexation of host [n]cycloparaphenylene ([n]CPP) and Tb@C2v(4348)-C66 was simulated, showing that－ 60 －

Ⅳ 研究業績 (2016)[10]CPP exhibits the best affinity toward Tb@C66, which provides a new opportunity for isolation andcharacterization of C66-based mono-EMFs.

(e) Dispersion Forces, Disproportionation, and Stable High-Valent Late Transition Metal
Alkyls
The transition metal tetra- and trinorbornyl bromide complexes, M(nor)4, Ni(nor)3Br, and theirhomolytic fragmentations (M = Fe, Co, Ni and nor = 1-bicyclo[2.2.1]hept-1-yl) were investigatedcomputationally using hybrid density functional theory (DFT) at the B3PW91 and dispersion-corrected
B3PW91-D3 levels. Experimental structures were well replicated; the dispersion correction resulted in
shortened M-C bond lengths for the stable complexes, and it was found that Fe(nor)4 receives a remarkable
45.9 kcal/mol stabilization from the dispersion effects whereas the tetragonalized Co(nor)4 shows
stabilization of 38.3 kcal/mol. Ni(nor)4 was calculated to be highly tetragonalized with long Ni-C bonds,
providing a rationale for its current synthetic inaccessibility. Isodesmic exchange evaluation for Fe(nor)4
confirmed that dispersion force attraction between norbornyl substituents is fundamental to the stability ofthese species.

(f) A Dianionic Species with a Bond between pentacoordinated Sn Atoms: Bonding
Properties of the Sn-Sn bond
The first dianionic compound bearing a bond between two pentacoordinated tin atoms, a distannate,
was synthesized in a stable form by using two sets of an electron-withdrawing C,O-bidentate ligand on eachtin atom. The structure of the distannate was determined by NMR spectroscopy and X-ray crystallographic
analysis. The Sn–Sn bond of the distannate was shown to be a single bond featuring high s-character. The
1

J(Sn–Sn) coupling constant was larger than that of Sn(sp3)–Sn(sp3) bonds found in mosthexaorganodistannanes. This bond feature was also supported by computational studies. The Sn–Sn bondwas cleaved by treatment with hydrochloric acid, which shows a different reactivity to the homonuclear
bonds of pentacoordinated disilicates and digermanates.

(g) Other Research Subjects(1) "Computed Relative Populations of D2(22)-C84 Endohedrals with Encapsulated Monomeric andDimeric Water", (2) "Regioselective Multistep Reconstruction of Half-Saturated Zigzag Carbon
Nanotubes", (3) "Strong Electronic Coupling and Electron Transfer in a Ce2@Ih-C80-H2P Electron Donor
Acceptor Conjugate", (4) "Sc3N@Cs(39715)-C82: A Missing Isomer Linked to Sc3N@C2v(39718)-C82 by aSingleStep

Stone-Wales

Chlorination/Dechlorination

Transformation",
Mechanisms

of

(5)
#1911

C64

"Unconventional
Fullerene",(6)

Electronic

Structureand"Dispersion-Force-Assisted

Disproportionation: A Stable Two-Coordinate Copper (II) Complex", (7) "(4-Butadiene)Sn(0)Complexes: A New Approach for Zero-Valent p-Block Elements Utilizing a Butadiene as a 4π-Electron
Donor ", (8) "Isolation and Ambident Reactivity of a Chlorogermylenoid", (9) "Synthesis of a
1-Aryl-2,2-chlorosily(phospha)silene Coordinated by an N-Heterocyclic Carbene", (10) "Tuning of the
Photoluminescence and Up-Conversion Photoluminescence Properties of Single-Walled Carbon Nanotubes－ 61 －

Ⅳ 研究業績 (2016)

by Chemical Functionalization", (11) "Thermal Stability of Oxidized Single-Walled Carbon Nanotubes:
Competitive Elimination and Decomposition Reaction Depending on their Degree of Functionalization"(12) "Reaction of a Stable Digermyne with Acetylenes: Synthesis of a 1,2-Digermabenzene and a
1,4-Digermabarrelene", (13) "The Unanticipated Dimerization of Ce@C2v(9)-C82 upon Cocrystallization
with Ni(octaethyporphyrin) and Comparison with Monomeric M@C2v(9)-C82 (M = La, Sc, and Y)"

2. Original papers(1) W. –W. Wang, J. –S. Dang, X. Zhao, and S. Nagase,"Formation Mechanisms of Graphitic-N: Oxygen Reduction and Nitrogen Doping of Graphene
Oxides"J. Phys. Chem. C, 120, 5673-5681 (2016).
(2) Z. Slanina, F. Uhlík, S. Nagase, X. Lu, T. Akasaka, and L. Adamowicz,"Computed Relative Populations of D2(22)-C84 Endohedrals with Encapsulated Monomeric andDimeric Water"
ChemPhysChem, 17, 1109-1111 (2016).
(3) W. –W. Wang, J. –S. Dang, X. Zhao, and S. Nagase,"Regioselective Multistep Reconstruction of Half-Saturated Zigzag Carbon Nanotubes"
J. Comput. Chem., 37, 1363-1366 (2016).
(4) Y. Takano, R. Tashita, M. Suzuki, S. Nagase, H. Imahori, and T. Akasaka,"Molecular Location Sensing by Anisotropic Magnetism of an Endohedral Metallofullerene"
J. Am. Chem. Soc., 138, 8000-8005 (2016).
(5) M. Rudolf, L. Feng, Z. Slanina, W. –W. Wang, S. Nagase, T. Akasaka, and D. M. Guldi,"Strong Electronic Coupling and Electron Transfer in a Ce2@Ih-C80-H2P Electron Donor Acceptor
Conjugate"
Nanoscale, 8, 13257-13262 (2016).
(6) J. –S. Dang, W. –W. Wang X. Zhao, and S. Nagase,"Unconventional Electronic Structure and Chlorination/Dechlorination Mechanisms of #1911C64
Fullerene"
Inorg. Chem., 55, 6827-6829 (2016).
(7) Q. –Z. Li, J. –J. Zheng, L. He, S. Nagase, and X. Zhao,"Stabilization of a Chlorinated #4348C66:C2v Cage by Encapsulating Monometal Species: Coordination
between Metal and Double Hexagon-Condensed Pentalenes"
Inorg. Chem., 55, 7667-7675 (2016).
(8) W. –J. Guan, P. Zhao, Q. –Z. Li, S. Nagase, M. Ehara, and X. Zhao,"Sc3N@Cs(39715)-C82: A Missing Isomer Linked to Sc3N@C2v(39718)-C82 by a Single Step
Stone-Wales Transformation"
RSC Adv., 6, 75588-75593 (2016).
(9) C. L. Wagner, L. Tao, E. J. Thompson, T. A. Stich, J. –D. Guo, J. C. Fettinger, L. A. Berben, R. D.
Britt, S. Nagase, and P. P. Power,－ 62 －

Ⅳ 研究業績 (2016)"Dispersion-Force-Assisted Disproportionation: A Stable Two-Coordinate Copper (II) Complex"
Angew. Chem. Int. Ed., 55, 10444-10447 (2016).
(10)T.

Kuwabara,

M.

Nakada,J.

Hamada,

J.

–D.

Guo,

S.

Nagase,andM.

Saito,

4"( -Butadiene)Sn(0) Complexes: A New Approach for Zero-Valent p-Block Elements Utilizing a
Butadiene as a 4π-Electron Donor "J. Am. Chem. Soc., 138, 11378-11382 (2016).
(11) Y. Suzuki, T. Sasamori, J. –D. Guo, S. Nagase, and N. Tokitoh,"Isolation and Ambident Reactivity of a Chlorogermylenoid"
Chem. Eur. J., 22, 13784-13788 (2016).
(12) A. W. Kyri, P. K. Majhi, T. Sasamori, T. Agou, V. Nesterov, J. –D. Guo, S. Nagase, N. Tokitoh,
and R. Streubel,"Synthesis of a 1-Aryl-2,2-chlorosily(phospha)silene Coordinated by an N-Heterocyclic Carbene"
Molecules, 21, 1309 (10 pages) (2016).
(13) Y. Maeda, S. Minami, Y. Takehana, J. –S. Dang, S. Aota, K. Matsuda, Y. Miyauchi,

M. Yamada,

M. Suzuki, R. –S. Zhao, X. Zhao, and S. Nagase,"Tuning of the Photoluminescence and Up-Conversion Photoluminescence Properties

ofSingle-Walled Carbon Nanotubes by Chemical Functionalization"
Nanoscale, 8, 16916-16921 (2016).
(14) Y. Maeda, E. Sone, A. Nishio, Y. Amagai, W. –W. Wang, M. Yamada, M. Suzuki, J. Matsui, M.
Mitsuishi, T. Okazaki, and S. Nagase,"Thermal Stability of Oxidized Single-Walled Carbon Nanotubes: Competitive Elimination andDecomposition Reaction Depending on their Degree of Functionalization"
Chem. Eur. J., 22, 15373-15379 (2016).
(15) T. Sugahara, J. –D. Guo, T. Sasamori, Y. Karatsu, Y. Furukawa, A. E. Ferao, S. Nagase, and N.
Tokitoh,"Reaction of a Stable Digermyne with Acetylenes: Synthesis of a 1,2-Digermabenzene and a
1,4-Digermabarrelene"
Bull. Chem. Soc. Jpn., 89, 1375-1384 (2016).
(16) D. J. Liptrot, J. –D. Guo, S. Nagase, and P. P. Power,"Dispersion Forces, Disproportionation, and Stable High-Valent Late Transition Metal Alkyls"
Angew. Chem. Int. Ed., 55, 14766-14769 (2016).
(17) S. Tsukada, N. J. O’Brien, N. Kano, T. Kawashima, J. –D. Guo, and S. Nagase,"The Synthesis and Structure of a Dianionic Species with a Bond between Pentacoordinated Tin
Atoms: Bonding Property of the Tin-Tin Bond"
Dalton Trans., 45, 19374-19379 (2016).
(18) M. Suzuki, M. Yamada, Y. Maeda, S. Sato, Y. Takano, F. Uhlík, Z. Slanina, Y. Lian,

X. Lu, S.

Nagase, M. M. Olmstead, A. L. Balch, and T. Akasaka,"The

Unanticipated

Dimerization

of

Ce@C2v(9)-C82

upon

Cocrystallization

Ni(octaethyporphyrin) and Comparison with Monomeric M@C2v(9)-C82 (M = La, Sc, and Y)"－ 63 －

with

Ⅳ 研究業績 (2016)

Chem. Eur. J., 22, 18115-18122 (2016).
(19) M. Yamada, Y. Tanabe, J. –S. Dang, S. Sato, N. Mizorogi, M. Hachiya, M. Suzuki, T.

Abe, H.

Kurihara, Y. Maeda, X. Zhao, Y. Lian, S. Nagase, and T. Akasaka,"D2d(23)-C84 versus Sc2C2@D2d(23)-C84: Impact of Endohedral Sc2C2 Doping on Chemical
Reactivity in the Photolysis of Diazirine"
J. Am. Chem. Soc., 138, 16523-16532 (2016).

3. Books
赤阪 健，山田道夫，前田優，

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.

－ 64 －

Ⅳ 研究業績 (2016)

３．シニアリサーチフェロー

Shigeyoshi Sakaki
Shigeyoshi Sakaki

Research
Leader,Kenichi
Fukui
Memorial
Research
Groups
II II
SeniorResearch
Fellow,
Kenichi
Fukui
Memorial
Research
Groups
1. Summary of the research of 2016
The complex systems consisting of transition metal element(s), heavy main-group element(s), organicgroup(s) are importnat research targets in wide areas of modern chemistry. Such complex systems 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 physicalchemistry and molecular science, because they exhibit a variety of new geometry, new bonding nature, richmolecular property, rich reactivity, and various catalyses. 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 the theoretical calculation. Another example is the significantly
large coupling of surrounding atmosphere (such as solvation effects, molecular crystal effects and so on)with electronic structure.
Our group is theoretically investigating the complex systems bearing complicated electronic structurewith electronic structure theory. In 2016, we performed various theoretical studies, as follows: (i) CASPT2
study of inverse sandwich-type dinuclear 3d transition metal complexes with two different metal centers, (ii)theoretical study of unusual solvation structure of water with Pt(II) and Pd(II) complexes, (iii) theoreticalprediction of new catalysis of three-coordinate phosphorus compound, (iv) theoretical analysis of reaction
mechanism of Pd/Cu-cooperative catalysis in reductive cross-coupling of styrene and aryl bromides, (v)theoretical study of para-selective alkylation of benzamides and aromatic ketones by cooperative
nickel/aluminum catalysis, and (vi) Activation of Strong Boron–Fluorine and Silicon–Fluorine -Bonds:
Theoretical Understanding and Prediction. We wish to report some of them, below.
(i) CASPT2 study of inverse sandwich-type dinuclear 3d transition metal complexes with two different
metal centers
Spin multiplicities and coordination structures of dinitrogen-bridged hetero-dinuclear complexes of 3d
metals, (μ-N2)[M1(AIP)][M2(AIP)] (AIPH = (Z)-1-amino-3-imino-prop-1-ene; M1, M2 = V(I) to Co(I)),

Figure 1. Mn-Cr heterodinucler inverse sandwich complex with the highest spin multiplicity of dectet.
－ 65 －

Ⅳ 研究業績 (2016)

were investigated with CASPT2 method. (μ-N2)[V(AIP)][Cr(AIP)] has a low spin doublet (2B2) ground statewith an η2-side-on dinitrogen coordination structure but (μ-N2)[Mn(AIP)][Fe(AIP)] has a high spin octet(8A2) ground state with an η1-end-on coordination structure. These results are similar to those of thehomo-dinuclear Cr and Fe analogues, respectively. In (μ-N2)[Cr(AIP)][M(AIP)] (M = Mn(I), Fe(I), or Co(I))
consisting of the early 3d metal (Cr) and late one (Mn to Co), on the other hand, we found characteristicfeatures in the geometry and the ground state electronic structure which are different from those ofhomo-dinuclear analougues. The Cr-Mn complex has a high spin decets (10B1) ground state with anη2-side-on structure. This decets state is the highest spin multiplicity in the dinuclear transition metal
complexes, to our knowledge. The A2 state with a doublet spin multiplicity is moderately less stable than the
10B1 state. The optimized structures and the molecular orbitals indicate that the Cr atom strongly interacts
with the N2 moiety in the 10B1 state but the Mn atom strongly interacts with the N2 moiety in the 2A2 state.
The Cr-Fe complex has a high spin nonet (9B1) ground state with an η2-side-on structure like the Cr-Mn
complex, but only the Cr-Co complex has a medium spin quartet 4A2 ground state with an η2-side-on
structure. The different ground electronic state of the Cr-Co complex arises from the presence of 3d orbital at
low energy. Based on these results, it is concluded that the geometry is determined by the Cr center but theelectronic structure and the spin multiplicity are determined by the combination of early and late 3d metals inthe dinitrogen-bridged hetero-dinuclear chelates of 3d metals.
(ii) Theoretical Study of unusual solvation structure of water with Pt(II) and Pd(II) complexes
Solvation of transition metal complexes with water has been one of the fundamental topics in physicaland coordination chemistry. In particular, Pt(II) complexes have recently attracted considerable interest for
their relation to anticancer activity in cisplatin and its analogues, yet the interaction of the water moleculeand the metal center has been obscured. The challenge from a theoretical perspective remains that both themicroscopic solvation effect and the dynamical electron correlation (DEC) effect have to be treatedsimultaneously in a reasonable manner. In this work we derive the analytical gradient for thethree-dimensional reference interaction site model Møller−Plesset second order (3D-RISM-MP2) free energy.

Figure 2. Micro-solvation structure of H2O with neutral Pt(II) and cationic Pt(II) complexes optimized by the
3D-RISM-SCF-MP2 method.

On the basis of the three-regions 3D-RISM self-consistent field (SCF) method recently proposed by us, weapply a new layer of the Z-vector method to the CP-RISM equation as well as point-charge approximation to
the derivatives with respect to the density matrix elements in the RISM-CPHF equation to remarkably reducethe computational cost. This method is applied to study the interaction of H2O with the d8 square planartransition metal complexes in aqueous solution, trans-[PtIICl2(NH3)(glycine)] (1a), [PtII(NH3)4]2+ (1b),－ 66 －

Ⅳ 研究業績 (2016)[PtII(CN)4]2− (1c), and their Pd(II) analogues 2a, 2b, and 2c, respectively, to elucidate whether the usual H2O
interaction through O atom (O-ahead mode) or unusual one through H atom (H-ahead mode) is stable inthese complexes. We find that the interaction energy of the coordinating water and the transition metal
complex changes little when switching from gas to aqueous phase, but the solvation free energy differs
remarkably between the two interaction modes, thereby affecting the relative stability of the H-ahead andO-ahead modes. Particularly, in contrast to the expectation that the O-ahead mode is preferred due to thepresence of positive charges in 1b, the H-ahead mode is also found to be more stable. The O-ahead mode isfound to be more stable than the H-ahead one only in 2b. The energy decomposition analysis (EDA) at the
3D-RISM-MP2 level revealed that the O-ahead mode is stabilized by the electrostatic (ES) interaction,
whereas the H-ahead one is mainly stabilized by the DEC effect. The ES interaction is also responsible forthe difference between the Pd(II) and Pt(II) complexes; because the electrostatic potential is more negative
along the z-axis in the Pt(II) complex than in the Pd(II) one, the O-ahead mode prefers the Pd(II) complexes,
whereas the H-ahead becomes predominant in the Pt(II) complexes.
(iii) Theoretical prediction of new transfer-hydrogenation catalysis of three-coordinate phosphorus
compound: Application to aldehyde and ketone
Catalysisofphosphorus
compound
10-P-323,7-di(tert-butyl)-5-aza-2,8-dioxa-lphosphabicyclo[3.3.O]octa-2,4,6-triene 1P and its analogues in transfer hydrogenation of azobenzene withammonia-borane (NH3BH3) was investigated using DFT, CCSD(T), and ONIOM(CCSD(T):MP2) methods,
to elucidate the electronic process of their reaction, to find a more active catalyst, and to broaden the

Scheme 1. Catalysts examined here.
application scope as a catalyst.
The reaction occurs through thephosphorus-ligand
cooperative
catalysis
function, where the oxidation state of thephosphorus center changes between +I and +III.
This is a characteristic difference from that of
the metal–ligand cooperative function in which
the oxidation state of the metal center does notchange. The phosphorus–ligand cooperative Figure 3. Hydrogenation of azobenzene byfunction with the change in the phosphorus three-coordinate P compounds
oxidation state should be noted as a new featureof the main-group element compound because the oxidation state does not easily change in the main group－ 67 －

Ⅳ 研究業績 (2016)

element compound in general.
In the dehydrogenation reaction of NH3BH3, the approach of the B–H bonding MO to the P atom
induces an antibonding overlap with the P–O MO and a bonding overlap with the P–O * MO. As a result,the P atomic population decreases considerably in the early stage of the reaction, which corresponds to thechange in the phosphorus oxidation state from +I to +III. Orbital mixing of the * MO also engenders anincrease in the electron population of the (CH=CH)-Me moiety. Because of the importance of these orbital
mixings, the use of an electron-withdrawing substituent and conjugate C6H4 group in the ONO ligand
enhances the activity for the dehydrogenation step. Simultaneously, the CT occurs from the P−O π MO to theN−H σ* MO of ammonia-borane to form the O–H bond. In the hydrogenation of azobenzene, the electronic
process is almost opposite to that of dehydrogenation.
The O−H bond energy of 4OP is an important factor for determination of the catalyst activity. Acr−1P
is theoretically predicted to be much more active than 1P-tBu experimentally reported. This compound isconstructed by substituting two C6H4 groups for the (CH=CH)R moieties on the ONO ligand and connecting
these C6H4 groups with a CH2 linkage. This Acr−1P has the best O–H bond strength for the catalysis. The
1P-like catalyst is useful for transfer hydrogenation of substrate bearing a polar double bond. Actually,Acr−1P exhibits wide application scope as a catalyst in transfer hydrogenations of such substrates as
hexafluoroacetone, benzophenone, acetophenone, acetaldehyde, and acetone. Phosphorus compounds of thistype are interesting catalysts for transfer hydrogenation reactions of many substrates with ammonia-borane.
Further work to investigate a new reaction is in progress in our group.
(iv) Theoretical prediction of new transfer-hydrogenation catalysis of three-coordinate phosphorus
compound: Application to CO2 Hydrogenation
The chemical conversion of carbon dioxide (CO2) to value-added chemicals and renewable energy is
an appealing strategy to address both thegreenhouse effect and energy crisis issues.
However, the CO2 conversion is challenging due
to the inherent thermodynamic and kinetic
stabilities of CO2. Therefore, such processusually asso-ciates with precious-metal catalysts,
for which the toxicity of the catalyst brings new Scheme 2. Three-coordinated P catalysts examinedenvironmental issues. In recent years, the here.
employment of the main-group element
com-pounds, which are abundant, cheap, and green, in the CO2 conversion starts to emerge. For instance,
several Frustrated Lewis Pairs (FLPs) have been applied to the conversion of CO2 to CH3OH, CH4, and CO.
In 2012, a pincer-type phosphorus compound 1OP−tBu (Scheme 2) was found to be active for thetransfer hydrogenation of azobenzene with ammonia-borane (NH3BH3). The mechanistic study showed that
this reaction occurs through the phosphorus−ligand cooperative catalysis function, which resembles themetal−ligand cooperative catalysis function that is powerful in chemical transformations by transition-metal
complexes.
Here, we wish to report the first computational investigation on hydrogenation of CO2 with NH3BH3
4. 3Energy
and geometry
in the CO2
by the pincer-type phosphorus compounds. The use Figureof NH3BH
as the hydro-gen
sourcechanges
is not unreasonable,
byrecently.several
three-coordinated
P compounds
pincer-type
phosphorus
because it has been employed in the hydrogenation hydrogenationof CO2 by FLPs
compounds were theoretically predicted to be active for the hydrogenation of CO2 with NH3BH3. The
reaction occurs through a phosphorus-ligand cooperation cata-lytic cycle; see Scheme 1. The phosphorus－ 68 －

Ⅳ 研究業績 (2016)

catalysts with the NNN ligand are more active than those with the ONO ligand and Acr−1NP is the best
catalyst theoretically designed here. The activi-ty of the catalyst was greatly improved by introducing planar
and the conjugate ligand. These results clearly demonstrate that the pincer-type phosphorus compound is a
new promising catalyst for the metal-free conversion of CO2.
(v) Theoretical analysis of reaction mechanism of Pd/Cu-cooperative catalysis in reductive
cross-coupling of styrene and aryl bromides
Transition metal catalyzed cross-coupling reactions of alkyl and alkenyl organometallic reagents
represent a powerful method for the alkylation and alkenylation, respectively, of organic electrophiles. The
hydrometallation of alkenes and alkynes is an atom-efficient and practical way to prepare alkyl and alkenyl
metal reagents, respectively, because a variety of main-group metal hydrides, alkenes, and alkynes arereadily available. However, these organometallic nucleophiles are usually presynthesized and often purified
prior to subsequent cross-coupling reactions, and such processes generally involve multistep operations.
Nakao and Semba and coworkers succeededcross-coupling reactions based on organometallic
nucleophiles generated by hydrometallation ofalkenes and alkynes with a catalytic amount oftransition-metal hydrides in situ.
The reaction mechanism has been unclear.
One of the important steps is transmetallation; if
this transmetallation does not occur easily, thecross-coupling reaction is not successful. We
Figure 5. Changes in energy by transmetallation
investigatedthistransmetallation
between between Pd(II)-phenyl and Cu(I)-alkyl species.
Pd(II)-phenyl and Cu(I)-alkyl complexes and foundthat the transmetallation occurs with somewhat large activation barrier through inversion stereochemistryaround the sp3 carbon atom. It is of considerable interest to elucidate the reason why not the retention but
inversion transmetallation occurs in this case and what are determining factor(s).
2. Original Papers(1) Shinji Aono, Toshifumi Mori, and Shigeyoshi Sakaki,“3D-RISM-MP2 Approach to Hydration Structure of Pt(II) and Pd(II) Complexes: Unusu-al
H‑Ahead Mode vs Usual O‑Ahead One”
J. Chem. Theory Comput., 12, 1189−1206 (2016).
(2) Tetsuya Fukuda, Hisako Hashimoto, Shigeyoshi Sakaki, and Hiromi Tobita," Stabilization of a Silaaldehyde by its 2 Coordination to Tungsten”
Angew. Chem. Int. Ed., 55, 188 –192 (2016).
(3) Yuta Takano, Tomohiro Numata, Kazuto Fujishima, Kazuaki Miyake, Kazuya Nakao, WesleyDavid Grove, Ryuji Inoue, Mineko Kengaku, Shigeyoshi Sakaki, Yasuo Mori, Ta-tsuya Murakamiand Hiroshi Imahori“Optical control of neuronal firing via photoinduced electron transfer in donor–acceptor
conjugates”
Chem. Sci., 7, 3331-3337 (2016).
(4) H. Kameo, K. Ikeda, S. Sakaki, S. Takemoto, H. Nakazawa, H. Matsuzaka,“Experimental and theoretical studies of Si-Cl and Ge-Cl sigma-bond activation reactions byiridium-hydride”
Dalton Trans., 45, 7570-7580 (2016).
(5) H. Kameo, T. Kawamoto, S. Sakaki, D. Bourissou, H. Nakazawa,“Transition-Metal-Mediated Cleavage of Fluoro-Silanes under Mild Conditions”－ 69 －

Ⅳ 研究業績 (2016)

Chem. Euro. J. 22, 2370-2375 (2016).
(6) K. Kikui, S. Hayaki, K. Kido, D. Yokogawa, K. Kasahara, Y. Matsumura, H. Sato, S. Sakaki,“Solvent structure of ionic liquid with carbon dioxide”
A Mol. Simu., SI. 41, 881-891 (2015).
(7) K. Semba, K. Ariyama, H. Zheng, R. Kameyama, S. Sakaki, Y. Nakao,“Reductive Cross-Coupling of Conjugated Arylalkenes and Aryl Bromides with Hy-drosilanes by
Cooperative Palladium/Copper Catalysis”
Angew. Chem., Int. Ed. 55, 6275-6278 (2016).
(8) G. Zeng, S. Maeda, T. Taketsugu, S. Sakaki,“Theoretical Study of Hydrogenation Catalysis of Phosphorus Compound and Prediction of
Catalyst with High Activity and Wide Application Scope”
ACS Cat., 6, 4859-4870 (2016).
(9) M. Nakagaki, S. Sakaki,“Hetero-dinuclear complexes of 3d metals with a bridging dinitrogen ligand: theoretical predictionof the characteristic features of geometry and spin multiplicity”
Phys. Chem. Chem. Phys., 18, 26365-26375 (2016).
(10) GX. Zeng, S. Maeda, T. Taketsugu, S. Sakaki,“Catalytic Hydrogenation of Carbon Dioxide with Ammonia-Borane by Pincer-Type Phosphorus
Compounds: Theoretical Prediction”
J. Am. Chem. Soc., 138, 13481-13484 (2016).
(11) S. Okumura, SW. Tang, T. Saito, K. Semba, S. Sakaki, Y. Nakao,“para-Selective Alkylation of Benzamides and Aromatic Ketones by Cooperative
Nickel/Aluminum Catalysis”
J. Am. Chem. Soc., 138, 14699-14704 (2016).
3. Presentation at academic conferences(1) S. Sakaki,“Complex Systems Consisting of Transition Metal and Heavy Main Group Elements: Theoretical
Study of Structure and Bonding Nature”
The 70th Fujihara Seminar “New Development of PhysicalOrganic Chemistry: Construction ofChemical Principles Determining Structures, Reactions, and Properties, April 18-20, 2016, Fukuoka,
Japan (Invited)(2) S. Sakaki“Crucial Role of Lewis Acid in Enhancing Reactivity of Organometallic Complex”
The 1’st International Conference for Organometallic Chemistry (ICOC) Oct. 20-23, 2016,
Beiging (Keynote lecture)(3) 榊 茂好
「触媒の理論化学 /計算化学研究：元素戦略的触媒開発へ貢献を目指して 」
第四回元素戦略に基づいた触媒設計シンポジウム
首都大学東京 秋葉原サテライトキャンパス 2016 年 11 月 25 日（金）(招待講演）
4. Others: Review article(1) G. Guan, GX. Zeng, H. Kameo, Y. Nakao, S. Sakaki,
Cooperative Catalysis of Combined Systems of Transition-Metal Complexes with Lewis Acids:
Theoretical Understanding
Chem. Rec.. 16, 2405-2425 (2016).

－ 70 －

Ⅳ 研究業績 (2016)

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
比較的自由に電子を収容あるいは放出できる機能を持つ材料として電子化物がある。これらには電子親和力が適度に大きいことなど電子の授受に対して柔軟な電子物性を有することや、具体的な電子の収容サイトを持つ必要性がある。今年度は電子化物としての機能を備えたソフトマテリアルを得るために必要な電子を安定に補足しうる無機元素ブロック
として、無機カゴ型分子の理論的分子設計を行った。
【始めに】 高分子に組み込むための部分素材として、元素ブロックの開発が現在活発に行われている 1)。この元素ブロックは単に高分子の構造修飾のみならず、特異な反応性や電気・電子・光・磁
気物性などにからむ有用な機能を高分子に付与するために有効な戦略を提供する。無機元素を含む
カゴ型分子であるオクタシルセスキオキサンは一般には(RSiO1.5)8 と表される POSS（Polyhedral
Oligomeric Silsesquioxane）の代表例であり、種々の観点から研究がなされている。POSS の電子物性として最も興味深いと考えられるものの一つに、その LUMO のエネルギー準位が低く電子親和力が大きいことがある(表 1)2)。このことは POSS が電子を捕捉しやすいという蓋然性を示すが、実際に電子を収容した POSS モノアニオンは表 1 に示すように中性状態よりも不安定であり、電子吸引基などによる修飾を行わない限りは電子を長時間安定に捕捉できる性質を示すことは考えにくい。ここでは、POSS 以上に安定な電子捕捉能を示すと期待される無機カゴ型分子である As4S6 及び[HPO3BH]4（POB と略）を無機元素ブロックとして提案し、それらの電子物性についての解析を行った 3,4)。
【計算方法】 直径が 5 Å 程度の無機カゴ状分子である As4S6 と POB（図 1）について、その電子捕捉の可能性についての理論的検討を行った。計算は密度汎関数理論(DFT)に基づく B3LYP 法及びUB3LYP 法によって行い、基底としては 6-31+G**を用いた。計算には Gaussian09 ソフトを使用した 5)。具体的には上記の分子について、中性及びそのモノアニオン状態における構造最適化を行い、そのエネルギーを計算することによってアニオンの安定化についての予測を行った。また余剰電子を収容する SOMO（半占 MO）の軌道相などの解析も行った。
Table 1. Energetical stabilization
upon the ionization
LUMO
level
Species (neutral
state)a
As4S6
2.702POB
0.502
POSSc 0.157

Stabilizationenergy ofthemonoanionicstateb
46.17
11.32
11.51ain eV, bin kcal/mol, and cR = H.

Fig. 1

Molecular structures of caged shape:(a) As4S6 and (b) [HPO3BH]4 (POB).
－ 71 －

Ⅳ 研究業績 (2016)【As4S6 と POB の解析結果】
表 1 に示す As4S6 の計算結果では、中性状態よりもモノアニオンの方がエネルギー的にかなり安定であり、この分子は電子を安定的に捕捉する能力を持つことが分かる。また図 2(a)のように、この余剰電子を収容する SOMO は中性 As4S6 分子の LUMO よりも準位が一つ上にある三重縮退した
LUMO+1 の一つであることが分かった。これにより Jahn-Teller 変形が起こって、モノアニオンでは中性状態の Td から Cs に対称性が下がる。この SOMO を構成するのは、Cs 面上にある As と隣接す
る S との間の sp*性の反結合性軌道である。モノアニオンの余剰電子は当該 As 原子の正電荷を減ずる役割をし、結果として As 原子のローンペア性を高めている 3)。
POB でも表 1 が示すように中性状態よりモノアニオンの方がエネルギー的に安定であり、やはり電子を安定的に捕捉する能力を持つことが分かる。図 2(b)が示すように、POBの SOMO の起源となるのは中性 POB 分子の LUMO で縮退はしていないが、モノアニオンでは構造緩和が起こって中性状態の T から C3 に対称性が下がる。余剰電子が入る SOMO を構成するのは C3 軸上にある P と隣接する O との間の sp*性の反結合性軌道である。余剰電子はこの P 原子の正荷電を減ずる役割をし、結果として P 原子のローンペア性を高めている。

(a)

(b)
Fig. 2

Molecular-orbital energy diagrams of neutral (a) As4S6 and (b) POB.

One of the(LUMO+1)’s of the former changes into the SOMO of As4S6 and the LUMO of the latter intothat of POB.

The MO patterns of those are also shown.

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Ⅳ 研究業績 (2016)

さらに検討した POB のホウ素をアルミニウムに変えた POAl や上記の POSS では、電子親和力は正であるが、中性状態よりもモノアニオンの方がエネルギー的に若干不安定となることも分かった。
【まとめ】
以上から As4S6 と POB では少なくとも１個の余剰電子を安定的に捕捉すると期待できる。一方、
POAl と POSS でも余剰電子の捕捉は可能であるが、同時に比較的これを放しやすい性質も持つと予想できる。すなわち電子化物を与えるカゴ状分子であっても電子の捕捉性質には差異があり、これによって相対的に電子滞留型および電子移動型の電子化物を作り分けることができよう。
つまり用いる元素の種類やカゴ状構造の選択により異なる性質を持つ元素ブロックの作り分けが可能である。これらのカゴ状分子の両側に適切な官能基をつけて図 3 のように高分子に組み込むことができれば、導電性、誘電性、磁性、特徴的な光物性など種々の機能を持つソフトマテリアル
電子化物の作製が可能になると考えられる。現在そのような分子設計をさらに開始している。

e-

e-

(a)

(b)

eFig. 3e-e-Concepts of soft-material electride consisting of polymer chain and As4S6 or

POB element-block. (a) Catenated and (b) suspended types.

【文献】 1) Y. Chujo and K. Tanaka, Bull. Chem. Soc. Jpn., 88, 633-643 (2015). 2) K. Tanaka, H. Fueno, and
K. Naka, Polym. Prep. Jpn., 63, 4546-4547 (2014). 3) 田中一義, 笛野博之, セラミックス, 51, 739-742(2016). 4) J. Zapico, M. Shirai, R. Sugiura, N. Idota, H. Fueno, K. Tanaka, and Y. Sugahara, Chem. Lett., 46,
181-184 (2017). 5) Gaussian 09, Revision D.01, M. J. Frisch et al., Gaussian Inc., Wallingford, CT (2009).

－ 73 －

Ⅳ 研究業績 (2016)

2. 論文
(1)
Shun GODA, Masanori NIKAI, Mikinao ITO, Daisuke HASHIZUME, Kohei TAMAO, Atsushi
OKAZAWA, Norimichi KOJIMA, Hiroyuki FUENO, Kazuyoshi TANAKA, Yoshio KOBAYASHI,
and Tsukasa MATSUO,“Synthesis and magnetic properties of linear two-coordinate monomeric
diaryliron (II) complexes bearing fused-ring bulky “Rind” groups”
Chem. Lett. 45, 634-636 (2016).
(2)
Tohru SATO, Naoki HARUTA, and Kazuyoshi TANAKA,“Thermodynamical vibronic coupling constant and density: Chemical potential
and vibronic coupling in reactions”
Chem. Phys. Lett. 652, 157-161 (2016).
(3)
Hiroyuki WATANABE, Masataka HIROSE, Kazuyoshi TANAKA, Kazuo TANAKA, andYoshiki CHUJO,“Color tuning of alternating conjugated polymers composed ofpentaazaphenanthrene by modulating their unique electronic structures
involving isolated-LUMOs”
Polym. Chem. 7, 3674-3680 (2016).
(4)
Yoshimasa MATSUMURA, Makoto ISHIDOSHIRO, Yasuyuki IRIE, Hiroaki IMOTO, Kensuke
NAKA, Kazuyoshi TANAKA, Shinsuke INAGI, and Ikuyoshi TOMITA,“Arsole-containing -conjugated polymer by the post-element-transformation
technique” Angew. Chem. Int. Ed. 55, 15040-15043 (2016).
(5)
Akihiro ITO, Ryohei KURATA, Yusuke NOMA, Yasukazu HIRAO, and Kazuyoshi TANAKA,“Radical cation of an oligoarylamine having a nitroxide radical substituent:
A coexistent molecular system of localized and delocalized spins”
J. Org. Chem. 81, 11416-11420 (2016).
(6)
Julián ZAPICO, Marie SHIRAI, Ryo SUGIURA, Naokazu IDOTA, Hiroyuki FUENO,
Kazuyoshi TANAKA, and Yoshiyuki SUGAHARA,“Borophosphonate cages as element-blocks: Ab initio calculation of theelectronic structure of a simple borophosphonate, [HPO3BH]4, and synthesis of
two novel borophosphonate cages with polymerizable groups”
Chem. Lett. 46, 181-184 (2017).
3. 総説(1) 田中一義、笛野博之「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」
セラミックス 51, No. 11, 739-742 (2016).
(2) 田中一義「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？」－ 74 －

Ⅳ 研究業績 (2016)

化学

21, No. 12, 24-27 (2016).

4. 学会発表(1) 渡辺浩行、広瀬仁敬、田中一義、田中一生、中條善樹「ペンタアザフェナレンを含む共役系高分子の合成とその電子状態」
第 65 回高分子討論会 横浜 2016/9/14 1B04
(2) Kazuyoshi Tanaka,“Dawn of electronic-structure study of CNT and its relatives”
2016-CNT25 (International Symposium on Carbon Nanotube in Commemoration of
Its Quarter-Century Anniversary) 東京 2016.11.17 （講演番号なし）(3) Hiroyuki Watanabe, Masataka Hirose, Kazuyoshi Tanaka, Kazuo Tanaka, andYoshiki Chujo,“Pentaazaphenalene based π-conjugated system”
The 11th SPSJ International Polymer Conference (IPC 2016)、Fukuoka
2016.12.16 16E-08(4) Kazuyoshi Tanaka“Toward soft-material electrides with use of element-blocks of caged-shape”
The 2nd International Symposium on Polymeric Materials Based on
Element-Blocks、
Kyoto 2016.1.19 IL-20(5) Kazuyoshi Tanaka, Hiroyuki Fueno, Kazunobu Ishibashi, Hiroyuki Suto, Mitsuru
Matsumoto, Naoki Hasegawa, Hiroyuki Kawaguchi, Hiroki Nishiyama, andIkuyoshi Tomita,“Theoretical examination on absorption of hydrogen molecules to titanocene
Complex”
日本化学会第 97 春季年会(2017) 横浜 2017/3/17 2PA-117(6) 中西勇介、石田豊、川口博之、石橋一伸、須藤裕之、松本満、長谷川直樹、冨田
育義、西山寛樹、田中一義「フェノキシド-ホスフィン混合系型配位子を持つカチオン性ジルコニウム錯体と水素の反応」
日本化学会第 97 春季年会(2017) 横浜 2017/3/17 2PA-118(7) 西山寛樹、石橋一伸、須藤裕之、松本満、長谷川直樹、川口博之、田中一義、稲木信介、冨田育義「ホスファメタロセン骨格を有する有機金属ポリマーの水素分子吸着に関する研究」
日本化学会第 97 春季年会(2017) 横浜 2017/3/17 2PA-119(8) Julián Zapico, Kazuyoshi Tanaka, and Yoshiyuki Sugahara,“Borophosphonate cages as element-blocks: Ab initio study of simple [HPO3BH]4and synthesis of two novel polymerizable borophosphonate cages”－ 75 －

Ⅳ 研究業績 (2016)

日本化学会第 97 春季年会(2017) アジア国際シンポジウム 横浜 2017/3/18
3G1-31
5. その他(1) 田中一義「元素ブロック設計のための計算化学とその実例」日本化学会秋季事業 第６回 CSJ
化学フェスタ 2016 特別企画、江戸川区（タワーホール船堀） 2016/11/15 H2-06(2) 田中一義「企業研究者のための計算化学」京都グリーンケミカル・ネットワーク人材育成事
業第３回、京都（京都市成長産業創造センター）2016/12/6 （講演番号なし）－ 76 －

Ⅳ 研究業績 (2016)

４．リサーチリーダー

Kazuo
Takatsuka
Name
Kazuo
Takatsuka
Research Leader

1. Summary of the research of the year
Synchronizing with rapid progress in cutting-edge experimental methodologies such as ultrafast andintense pulse laser technology, we have been developing a basic framework of theoretical chemistry, which
we call the theory of nonadiabatic electron wavepacket dynamics, with an aim of applications to real-timetracking of the coupled dynamics of electron and nuclear wavepakets within a molecule and to control ofchemical reactions based on insights thus attained.
(i) Lorentz-force-like multidimensional effects of nonadiabatic interactions that can mechanicallybreak the symmetric production of optical isomers [9]The Longuett-Higgins (Berry) phase arising from nonadiabatic dynamics and the Aharonov-Bohm phaseassociated with the dynamics of a charged particle in electromagnetic vector potential are well known to be
individually a manifestation of a class of the so-called geometrical phase. We have found and discussed
another similarity between the force working on a charged particle moving in a magnetic field, the Lorentz
force, and a force working on nuclei while passing across a region where they have a strong quantum
mechanical kinematic (nonadiabatic) coupling with electrons in a molecule. This kinematic force is indeed
akin to the Lorentz force in that its magnitude is proportional to the velocity of the relevant nuclei and works
in the direction perpendicular to its translational motion. Hence this Lorentz-like nonadiabatic force isrealized only in space of more or equal to three dimensions, thereby highlighting a truly multi-dimensional
effect of nonadiabatic interaction. We have investigated its physical significance qualitatively in the context
of breaking of molecular spatial symmetry, which is not seen otherwise without this force. This particularsymmetry-breaking is demonstrated in application to a coplanar collision between a planar molecule and an
atom sharing the same plane. It has been found that the atom is guided by this force to the direction out fromthe plane, resulting in a configuration that distinguishes one side of the mirror plane from the other. This canserve as a trigger for the dynamics towards molecular chirality.

(ii) Application of the nonadiabatic electron wavepacket theory to chemical reactions in excited statesii-1) Chemistry beyond the notion of potential energy surface [4]Following the previous study on nonadiabatic reaction dynamics including boron clusters [Yonehara and
Takatsuka, J. Chem. Phys. 137, 22A520 (2012) ], we explored deep into highly excited electronic states ofthe singlet boron cluster (B��) to find the characteristic features of the densely quasi-degenerate electronic
state manifold, which undergo extremely frequent nonadiabatic transitions and thereby intensive electronic
state mixing among very many of the relevant states. So much so, isolating the individual adiabatic states and－ 77 －

Ⅳ 研究業績 (2016)

tracking the expected potential energy surfaces both lose the physical sense. This domain of molecularsituation is far beyond the realm of the Born-Oppenheimer approximation. To survey such a violent
electronic state-mixing, we applied a method of nonadiabatic electron wavepacket dynamics, here actually
the semiclassical Ehrenfest method. We have tracked those electron wavepackets and found the electronic
state mixing looks like an ultrafast diffusion (actually, a fractional Brownian motion) in the Hilbert space,which results in huge fluctuation in the electronic-state space. Furthermore, due to such a violent mixing, thequantum phases associated with the electronic states are swiftly randomized, and consequently the coherence
among the electronic states are lost quickly. Besides, these highly excited states are mostly of highly
poly-radical nature, even in the spin singlet manifold and the number of radicals amounts up to 10 electrons
in the sense of unpaired electrons. Thus the electronic states are summarized to be poly-radical anddecoherent with huge fluctuation in shorter time scales of vibrational motions. The present numerical study
thus sets a theoretical foundation for unknown molecular properties and chemical reactivity of such densely
quasi-degenerate chemical species.
ii-2) Coupled proton and electron-wavepacket transfer (CPEWT) as a universal mechanism of charge
separation in organic and biological molecular systems [5,8]We have proposed an excited-state mechanism of charge separation (proton-electron pair creation) relevantto the photoinduced water-splitting reaction (2H₂ O → 4H⁺ + 4e⁻ + O₂ ) catalyzed by Mn-H�O systems.
The water splitting is conceived to be triggered by photoinduced charge separation, in which electrons aredetached from a proton in water. We here study the detailed mechanism of the charge separation by means of
the theory of nonadiabatic electron wavepacket dynamics, in which all the electrons and nuclei of themolecules are considered. The mechanism has been examined in terms of simple model systems generally
expressed as X--Mn--OH�⋯A, where X = (OH, Ca(OH)�) and A = (N-methylformamidine, guanidine,
imidazole or ammonia cluster). We have found that both an electron and a proton are simultaneouslytransferred from donor site to the acceptors through conical intersections. In this mechanism, the electron
takes different pathways from that of the proton and reach the Rydberg--like states of the acceptors, thereby
inducing charge separation. We have found another crucial nonadiabatic process that deteriorates theefficiency of charge separation by rendering the created pair of proton and electron back to the originallydonor site through the states of d-d band originated from Mn atom. Repetition of this process graduallyannihilates the created pair of proton and electron in a way different from the usual charge recombination
process. We addressed this dynamics also by means of a path--branching representation. The dynamical rolesof doped Ca atom are also revealed, such as the change of the pathways of electron flow and reducing theannihilation dynamics of proton-electron pair.
ii-3) Substituent effects on photoisomerization in polyene; which double-bond will be broken to asingle-bond in radiationless transition? [7]Guided by a notion of symmetry-breaking modulation or control of the so-called symmetry allowed conicalintersection by shining laser pulses [Y. Arasaki et al. PCCP, 2010, 12, 1239], we have explored a possibilityof the modulation of the symmetry allowed conical intersection by chemical substitution with functional－ 78 －

Ⅳ 研究業績 (2016)groups. As a first case study, we chose photoisomerization dynamics of s-trans-1,3-butadieneH�C=CH-CH=CH� with one of the terminal hydrogen atom being replaced by -CF�. The target here is not
the control of the rate of nonadiabatic transition but to know which one of the double bonds is more
frequently isomerized in the radiationless quenching process on the way back to the ground state. We haveanalyzed when and how the symmetry is broken by tracking ab initio molecular dynamics paths, themean-field paths with use of the nonadiabatic electron wavepacket dynamics, and the associatedbranching-paths.
(iii) Dynamics of ultrafast photoionozation and Auger process from electronic wavepacket states [10]One of the critical difficulties in the present theory of molecular science is the lack of an appropriate
method to cope with ionization dynamics of polyatomic molecules, which is induced by multiphoton
electronic-state excitation due to pulse laser through wavepacket state or by electronic avalanche dynamics(the Auger process) to fill up a hole laser-created in inner shells. We have proposed a practical theory for
dynamics of molecular photoionization from nonadiabatic electron wavepackets driven by intense pulse
lasers Herein theime evolution of photoelectron distribution is evaluated in terms of out-going electron flux
(current of the probability density of electrons) that has kinetic energy high enough to recede from themolecular system. The relevant electron flux is in turn evaluated with the complex-valued electronic
wavefunctions that are time evolved in nonadiabatic electron wavepacket dynamics in laser fields. To
uniquely rebuild such wavefunctions with its electronic population being lost by ionization, we adopt thecomplex-valued natural orbitals emerging from the electron density as building block of the total
wavefunction. The method has been implemented into a quantum chemistry code, which is based on
configuration state mixing for polyatomic molecules. Some of the practical aspects needed for its application
will be presented. As a first illustrative example, we show the results of hydrogen molecule and its isotope
substitutes (HD and DD), which are photoionized by a two-cycle pulse laser. Photon emission spectrum
associated with above threshold ionization is also shown. Another example is taken from photoionization
dynamics of a water molecule. Qualitatively significant effects of nonadiabatic interaction on thephotoelectron spectrum are demonstrated. Thus we have opened a gate to proceed into a new field ofchemical physics.
(iv) Ultrafast nuclear wavepacket dynamics driven by intense pulse lasersiv-1) Creation of a novel molecular state created by an interplay between laser and nonadiabaticinteractions[1]

When a nonadiabatic system that has an ionic state (large dipole moment) and a covalent state (small dipole
moment) is located in a strong laser field, the crossing point of the two potential energy curves is forced tooscillate due to the oscillating laser field and to meet wavepackets moving on the potential curves manytimes. This leads to additional transitions between the two states, and under favorable conditions, thewavepacket may be confined in a spatial region rich in nonadiabatic interaction. In this paper, taking the LiF
molecule system in a continuous-wave driving field as a prototypical example, the dynamical origins of the－ 79 －

Ⅳ 研究業績 (2016)

wavepacket confinement has been investigated. Identification of such new states that is not found in mothernature will extend our realm of chemistry.
iv-2) Very characteristic photon emission induced by CW laser on molecules having intramolecularelectron transfer through nonadiabatic transitions [3,6]We have proposed a theoretical principle to directly monitor the bifurcation of quantum wavepackets
passing through nonadiabatic regions of a molecule that is placed in intense continuous wave (CW) laser
fields. This idea makes use of the phenomenon of laser-driven photon emission from molecules that canundergo nonadiabatic transitions between ionic and covalent potential energy surfaces like Li⁺ F⁻ and LiF.
The resultant photon emission spectra are of anomalous yet characteristic frequency and intensity, if pumped
to an energy level in which the nonadiabatic region is accessible and placed in a CW laser field. The
proposed method is designed to take the time-frequency spectrogram with an appropriate time-window fromthis photon emission to detect the time evolution of the frequency and intensity, which depend on the
dynamics and location of the relevant nuclear wavepackets. This method is specifically designed for the
study of dynamics in intense CW laser fields and is rather limited in scope than other techniques forfemtosecond chemical dynamics in vacuum. The following characteristic features of dynamics can bemapped onto the spectrogram: (1) the period of driven vibrational motion (temporally confined vibrational
states in otherwise dissociative channels, the period and other states of which dramatically vary dependingon the CW driving lasers applied), (2) the existence of multiple nuclear wavepackets running individually on
the field-dressed potential energy surfaces, (3) the time-scale of coherent interaction between the nuclear
wavepackets running on ionic and covalent electronic states after their branching (the so-called coherencetime in the terminology of the theory of nonadiabatic interaction), and so on.
(v) Theory of embedding mechanics in statistical environment; real-time chemical dynamics instatistically treated solvents [2]We have proposed a basic theory to study real-time dynamics embedded in a large environment that istreated with statistical method. In light of great progress in the molecular-level studies on time-resolved
spectroscopies, chemical reaction dynamics, and so on, not only in gas phase but in condensed phases likeliquid solvents and even in crowded environments in living cells, we need to bridge over a gap between
statistical mechanics and microscopic real-time dynamics. For instance, an analogy to gas-phase dynamics inwhich molecules are driven by the gradient of the potential energy hyper-surfaces (PES) suggests thatparticles in condensed phases should run on the free energy surface instead. Question is whether thisanticipation is correct. To answer it, we here propose a mixed dynamics and statistical representation to treat
chemical dynamics embedded in statistical ensemble. We first define entropy functional, which is a functionof the phase-space position of the dynamical subsystem, being dressed with statistical weights from thestatistical counterpart. We then consider the functionals of temperature, free energy, and chemical potential
as their extensions in statistical mechanics, through which one can clarify the relationship between real-time
microscopic dynamics and statistical quantities. As an illustrative example we show that molecules in the
dynamical subsystem should run on the free-energy functional surface, if and only if the spatial gradients of－ 80 －

Ⅳ 研究業績 (2016)

temperature functional are all zero. Otherwise, additional forces emerge from the gradient of the temperaturefunctional. Numerical demonstrations are presented in the very basic level of this theory of moleculardissociation in atomic cluster solvent. This theory is being extended to treat nonadiabatic electron wavepaket
dynamics in statistical solvents.

2. Original papers
1.

Stark-assisted quantum confinement of wavepackets. A coupling of nonadiabatic interaction
and CW-laser.
Y. Arasaki, Y. Mizuno, S. Scheit, and K. Takatsuka, J. Chem. Phys. 144, 044107 (10pages) (2016).

2.

Classical and semiclassical dynamics in statistical environments with a mixed dynamical andstatistical representation.
K. Takatsuka and K. Matsumoto, PCCP, 18, 1771-1785 (2016).

3.

A perturbation theoretic approach to the Riccati equation for the Floquet energies, spectral
intensities, and cutoff energy of harmonic generation in photoemission from nonadiabatic
electron-transfer dynamics driven by infrared CW laser fields.
Yuta Mizuno, Yasuki Arasaki, and Kazuo Takatsuka, J. Chem. Phys. 144, 024106 (13pages) (2016).

4.

Nonadiabatic electron dynamics in densely quasidegenerate states in highly excited boron
cluster.
Takehiro Yonehara and Kazuo Takatsuka, J. Chem. Phys. 144, 164304 (15 pages)(2016).

5.

Dynamical mechanism of charge separation by photoexcited generation of proton-electron pairs
in organic molecular systems.
A nonadiabatic electron wavepacket dynamics study.
Kentaro Yamamoto and Kazuo Takatsuka, Chemical Physics Perspective (invited andreviewed), 475, 39- 53 (2016).

6.

Real-time observation of wavepacket bifurcation on nonadiabatically coupled field-dressed
potential energy curves by means of spectrogram of induced photon-emission from molecules
driven by CW laser.
Yuta Mizuno, Yasuki Arasaki, and Kazuo Takatsuka, J. Chem. Phys. 145, 184305 (11－ 81 －

Ⅳ 研究業績 (2016)

pages) (2016).
7.

Chemical modification of conical intersections in photoisomerization dynamics of butadienederivatives.
Hiroki Ichikawa and Kazuo Takatsuka, J. Phys. Chem. A, 121, 315-325 (2017).
(Also published in Mark S. Gordon Festschrift (virtual issue))

8.

Photoinduced charge separation catalyzed by Mn-oxides onto a Y-shaped branching acceptor
efficiently preventing charge recombination
Kentaro Yamamoto and Kazuo Takatsuka, ChemPhysChem, 18, 1-13 (2017).

9.

Lorentz-like force emerging from kinematic interactions between electrons and nuclei inmolecules. A quantum mechanical origin of symmetry breaking that can trigger molecularchirality.
Kazuo Takatsuka, J. Chem. Phys. 146, 084312 (10 pages) (2017).

10. Dynamics of photoionization from molecular electronic wavepacket states in intense pulse laser
fields: A nonadiabatic electron wavepacket study.
Takahide Matsuoka and Kazuo Takatsuka, J. Chem. Phys. 146,134114 (14 pages)(2017).

3. Presentation at academic conferences(1) 高塚和夫「溶媒中の電子移動の非断熱電子動力学： Marcus 理論の分子論」
第 19 理論化学討論会，2016 年 5 月 23 日～2016 年 5 月 25 日，早稲田大学(2) Kazuo Takatsuka“Quantum Chemistry beyond the Born-Oppenheimer Approximation”
JFS 2016.10.26-28, FIFC, 2016 年 10 月 26 日～2016 年 10 月 28 日 福井謙一記念研究センター(3) Kazuo Takatsuka“Molecular Science of Nonadiabatic Electron Wavepackets: Trying to bridge
betweenultrafast nonadiabatic dynamics and chemistry”
The 77th Okazaki Conference Series: International Symposium on Ultrafast Dynamics－ 82 －

Ⅳ 研究業績 (2016)

in Molecular and Material Sciences, 2017 年 3 月 6 日～2017 年 3 月 8 日, 岡崎コン
ファレンスセンター(4) Kazuo Takatsuka“Chemistry of nonadiabatic electron flow ：Reactions”
GAMESS7557, 2017.1.16-18, Kauai, Hawaii

Symmetry Breaking in Chemical(5) 高塚和夫「化学反応における電子動力学－電子の運動が観える時代の基礎化学－」
福井センターシンポジウム FIFC 1.27.2017(6) 新崎康樹，高塚和夫“Semiclassical computation of photoelectron signals from conical intersection
dynamics”
International Symposium on Ultrafast Dynamics in
Molecular and Material
Sciences, 2017 年 3 月 6 日〜2017 年 3 月 8 日岡崎コンファレンスセンター(7) Kentaro Yamamoto, Kazuo Takatsuka“Photochemical mechanism of charge separation taken out of water molecule”
第 19 理論化学討論会，2016 年 5 月 23 日～2016 年 5 月 25 日，早稲田大学(8) Kentaro Yamamoto, Kazuo Takatsuka「 光 化 学 系 II に お け る 水 分 解 の 初 期 段 階 の 機 構 に つ い て ; Y 字 型 Coupled
Proton-Electron Transfer
第 20 回分子科学討論会」，2016 年 9 月 13 日～2016 年 9 月 15 日，神戸ファッションマート(9) Kentaro Yamamoto, Kazuo Takatsuka“Photoinduced Charge Separation Catalyzed by Mn-Oxides onto a Y-shaped Branching
Acceptor Efficiently Preventing Charge Recombination”
JFS-Joint Symposium on Theoretical and Computational Science of Complex Systems，
2016 年 10 月 26 日～2016 年 10 月 28 日，福井謙一記念研究センター(10) Kentaro Yamamoto, Kazuo Takatsuka“Photoinduced Charge Separation Catalyzed by Mn-Oxides onto a Y-shaped Branching
Acceptor Efficiently Preventing Charge Recombination”
第 14 回京都大学福井謙一記念研究センターシンポジウム，2017 年 1 月 27 日，福井謙一記念研究センター－ 83 －

Ⅳ 研究業績 (2016)(11) Kentaro Yamamoto, Kazuo Takatsuka“Photodynamical electron-wavepacket mechanism of water-splitting catalyzed bymanganese oxides involving hydrogen-bond network”
The 77th Okazaki Conference Series: International Symposium on Ultrafast Dynamics
in Molecular and Material Sciences，2017 年 3 月 6 日～2017 年 3 月 8 日，岡崎コンファレンスセンター(12) 松岡貴英，高塚和夫「強レーザー場中の励起分子からのイオン化過程の非断熱電子動力学」
第 19 回 理論化学討論会，2016 年 5 月 23 日～2016 年 5 月 25 日
早稲田大学(13) 松岡貴英，高塚和夫「強光子場中多原子分子の電離過程における非断熱電子動力学」
第 10 回分子科学討論会 2016 神戸，2016 年 9 月 13 日～2016 年 9 月 15 日，神戸ファッションマート(14) Takahide Matsuoka, Kazuo Takatsuka“Effect of Nonadiabatic Interactions in Ionization Process of Multi-Electron
Polyatomic Molecule”
Japan-France-Spain Joint-Symposium on Theoretical and Computational Science ofComplex Systems，2016 年 10 月 26 日～2016 年 10 月 28 日，福井謙一記念研究センター(15) 松岡貴英，高塚和夫「高強度パルスレーザー場中のイオン化過程の非断熱電子ダイナミックス」
第 14 回京都大学福井謙一記念研究センターシンポジウム，2017 年 1 月 27 日，福井謙一記念研究センター(16) Takahide Matsuoka, Kazuo Takatsuka“Dynamics of photoionization from molecular electronic wavepacket states inintense pulse laser fields”
第 77 回岡崎コンファレンス，2017 年 3 月 6 日～2017 年 3 月 8 日，岡崎カンファレン
スセンター－ 84 －

Ⅳ 研究業績 (2016)

５．研究員

北浦

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－ 85 －

Ⅳ 研究業績 (2016)N

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Ⅳ 研究業績 (2016)īĚïń  . ČĉouwZ ®Ê>NeZīĚïńh
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【文 献 】 1) Gordon, M. S.; Pruitt, S. R.; Fedorov, D. G.; Slipchenko, L. V. Chem. Rev. 2012, 112, 632–672, 2) S.
Huzinaga and A. A. Cantu, J. Chem. Phys. 55,5543 (1971), 3) T. Shimazaki, M. Hashimoto and T. Maeda,
Proceedings of the 3rd International Workshop on Software Engineering for High Performance
Computing in Computational Science and Engineering, Association for Computing Machinery
9(2015).

İê(1) Tomomi Shimazaki, Kazuo Kitaura, Dmitri G. Fedorov, Takeshi Nakajima“Gropup molecular orbital approarch to solve Huzinaga subsystem self-consistent-field
equations”
J. Chem. Phys. 146(8) 084109(2017).
(2) Dmitri G. Fedorov, Kazuo Kitaura"Many-body expansion of the Fock matrix in the fragment molecular orbital method"
J. Chem. Phys. 147(10)104106(2017).
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Ⅳ 研究業績 (2016)

６．博士研究員

Takuya Saito
Saito
TakuyaFIFC Fellow
FIFC Fellow (To 31 Oct. 2016)
1. Summary of the research of the year
Complementary mode analyses for sub- and superdiffusion
A tagged monomer of a polymer undergoes anomalous diffusion. Through the fluctuation-dissipation
relation, the diffusion is associated with a response. To verify the relation between the diffusion and response,
there are two typical protocols; (i) observing the position while pulling with the constant force, (ii) the
momentum transfer while pulling with the constant velocity (the momentum transfer is monitored byintegrating the force acting on the tagged monomer with respect to time). The generalized Langevinequations with the power-law kernels describe those dynamics. The one kernel is converted into the otherwith the Laplace transform so that the sum of the exponents for sub- and superdiffusion is constant value 2,i.e.,x (t )2 ~ t ,p(t ) 2 ~ t 2  . This means that, if the one shows subdiffusion, the other does

invariably superdiffusion.
In the protocol (i) for the polymer, the tagged monomer shows the subdiffusion. The GLE generating
the subdiffusion is decomposed into equations of motion in mode space with the restoring force. On the other
hand, the superdiffusion is observed at the constant velocity protocol (ii). The mode analysis for thesubdiffusion is no longer applied to the superdiffusion, since the subdiffusion mode analysis generates thesubdiffusion, but not the superdiffusion even if tuning the exponents of the power law in the coefficients.
We then proposed the mode analysis for the superdiffusion. Equation of motion in the mode space forthe superdiffusion has the form of the underdamped
Langevinequation,

which

is

derivedbyinvestigating the decomposition of the kernel in thegeneralized Langevin equation. Superimposing themodes, the GLE for the superdiffusion of the
momentum transfer is reproduced. In a similar way,
Fig 1. Schematic representation of a polymer
in near-equilibrium state when weakly pullingat constant force f or velocity v.

the numerical verifications suggested that the mode
analysis for the superdiffusion generates thesuperdiffusion, but not the subdiffusion.
Themode analyses for the sub- andsuperdiffusion is complimentary, totally covering
the exponents range 0    2 .

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Ⅳ 研究業績 (2016)

Nonequilibrium mode analyses for superdiffusion
The fluctuation-dissipation relation (FDR) is not ensured in the nonequilibrium condition. Indeed, theFDR derivation was found in the polymer stretching at the constant force protocol, where the subdiffusion
was observed. The mode analysis for the subdiffusion can qualitatively describe the FDR derivation by
giving the Langevin equation for the stretching state, which has the form of the overdamped Langevinequation with harmonic potential in the normal mode.
However,asclarifiedintheequilibrium mode analyses, the mode forthe subdiffusion cannot be applied to
dynamics for the superdiffusion and viceversa. To describe superdiffusion in the
Fig 2. Schematic representation of a polymer in transient

nonequilibrium,

we

then

need

the

stretching process.

different approach and studying thenonequilibrium mode analysis for thesuperdiffusion.
First we performed the molecular

dynamics (MD) simulation for the polymer stretching at the constant velocity protocol. To achieve thenonequilibrium, the operation velocity is set to be high. We established the plot of the normalized ratio of thevariance to the average momentum, which takes a value 2 if the FDR holds. The results show that (1) the
ratio almost retains the value 2 at the beginning, but (2) it goes upward and peaks, (3) it eventually turns
back to the value 2. This is interpreted by the following scenario: (1) the equilibrium modes are monitored
until the first blob forms. As a result, the FDR is maintained. (2) The transient nonequilibrium modes show
up and the ratio deviates from the value 2. (3) The center of mass mode dominates after the internal modes
relax. The FDR then finally recovers. To explain the simulation results, we discussed the mode analysis forthe superdiffusion.

Active diffusion driven by athermal noise
Besides the thermal noise, studying athermal noise could shed a new insight into the fluctuation in aliving cell. We then theoretically investigate the active diffusion driven by athermal noise. By introducing theeffective friction, we drive the scaling laws for the athermally driven system. In addition, in the presence of
the active noise, we discussed the various polymeric characteristics or situations, which include theself-avoiding effect, hydrodynamic interactions, branching and the viscoelastic conditions.

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2. Original papers(1) Takahiro Sakaue, and Takuya Saito,“Active diffusion of model chromosomal loci driven by athermal noise”
Soft matter 13, 81(2017).
3. Presentation at academic conferences(1) Takuya Saito and Takahiro Sakaue“Fluctuations in driven polymer stretching with constant velocity”
Kakuma Campus, Kanazawa University, Ishikawa, Sep 16, 2017
4. Others(1) Takuya Saito“駆動される高分子の標識されたモノマーの異常拡散”
ERI, The University of Tokyo, Tokyo, Sep. 21, 2016.

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Ⅳ 研究業績 (2016)

Mitsusuke Tarama
Mitsusuke Tarama
FIFC
Fellow
FIFC Fellow
1. Summary of the research of the year
Swinging motion of active deformable particles in Poiseuille flow

Active matter is an object that possesses machinery to convert potential energy tokinetic energy and consequently exhibits movement by breaking symmetry. It is a broadconcept including both biological and artificial systems. Well-studied active particles are
rigid ones, which have prescribed undeformable shape, such as self-propelled camphor
particles and active colloids as well as microswimmers such as bacteria. There also exist
deformable active particles that change their shape during the active movement. Shapedeformation is of basic importance for living cells and micro-organisms like eukaryotes.
Besides, artificial active particles accompanied by shape deformation are realised in liquid
droplets and vesicles. For such active deformable particles, various dynamical states havebeen obtained even for an isolated single self-propelled object. The theoretical study of suchactive particles are briefly divided into two approaches. One is a detailed modeling of eachspecific example, which enables us to clarify the mechanisms and the properties of thesystem. Besides, since the examples of active particles range from biological to artificial
systems, it is also important to develop general descriptions to elucidate universal featuresof miscellaneous active particles. We are interested in the latter aspect and have pushedforwards the development of a general description of active deformable particles.
Although by breaking symmetry active particles achieve spontaneous motion, in mostpractical situations this motion is influenced by the environment in various manners. Indeed
it is an interesting problem how active particles behave as a consequence of the interplay
between active motion and external stimuli. For active particles swimming in a fluid
environment the effect of the external flow field is crucial. A simple linear shear flow,
Poisueille flow, and swirl flow are characteristic flow profiles. Here we discuss the case of a
Poisueille flow, which often appears in a flow channel.
In particular, we are interested in the effect on deformable active particles such as
liquid droplets that self-propel due to Marangoni effect. Based on symmetry considerations,
we have derived a set of coupled nonlinear time-evolution equations that models active
deformable particles under an external flow field [1]. Here we considered the Poiseuilleflow profile of the form u = (u0(1-Y), 0), as sketched in Fig. 1(a). The effect of the boundary
walls placed at Y = ±1 are taken into account by asoft repulsive potential and the hydrodynamic
interaction is omitted. For simplicity, we take into
consideration the lowest mode deformation, i.e.,the second-mode deformation which represents anelliptical (ellipsoidal in 3d) deformation, and we
confine ourselves to a two-dimensional space.
From symmetry, the particles tend to self-propelin either parallel or perpendicular direction withrespect to the longitudinal axis of the elliptical Fig. 1: Sketches of (a) the flow velocity u(Y) andvorticity W, the particles with (b) parallel andshape deformation, as sketched in Figs. 1(b) and(c) perpendicular configurations, and (d) the1(c). We refer to these cases as parallel andvalue of the angle φ. This figure is reproduced
from Ref. [3].
perpendicular particles, respectively.
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For the case of rigid active particles, or active
colloids, the dynamics in Poiseuille flow have beenstudied in detail [2]. Zöttl and Stark showed that both,the circular active colloids and the slender ellipticalactive colloids, that correspond to the parallel
particles, undergo swinging motion around thecenterline of the flow as well as tumbling motion. In
the limit of a rigid elliptical shape and in the overdamped limit, our model is reduced to the one studied
by Zöttl and Stark. Then, we solved the equations of
motion analytically. The solutions are characterized by
the vertical position Y to the streamline and the
direction of the active velocity φ, as shown in Fig. 2.
See Fig. 1(d) for the definition of φ. We found that theparallel and perpendicular particles show qualitatively
the same dynamics. Namely, in both cases the particles
exhibit swinging motion around the centerline andtumbling motion, which are displayed by the graysolid lines and the black broken lines in Fig. 2. Those
solutions are divided by the separatrix plotted by theblue solid line in Fig. 2.
When the active particle is deformable, the timeevolution equations are too complicated to solve
analytically and therefore we integrated them
numerically [3]. We varied the strength of the selfpropulsion α and the external Poiseuille flow u0. We
found that the parallel and perpendicular particles
exhibit different dynamics. Note that, in the absenceof the external flow, there is a bifurcation fromstraight motion to circular motion at α = αc [4].
First, we explain the motion of the parallel
particles. The results are summarized in the phase
diagram in Fig. 3(a). For 0 < α < αc, these particles
showed swinging motion around the centreline for theparameters indicated by the black open circles in Fig.
3(a). Although most swinging particles moved
downstream as depicted in Fig. 3(d), upstream
swinging motion was also found for a relatively small
flow velocity as shown in Fig. 3(c). For very small u0
as indicated by the pluses in Fig. 3(a), the particle
touched the confinement at Y = ±1, as displayed inFig. 3(b). These solutions coexisted with tumbling

Fig. 2: The trajectories in the Y-φ space ofthe solutions of rigid active particles
with [(a)–(c)] the parallel configuration
and[(d)–(f)]theperpendicularconfiguration. The gray solid lines andthe black broken lines correspond to theswinging motion around the centerline
and the tumbling motion, respectively,
which are separated by the separatrix
displayed by the dark gray solid line.
The flow velocity is chosen as u0 = 0.25
for (a) and (d), 0.6 for (b) and (e), and 1for (c) and (f). This figure is reproduced
from Ref. [3].

Fig. 3: Dynamics of parallel particles in the Poiseuille flow. (a) Dynamical phase diagram. (b)–(f) Characteristic realspace trajectories of (b) bouncing motion between the two channel walls; (c) upstream swinging motion [dark grayline] and bouncing motion against the wall with the shape oscillating around θ = 0 [light gray line]; (d) downstream
swinging motion [dark gray line] and bouncing motion against the wall with the shape oscillating around the
diagonal direction [light gray line]; (e) cycloidal motion [dark gray line] and tumbling motion at the wall [light grayline]; (f) bouncing motion with excursion to the middle of the channel. This figure is reproduced from Ref. [3].
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motion, as shown in Fig. 3(e), and two types ofbouncing motion, as in Figs. 3(c) and 3(d), which wereobtained for the parameters indicated by the magenta
down triangles, pink up triangles, and purple
diamonds in Fig. 3(a), respectively. For α > αc, theparticles exhibited cycloidal motion, as shown in Fig.
3(e) for cyan dots in Fig. 3(a). At the orange crosses inFig. 3(a), the particle underwent bouncing motion
against one wall with an excursion to the middle of thechannel, as shown in Fig. 3(f).
Next, we discuss the motion of the perpendicularparticles. The results are summarized in the phase
diagram displayed in Fig. 4(a). In this case, swinging
motion was not observed. For α < αc, theperpendicular particles showed bouncing motion
between two walls as shown in Fig. 4(b), which wereobtained for the red plusses in Fig. 4(a). For large u0,
at the purple pentagons in Fig. 4(a), the particles
bounced against one wall as displayed in Fig. 4(c).
Interestingly, for further increased u0, theperpendicular particles exhibited straight motion along
Fig. 4: Dynamics of perpendicular particles
a streamline far from the channel walls as depicted inin the Poiseuille flow. (a) Dynamicalphase diagram. (b)–(f) Characteristic
Fig. 4(d). Such solution was observed at the blue
trajectories of each dynamical motion insquares in Fig. 4(a). For α > αc, cycloidal motion andreal space. (b) Bouncing between the
tumbling motion are obtained, as shown in Fig. 4(e), at
two channel walls; (c) Bouncing motion
the cyan dotes and at the magenta down triangles inagainst one of the two walls; (d)Straight motion far from the channel
Fig. 4(a). At the orange cross in Fig. 4(a), the particle
wall; (e) Cycloidal motion [dark graybounced against the one wall with an excursion to theline] and tumbling motion at the wall
middle of the channel, as shown in Fig. 4(f).
[light gray line]; (f) Bouncing against
the wall with an excursion to the middle
In summary, we investigated the dynamics ofof the channel. This figure is
active deformable particles in an external Poiseuillereproduced from Ref. [3].
flow. First, we clarified the relation of our model tothat of rigid active particles. Then, we studied the
dynamical modes that active deformable particles
exhibit by changing the strength of the external flow. We emphasized the difference between
the active particles that tend to self-propel parallel to the elliptical shape deformation andthose self-propelling perpendicularly. In particular, we found that the parallel particles
exhibit the swinging motion, whereas the perpendicular particles show a straight motion
along the stream line.
References:[1] M. Tarama, A. M. Menzel, B ten Hagen, R. Wittkowski, T. Ohta, and H. Löwen, J. Chem. Phys. 139
104906 (2013). [2] A. Zöttl and H. Stark, Phys. Rev. Lett. 108 218104 (2012); Eur. Phys. J. E 36 4 (2013).
[3] M. Tarama (under review). [4] T. Ohta and T. Ohkuma, Phys. Rev. Lett. 102, 154101 (2009).

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Ⅳ 研究業績 (2016)

2. Original papers(1) Mitsusuke Tarama and Takao Ohta
“Reciprocating motion of active deformable particles”
Europhys. Lett. 114, 30002 (2016).
3. Presentation at academic conferences(1) Mitsusuke Tarama, and Takao Ohta,“Appearance of reciprocating motion of active deformable particles”
Synergy of Fluctuation and Structure: Quest for Universal Laws in Non-Equilibrium
Systems: The third research area meeting, Kyushu University, Japan, 18 Jun., 2016 (poster).
(2) Mitsusuke Tarama, and Takao Ohta,“Reciprocating motion of active deformable particles in homogeneous media”
Statphys26, the Palais des Congrès de Lyon, Lyon, France, 18-22 Jul., 2016 (poster).
(3) Mitsusuke Tarama, and Takao Ohta,“Back-and-forth motion of active soft particle”
The 4th International Soft Matter Conference, the centre Alpes-Congrès at Alpexpo,
Grenoble, France, 15 Sep., 2016 (poster).
(4) Mitsusuke Tarama, and Takao Ohta
“Back-and-forth motion of active deformable particles”
Microswimmers – From Single Particle Motion to Collective Behaviour, theForschungszentrum caesar, Bonn, Germany, 6 Oct., 2016 (poster).
(5) Mitsusuke Tarama and Takao Ohta
“Reciprocating motion of active deformable particles”
Patterns in Nature Functions, Variations and Control, University of Bayreuth, Bayreuth,
Germany, 10 Oct., 2016 (poster).
(6) Mitsusuke Tarama,“Dynamics of active deformable particles: from swimming droplets to crawling cells”
Structured Soft Interfaces: Caught Between Multi-Scale Simulation and Application ,Lorentz Center, Leiden University, the Netherlands, 23 Jan., 2017 (poster).
(7) 多羅間充輔,“ポアズイユ流中での変形するアクティブマターのダイナミクス”
日本物理学会第 72 回年次大会, 大阪大学 豊中キャンパス, 17 Mar., 2017 (oral).
4. Others(1) Mitsusuke Tarama“アクティブマターの非線形ダイナミクス”
郡研セミナー, 御茶ノ水女子大学, 12 Apr., 2016.

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Masato Itami
FIFC Fellow
1. Summary of the research of the year
Universal Form of Stochastic Evolution for Slow Variables in Equilibrium Systems
The main purpose of the present work is to re-derive nonlinear, multiplicative Langevin equations for acomplete set of slow variables in equilibrium systems with particular emphasis of the separation of timescales and a universal asymptotic form of the probability density for time-averaged fluxes. We first assume acomplete set of slow variables. Let τmacro be the shortest time scale of the slow variables and τmicro be thelargest time scale of the other dynamical variables. Then, from the separation of time scales τmicro << τmacro we
can find Δt such that τmicro << Δt << τmacro. This Δt plays two crucial roles in the derivation of the equation forslow variables. First, because τmicro << Δt, we can consider the central limit theorem for the time averaged
flux as a universal form of the asymptotic behavior of the transition probability of the slow variables during atime interval Δt. The time reversibility in microscopic Hamiltonian systems provides a restriction on thetransition probability. Second, because Δt << τmacro, this universal form of the transition probability leads tothe path integral form of a stochastic system. This stochastic system is nothing but the nonlinear,
multiplicative Langevin equations. This concept is quite natural and general. Indeed, one can interpret thearguments of Onsager and Green through this concept. Nevertheless, as far as we know, there is no explicit
presentation of the derivation of the nonlinear, multiplicative Langevin equations with the universal
asymptotic form of the probability density for time-averaged fluxes and the path integral formulation underτmicro << Δt << τmacro. We thus expect that this result will be instructive for understanding the universal form,
and will also be useful for deriving the equation for slow variables even in systems out of equilibrium.
Here, we point out the difference between our and previous approaches. Our final goal is to establish afirm connection between a Langevin equation and a microscopic mechanical system. The previous studies
using a projection operator method or a nonequilibrium statistical operator method have the same motivationas ours. Their methods use some physical approximation (such as a markovian approximation) just before
obtaining a Langevin equation. The validity of the approximation depends on observation time scales anddetails of a system, and their formulation is based on only an identity, which is useful but far from a physicalprinciple. Thus, their assumptions are out of scope of the theories. Then, we aim to achieve our goal withphysical principles. From this motivation, we use the central limit theorem with the separation of time scales
for connecting a microscopic mechanical and mesoscopic stochastic description in a mathematically andphysically clear way. This work also differs from another type of derivation of the Langevin equation on thebasis of arguments within stochastic processes. Their derivation is self-contained and elegant, but arguments
relating to microscopic descriptions are out of scope of their theory. As a technical remark, we note that theyused the Kolmogorov forward and backward equations for restricting the form of the Langevin equation by
imposing a detailed balance condition, while we directly use the transition probabilities. Although we do not－ 95 －

Ⅳ 研究業績 (2016)

completely achieve our aim, we believe that it is important to show the outline of our approach even without
a rigorous proof. Our approach is not simply another derivation of known results, but provides a new
direction of future studies.

Setup and basic concept
We consider fluctuations of a system in equilibrium. There is a special set of variables whose timescales are well separated from those of the other dynamical degrees of freedom. We refer to such a set as acomplete set of slow variables and denote it by � � ��� � � � � � � � � �. For simplicity, we assume that the

Hamiltonian of the microscopic mechanical system is symmetric with respect to the time-reversal operation.

For such a system, the probability density of � is denoted by ��� ��� � exp��������, where � is thenormalization constant, and ���∗ � � ���� for the time reversal �∗ of �. The physical interpretation of �

depends on the system being studied. For example, ���� corresponds to entropy when thermodynamic
fluctuations in an isolated system are considered. For other cases, ���� should be read from the form of thestationary distribution. Suppose that the system is in equilibrium. We then expect that the time evolution of� can be described by a Langevin equation.

On the basis of a microscopic mechanical description, we can define the conditional probability densityof � � �� at time �, denoted by �� ��� |�� �, provided that � � �� at time 0. There are two important

properties of this probability density. First, following the central limit theorem, we assume the Gaussian formof form of the probability density for the time averaged flux written as ���� � �����. The result is given by��� � ��
����� � ������ ��� |�� � �
exp �� ����� ��� ��� � �� �� ��� �� � �� �� ��� ���� �1�4������4����� �e� ���� �1���

where �� is the most probable value of the time averaged flux, and ���� is the dispersion matrix. We
assume that the matrix � � ���� � is positive definite. Second, from the reversibility of microscopic
Hamiltonian systems, we can obtain��� ��� |�� ���� ��� � � ��� ��∗� |�∗� ���� ��� �.

(2)Then, by substituting (1) into (2), we obtain a possible form of �� ��� and a symmetry property of �. For
convenience, we denote �∗ by �� � �� � �� � � � � � � � � � � � � � , where � � � �1 �� � 1 for � � . We

� ���
� ���
� ���
decompose �� ��� into two parts, �� ��� � ����� ����
with ����
� [ �� ��� � � � �� ��∗ ���� and� ���� ��∗ �� ���.
� ��∗ �� ��������[�� ��� � � � �� ��∗ ����, which satisfy ����� �� � ����and ����� � � ����We also����define the matrix �� � ��� � by �� ��� � � � � � ��� ��∗ �. Note that �e� �� ��� � �e� ���∗ �.

Results

Direct substitution of (1) into (2) would result in a complicated form, so we use a trick. Using therelations between different discretization schemes in a path integral formulation as first derived by Wissel,
we can rewrite (1) in terms of �� � ��� � �� ��� as－ 96 －

Ⅳ 研究業績 (2016)��� ��� |�� � �1

��4����� ��� ���� �� ��� ��� �� �with��� ����� � ��
����� � �������� ��� ��� � �� ��� ��� �� � �
4
��
��
�,�

� �� �� �� �
������������� ��� �
��
�����
�
�
�
�
�
�
��
�
�
�
�
�
2
4
2
���
���
���
���
�

�

�,�

� ���
� ���
��� ��� � ����� ����
���

Substituting this into (2) with ��� ��� � �����������, we obtain����� ���.
����� � ��
����� � ���0 � ����� ��� ��� � �� ��� ��� �� � �� ��� ��� ��
4
��
��
�,�

�

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

�,�

��
�
��� ���� �1��� � ��� ����� ����� �� �
��
��
� �
��
, ���
� �� �� � ��� � log������ �� ��� �
4
��
2
���
���
���
�,�

� ���
� ���
� ����
�∑where ���� ��� � ���������� ���� �� ��� � ���� ����� �, and we have used ���� � � ���� � � �� ∑� �

��

�

�
���

�

� ����� � ��� � �. Note that the � ����� � ��� � � terms in (3) are irrelevant in the limit ��������� → 0.

�Because (3) holds for any ��� � ��� and ��, comparing the quadratic terms in ��� � ��� in (3) yields����� ��� � �� ���. Comparing the first terms in ��� � ��� in (3), we also have���� ���
�����
� ���
�� ���
��
,
� ��
����
���
���
�

�

which is called the fluctuation dissipation relation of the second kind. Comparing the zero-order terms in��� � ��� in (3), we finally obtain ∑�

�

�� �

� ���� ����.
�����
��

Now we go back to (1). This is interpreted as the transition probability for the discrete time Langevinequation. By taking the limit ��������� → 0, we obtain���� ���
�����
�� �
� ���
� ������� � � �� ��� ∙ � � ,� � ��� ���
���
���
��
�

�

�

�

where � �� ��� satisfies ��� ��� � ∑� � �� ���� �� ��� , � � is the zero-mean Gaussian white noise with
�

covariance 〈� � ���� � ���〉 � � �� ��� � ��, and ∙ denotes multiplication with the Ito rule. The form of thisequation is universal and equivalent to that obtained by Green.

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Ⅳ 研究業績 (2016)

2. Original papers(1) Masato Itami and Shin-ichi Sasa,“Universal Form of Stochastic Evolution for Slow Variables in Equilibrium Systems”
J. Stat. Phys. 167(1), 46–63 (2017).
3. Presentation at academic conferences(1) Masato Itami and Shin-ichi Sasa
“Derivation of Stokes’ law without the hydrodynamic equations”
STATPHYS26, Lyon, France, July 18-22, 2016 (poster).
(2) 伊丹將人、佐々真一「平衡系における遅い変数の発展方程式の微視的導出」
日本物理学会第72回年次大会、大阪大学、2017年3月17-20日（口頭）4. Others(1) Masato Itami and Shin-ichi Sasa
“Universal Form of Stochastic Evolution for Slow Variables in Equilibrium Systems”
The 14th symposium of Fukui Institute for Fundamental Chemistry, Kyoto, Jan. 27, 2017
(poster).

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Ⅳ 研究業績 (2016)

Shunsuke Yabunaka
FIFC
Fellow
FIFC Fellow
1. Summary of the research of the year
Dynamics of electric double layers in the presence of selective solvation effects
Structure formation due to ions plays an important role in dynamics of biomaterials, such as proteins, andsoft materials such as colloidal suspensions. There have been many theoretical studies on this topic
without taking into account ion-solvent interactions and physical significance of ion-solvent interaction
remains still elusive.
In liquid water, small metallic ions are surrounded by several water molecules to form a hydration shell
due to the ion-dipole interaction. As a result, such ions are strongly hydrophilic. On the other hand, someions are strongly hydrophobic. As an example, tetraphenylborate BPh4- with an 0.9nm has four phenyl
rings and, due to its large size, it deforms hydrogen bonding, leading to strong hydrophobicity.

Fig. 1 Calculated profiles of ions (left),composition of polar component (middle)
and electric potential (right) around themetallic

wall

with

positive

(top)

and

negative (bottom) surface charge.

I considered a mixture solvent (water-oil) with hydrophilic and hydrophobic ions near a charged metal
wall in collaboration with Prof. Onuki (Kyoto University) (A. Onuki, S. Yabunaka, T. Araki and R.
Okamoto, Current Opinion in Collioid Interface Science (2016)). Assuming that the system is uniform
parallel to the wall, it reduces to a one-dimensional problem. I calculated equilibrium profiles of ion
concentrations and composition as shown in Fig.1.
After completing this paper, we found that the surface voltage generally behaves as a nonmonotonous
function of the surface charge due to the inversion of the electric double layer near the wall. This behavior
indicates thermodynamic instability of laterally uniform one-dimensional solution. The simplest possible
situation is illustrated in Fig. 1. We actually calculated 2 dimensional coexistence profile of two kinds ofelectric double layers (S. Yabunaka and A. Onuki submitted).

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Ⅳ 研究業績 (2016)

Fig.

2

Schematic

representationofcoexistence of two kinds of electric double
layer containing small hydrophobic cations(Na+) and large hydrophobic anions (BPh4-)
in an aqueous mixture on a metal wall.

Collective motion of fluid droplets under chemical reaction
Recently, collective motion of self-propelled particles has attracted much attention because such system may
describe some universal features in collective motion of several biological systems, such as herd of animals,
fish school etc. However, in theoretical studies, the self-propulsion and the interaction between droplets are
introduced phenomenologically without deriving them from hydrodynamic equations.
As a first step toward understanding of collective motion, in collaboration with Dr. Yoshinaga, I
theoretically derived the interaction between two self-propelling droplets (S. Yabunaka and N.
Yoshinaga, Journal of Fluid Mechanics (2016)). As shown in Fig. 3, there are two contributions: (1)the hydrodynamic interaction due to the flow field and (2) the concentration-mediated interaction
due to the overlap between the cloud-like profiles of the third component.

Fig. 3 Schematic explanations of thehydrodynamic interaction (Left) and theconcentration-mediatedinteraction(Right)Continuum theory of growing tissues
Cellular tissues are soft viscoelastic materials, similar to conventional soft materials.
However there are several striking differences between tissues and conventional soft
materials: (a) Cells generate active contractile forces consuming energy. (b) Cell
motility. (c) Cell polarity. (d) Cell proliferation and death. To investigate properties ofsuch active materials is of paramount importance not only for fundamental science but
also for medical applications such as controlling organ formation in vitro, woundhealing and cure for cancer etc.
However, there had been no continuum theory for tissues that takes the features (a-d)－ 100 －

Ⅳ 研究業績 (2016)

into account. Recently, I constructed hydrodynamic equation describing (a-d) for
tissues in one-dimensional space with Dr. Philippe Marcq (Curie Institute) (S.
Yabunaka and P. Marcq, submitted). We applied the framework of active gel theory,
which has succeeded in describing several biomaterials such as motility assays, totissues. In this paper, we calculated tissue growth speed by taking into account a
coupling between stress and growth rate and we showed that this coupling can lead tosignificant increase of the front velocity near the stability threshold of the bulk uniform
state. We also examined emergence of mechanical wave, which has been observed inmany experiments (for example X. Serra-Picamal Nature Physics 2012). We found thatmechanical wave appears via Hopf bifurcation above threshold of active parameters.
2. Original papers(1) Akira Onuki, Shunsuke YABUNAKA, Takeaki ARAKI and Ryuichi OKAMOTO,“Structure formation due to antagonistic salts”
Current Opinion in Collioid Interface Science Volume 22, April 2016, Pages 59–64(2) Shunsuke Yabunaka and Natsuhiko Yoshinaga, "Collision between chemically-driven
self-propelled drops”
Journal of Fluid Mechanics, November 2016, Pages 205-233
3. Presentation at academic conferences(1) 藪中俊介、義永那津人,“化学反応で自己推進運動する液滴の衝突”
日本物理学会 2016 年秋季大会 15pBE, Kanazawa, Sep.15, 2016(2) 藪中俊介、Bertrand Delamotte,“O(N)*O(2)模型における多重臨界固定点の非摂動繰り込み群による研究”
日本物理学会2016年秋季大会16aAK, Kanazawa, Sep.16, 2016
4. Others(1) Shunsuke Yabunaka“Self-propelled motion of a droplet under chemical reaction”
Bio/Softmatter Seminar, Tokyo Metropolitan University, July 29, 2016(2) 藪中俊介“増殖を取り入れたアクティブマターの連続体理論”、 京都若手ソフトマター研究会,
Kyoto,Mar. 8, 2016.

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Ⅳ 研究業績 (2016)

Simon
K.K.
SchnyderSimon
SchnyderFIFC
FIFCFellow
FELLOW
1. Summary of the research of the year 2016a) Dynamic heterogeneities and non-Gaussian behavior in two-dimensional randomly
confined colloidal fluids
Slow relaxation phenomena are often linked to the appearance of a diverging lengthscale. While for the arrest of particles in glass-forming fluids the relevance of a divergent
length scale is a highly controversial issue, the existence of such a length scale is obvious if
the slowing down of the relaxation dynamics is associated with an underlying continuous
phase transition, such as, e.g., the critical point of a liquid-gas transition or a percolationtransition.
A paradigm for slow relaxation in combination with a percolation transition is the Lorentz gas where a single tracer particle moves through the free volume provided by an disordered matrix of obstacles. If the density of obstacles is sufficiently high the tracer does not findany percolating path through the system and is thus localized in a finite volume. At the percolation transition of the free volume, where the tracer particle exhibits a localization transition
from a delocalized to a localized state, the tracer particle probes the fractal structure of thefree volume. This is associated with an anomalous diffusion dynamics, as reflected in a sublinear growth of the mean-squared displacement (MSD). Generalizations of the Lorentz model,
for instance with many interacting particles, soft interaction potentials, or correlated matrix
structures, have been investigated in both simulation and theory.

Fig. 1 (a) Schematic of the experiment, a binary system of small and large particles confined between
two glass slides (particle diameters to scale). The large particles support the top slide. The magnetic
field B tunes the effective interaction between the particles. (b) Mean-squared displacement for the fluid particles in a very dilute cell. A dashed line indicating diffusive behavior, δr2(t) ∼ t , is shown as a
guide to the eye. (c) State diagram for the effective area fractions of the fluid (φF ) vs the matrix particles (φM). (d) Snapshot of the system at state point L1P6 in a quadrant of size 214 × 171 µm.

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Ⅳ 研究業績 (2016)

The original classical Lorentz-gas model assumes Newtonian dynamics for the tracer
particle and a hard-sphere potential for its interaction with the obstacles. Here, the “energy
barriers” that the tracer sees when it travels through the arrangement of obstacles are infinitely high. However, in a modified model with soft interactions between the tracer and the
obstacles this is no longer the case and the effective barrier height provided by the obstacles
depends on the energy of the tracer particle. Thus, for a given obstacle configuration, the effective free volume that the tracer can explore is strongly correlated with its energy.
As shown in a series of molecular dynamics (MD) simulations [1], in an ideal gas of tracer particles in a random arrangement of soft obstacles each particle sees a different percolation transition of the free volume according to the kinetic energy that has been assigned initially to each of the tracer particles. As a consequence, quantities like the self-diffusion coefficient, which have to be averaged over all particles, do not show the singular behavior expected
at the localization transition. Instead, all quantities exhibit nonuniversal behavior: the transition is rounded. Only if a special average over tracer particles with the same energy is performed, a sharp transition as in the hard-sphere Lorentz gas is recovered. These results suggest that the rounding of the transition is a generic feature of realistic, soft systems. The heterogeneous structure of the matrix leads to heterogeneous or non-Gaussian dynamics, as exemplified by the anomalous diffusion at the localization transition and other signatures suchas a large non-Gaussian parameter. The non-Gaussian parameter is often used to characterize
dynamical heterogeneities and in the Lorentz model has a weak divergence at the localizationtransition In a soft system, in which each particle sees a different matrix structure according
to its energy, it can be expected that the dynamics are even more heterogeneous. However, theconnection between this rounding of the transition in a soft heterogeneous medium and its
dynamical heterogeneities has not been explored, yet.
Recently, we have presented an experimental realization of a two-dimensional (2D) Lorentz-gas-like system [2], see also Fig. 1. It consists of a binary mixture of superparamagnetic
colloidal particles confined between two glass plates such that the larger colloidal particles areimmobilized and the smaller particles can move through the matrix formed by the larger ones.
In this experiment, the effective size of the particles is varied by exposing the particles to an
external magnetic field that induces magnetic dipoles in the particles, leading to a repulsive
r−3 interaction between them (here r is the distance between two particles). By varying thestrength of the external magnetic field, the effective density of the matrix is changed while thestructure of the matrix remains unaffected. We have demonstrated that the tracer particles,i.e., the smaller particles, exhibit a transition from a delocalized state at low effective matrix
densities to a localized state at high matrix densities [2]. This transition is rounded because
the energy of the Brownian particles is a fluctuating quantity and, due to the soft r−3 interaction with the obstacles, the barriers seen by the tracers are not infinitely high as for hard interactions.
We discuss generic features of the structure and dynamics in heterogeneous media bycomparing the results of colloidal experiments and MD simulations. First, we qualitatively
characterize the tracer dynamics by calculating the single-particle probability distributions
and discuss the structure of the matrix and fluid particles in terms of the partial pair distribution functions. We then show that around the transition from a delocalized to a localized state,
the dynamics of the tracer particles in both simulation and experiment exhibit strong dynamic
heterogeneities that are associated with strong non-Gaussian fluctuations. To this end, we－ 103 －

Ⅳ 研究業績 (2016)provide a detailed analysis of simulationand experiment in terms of the self-part ofthe intermediate scattering function(SISF), Fs(q,t), the mean-quartic displacement (MQD), δr4(t), and the non-Gaussian
parameter (NGP), α2(t), thereby extending
upon our previous work [2]. We find that alarge fraction of particles can already belocalized while the MSD still appears diffusive. While this heterogeneity is typical for
the Lorentz gas, we find it to be enhanced
when the artificial constraint of assigning
the same energy to all particles in the simulation is removed. As a consequence, therounded delocalized-to-localized transitionof the tracer particles is associated with astrong increase of α2(t) on rather small andintermediate time scales, whereas the α2 of
the Lorentz gas indicates only small deviations from Gaussian behavior, see Fig. 2.
This strong increase of α2(t) is found in theexperiment as well.
Fig. 2 Non-Gaussian parameter α2(t) for the experiment (a), and for the simulation in the (b)single-energy and (c) confined-ideal-gas cases.

References[1] S. K. Schnyder, M. Spanner, F. Höfling, T. Franosch, and J. Horbach, Soft Matter 11,
701 (2015).
[2] T. O. E. Skinner, S. K. Schnyder, D. G. A. L. Aarts, J. Horbach, and R. P. A. Dullens,
Phys. Rev. Lett. 111, 128301 (2013).

b) Collective motion of cells crawling on a substrate

Directional collective motion of cells is of fundamental importance for embryogenesis, wound healing
and tumor invasion. Cells move in clusters, strands or sheets to cover empty area, to grow or invade tissues.
How the cells coordinate and control their motion, is the subject of ongoing research. At the level of a single
cell, it is well established that its motion is intricately linked to its shape. The shape of crawling cells is highly variable, depending on the type of cell, the substrate, as well as a result of the migration process itself.
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Ⅳ 研究業績 (2016)

Fig. 3 (a) Schematic of the cell
model. (b) Forces acting on thetwo disks being at distance rbf.

Fig. 4 Snapshots of CIL and noCIL cells for a range of cell
shapes. Cell velocities are given
as arrows and color. Hue indicates deviation from average direction, and slower cells arelighter in color. The cells undergo
a transition from a clustering/disordered state to an ordered state upon change of thecell shape.

When a cell starts moving, its shape breaks symmetry, whereas circular cells typically cannot move. While
there is evidence that shape has a strong influence on scattering and can lead to clustering and collective directed motion of swimmers, less is known about the role of cell shape in organizing collective crawling. It
has been shown in simulations that inelastic collisions between crawling cells, e.g. due to deformation, canlead to coherent migration, suggesting the importance of deformability for collective behavior. When crawling cells come into contact, it inhibits their protrusions, which tends to change their shape and reorient them.
It was shown that this effect, called contact inhibition of locomotion (CIL), enables cells to follow chemical
gradients more effectively by aligning them. In growing colonies, CIL leads to a slowing down of the motility of individual cells when the density of their environment crosses a certain threshold. Thus, CIL is believedto play a crucial role in the control of collective tissue migration, tissue growth, morphogenesis, wound healing and in tumors. So, we built a minimal, mechanical model of cells crawling on a substrate, aiming to isolate behavior purely caused by the interplay of contact inhibition and deformable shape, while neglecting
properties such as cell-cell adhesion or chemotaxis.
By mimicking the mechanical motion of cells crawling on a substrate using a pseudopod, we constructed a minimal model for migrating cells which gives rise to contact inhibition of locomotion (CIL) naturally. The model cell consists of two disks, one in the front (a pseudopod) and the other one in the back (cellbody), connected by a finitely extensible spring, see Fig. 3. Despite the simplicity of the model, the cells’
collective behavior is highly nontrivial, depending on the shape of cells and whether CIL is enabled or not.
Cells with a small front disk (i.e. a narrow pseudopod) form immobile colonies. In contrast, cells with a large
front disk (i.e. such as a lamellipodium) exhibit coherent migration without any explicit alignment mecha－ 105 －Ⅳ 研究業績 (2016)

nism being present in the model, see Fig. 4. This suggests that crawling cells often exhibit broad fronts because it helps them align.

2. Original papers(1) 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).
3. Presentations at academic conferences(1) Simon K. Schnyder, John J. Molina, Ryoichi Yamamoto, “Collective dynamics of
migrating cells”, Workshop, Fukuoka, January 2017.
4. Others(1) Seminar, Simon K. Schnyder, John J. Molina, Ryoichi Yamamoto, “Collective dynamics of migrating cells”, R Lab, Nonlinear Physics Group, University of Nagoya, May
2016.
(2) Talk, Simon K. Schnyder, John J. Molina, Ryoichi Yamamoto, “Collective dynamics
of migrating cells”, Summer School: Active Complex Matter, Cargèse, Corsica Island,
France, July 2016.

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Ⅳ 研究業績 (2016)

Miho Isegawa
FIFC Fellow
1. Summary of the research of the year
Copper-catalyzed Enantioselective Boron Conjugate Addition: DFT and AFIR Studyon Different Selectivities of Cu(I) and Cu(II) Catalysts
We present a mechanistic survey on the LCu-catalyzed (L = chiral 2,2-bipyridine ligand)enantioselective boron conjugate addition reaction, carried out using density functional theory (DFT) and theartificial force induced reaction (AFIR) methods. The computed catalytic cycle for Cu(I)- and Cu(II)-based
catalysts consists of three steps: (a) boron–boron bond cleavage of B2(pin)2, (b) boron conjugate addition on
the -carbon of chalcone, and (c) protonation. The enantioselectivity of the reaction with LCu(I) or LCu(II)catalysts is solely governed at the boron conjugate addition step. The multicomponent (MC)-AFIR searchand the subsequent DFT calculations for the LCu(I) catalyst determined transition states (TSs), which lead toCu(I)-O-enolate and Cu(I)-C-enolate, and both equally contribute to the C–B bond formation with noenantioselectivity. On the other hand, a MC-AFIR search and the subsequent DFT calculations for the
analogous LCu(II) catalyst showed that only the transition state (TS) leading to Cu(II)-O-enolate contributes
to the reaction. Furthermore, the TSs leading to the R- and S-forms of Cu(II)-O-enolates are energeticallywell separated, with the R-form being of lower energy, which is consistent with experimental observations.
Our study provides important mechanistic insights for designing transition metal catalysts for Cu-catalyzed
enantioselective boron conjugate addition reaction.

(a) R-form

tB
u
N

O
H

C
uO
N B
O
O
H
H
tB
u
h
O P
P
h

(b) S-formtBuN

Figure

R (Cu−O) = 2.06
R (Cu−Cα) = 2.58
R (Cu−Cβ) = 2.06
R (B−Cβ) = 2.29

2.

O
H

C
uO
N B
O
O
H
P
h
tB
u
  H
P
h
O

R (Cu−O) = 2.01
R (Cu−Cα) = 3.20
R (Cu−Cβ) = 2.96
R (B−Cβ ) = 2.28

The

energylowesttransition state for each R-form(favorable)(TS1-R-b(II))

and

S-form (unfavorable) (TS10-S-b(II))
Figure 1. Calculated free energy profile forCu(II)-based catalyst. G and H (in parentheses)－ 107 －

in the Cu(II) system. Selected bondlengths are given in Å.

Ⅳ 研究業績 (2016)

Hydride Attack in Dioxygen Activation by a Biomimetic Model for Oxygen-Tolerant [NiFe]
Hydrogenase: A Density Functional Study for the Reaction Mechanism
The mechanism for the dioxygen activation by a biomimetic model complex of O2-tolerant[NiFe]-hydrogenase, [NiLFe(η5-C5Me5)]+ [L=N, N’-diethyl-3,7,-diazabiomimnonate-1,9-dithiolato] wasestablished by using density functional theory (DFT) and artificial force induced reaction (AFIR) method.
Particularly, the AFIR method was
employedbycombining

DFT

O1 O2

O1 O2

structures. Our computational results
suggests that the dioxygen activation is

X-ray

R (Ni−Fe) = 3.05
R (Ni−O1) = 3.30
R (Ni−O2) = 3.22
R (Fe−O1) = 1.89
R (Fe−O2) = 1.89
R (O1−O2) = 1.38

initiated by O2 binding to the electron
Then reduction of O2 coordinatedcomplex occurs in the presence ofstrong acid of BH4–, through hydride
transfer. Once the hydride transfer
occurs, the BH3 immediately attacks on
the electron rich oxygen, giving rise to
BH3OH–. The mechanistic insights of theO2 activation in this study are important inmechanism

of

O1

O2

O2

O1 O2

O1

O1

1C1
side-on

1C2
end-on1C3
end-on3C1side-on

3C2
bridge3C3
end-on∆∆ G = 0.00∆∆ G = 4.27∆∆ G = 5.92∆∆ G = 15.11∆∆ G = 7.46∆∆ G = 5.85

R (Ni−Fe) = 3.28
R (Ni−O1) = 3.64
R (Ni−O2) = 3.64
R (Fe−O1) = 1.88
R (Fe−O2) = 1.88
R (O1−O2) = 1.40

R (Ni−Fe) = 3.22
R (Ni−O1) = 2.87
R (Ni−O2) = 3.40
R (Fe−O1) = 2.74
R (Fe−O2) = 1.74
R (O1−O2) = 1.34

R (Ni−Fe) = 3.28
R (Ni−O1) = 3.22
R (Ni−O2) = 4.48
R (Fe−O1) = 1.80
R (Fe−O2) = 2.78
R (O1−O2) = 1.33

R (Ni−Fe) = 3.10
R (Ni−O1) = 3.44
R (Ni−O2) = 3.45
R (Fe−O1) = 1.88
R (Fe−O2) = 1.88
R (O1−O2) = 1.41

R (Ni−Fe) = 3.04
R (Ni−O1) = 1.99
R (Ni−O2) = 2.83
R (Fe−O1) = 2.71
R (Fe−O2) = 1.75
R (O1−O2) = 1.37

R (Ni−Fe) =3.17
R (Ni−O1) = 3.13
R (Ni−O2) = 3.90
R (Fe−O1) = 1.81
R (Fe−O2) = 2.89
R (O1−O2) = 1.33

ρ (Ni) = 0.00
ρ (Fe) = 0.00
ρ (O1) = 0.00
ρ (O2) = 0.00

ρ (Ni) = –0.02
ρ (Fe) = 0.40
ρ (O1) = –0.20
ρ (O2) = –0.11

ρ (Ni) = 0.01
ρ (Fe) = –0.62
ρ (O1) = 0.31
ρ (O2) = 0.18

ρ (Ni) = 1.36
ρ (Fe) = -0.27
ρ (O1) = –0.01
ρ (O2) = –0.01

ρ (Ni) = 1.43
ρ (Fe) = –0.42
ρ (O1) = 0.31
ρ (O2) = 0.11

ρ (Ni) = 0.00
ρ (Fe) = 1.30
ρ (O1) = 0.41
ρ (O2) = 0.40

O2

O1 O2

rich Fe(II) center in end-on fashion.

the

O2

for

obtaining “approximate” transition stateinterpreting

O1

the

O1

O2

O1

O2

O1

O1 O2

O2

5C1
side-on

5C2
bridge5C3
end-on7C1side-on

7C2
bridge∆∆ G = 18.82∆∆ G = 5.90∆∆ G = 15.21∆∆ G = 27.72∆∆ G = 22.27∆∆ G = 30.58

7C3
bridge’R (Ni−Fe) = 3.37
R (Ni−O1) = 3.34
R (Ni−O2) = 4.19
R (Fe−O1) = 1.83
R (Fe−O2) = 1.97
R (O1−O2) = 1.40

R (Ni−Fe) = 2.89
R (Ni−O1) = 1.99
R (Ni−O2) = 2.79
R (Fe−O1) = 2.73
R (Fe−O2) = 1.81
R (O1−O2) = 1.39

R (Ni−Fe) = 2.84
R (Ni−O1) = 3.32
R (Ni−O2) = 2.38
R (Fe−O1) = 2.56
R (Fe−O2) = 1.86
R (O1−O2) = 1.37

R (Ni−Fe) = 3.27
R (Ni−O1) = 3.91
R (Ni−O2) = 3.83
R (Fe−O1) = 2.11
R (Fe−O2) = 2.11
R (O1−O2) = 1.34

R (Ni−Fe) = 2.92
R (Ni−O1) = 2.00
R (Ni−O2) = 2.86
R (Fe−O1) = 2.73
R (Fe−O2) = 1.91
R (O1−O2) = 1.38

R (Ni−Fe) = 2.83
R (Ni−O1) = 3.16
R (Ni−O2) = 2.12
R (Fe−O1) = 3.28
R (Fe−O2) = 2.12
R (O1−O2) = 1.33

ρ (Ni) = 0.02
ρ (Fe) = 3.04
ρ (O1) = 0.18
ρ (O2) = 0.26

ρ (Ni) = 1.43
ρ (Fe) = 1.49
ρ (O1) = 0.35
ρ (O2) = 0.26

ρ (Ni) = 1.36
ρ (Fe) = 1.73
ρ (O1) = 0.33
ρ (O2) = 0.23

ρ (Ni) = 0.05
ρ (Fe) = 3.73
ρ (O1) = 0.65
ρ (O2) = 0.67

ρ (Ni) = 1.42
ρ (Fe) = 3.10
ρ (O1) = 0.42
ρ (O2) = 0.36

ρ (Ni) = 1.36
ρ (Fe) = 2.94
ρ (O1) = 0.61
ρ (O2) = 0.55

Figure 3. Binding modes of oxygen on [NiFe] core.
Relative free energy ΔΔ G (kcal/mol), bond length, andspin densities are shown. The free energies are given
relative to the most stable orientations 1C1side-on.

O2-tolerant hydrogenase and developing
superior molecular catalyst that combines“self-repairing” function from the oxidized
state to recover the catalytic function.

Figure 4 (a) Free energy profiles for four spinstates (S = 0, 1, 2, and 3) in (i) the first hydride
transfer, (ii) the second hydride transfer, and(iii) BH3OH– removal.
－ 108 －

Figure 5. Summary of catalytic cycle
for O2 activation by [NiFe]-complex.

Ⅳ 研究業績 (2016)

Fe centered H2 Molecule Activation by [NiFe] core: Density Functional Study for theReaction Mechanism
We performed theoretical study for a bio-inspired model of [NiFe] hydrogenase, using density
functional theory (DFT) and artificial force induced reaction (AFIR) methodology. The model system is the first
NiFe molecular catalyst which successfully extracts electrons from hydrogen molecule in addition to the hydride
transfer and hydrogen generation with addition of acid. Our aim in this study is to precisely reveal the reaction
mechanism for the whole catalytic cycle and to corroborate the experimental observations; spin state, oxidation
state, and the function. Our calculated free energy profile for the full catalytic cycle revealed that the NiFe
complex is not significantly stabilized by the H2 binding on the metal center, therefore the simultaneous additionof base with bubbling the H2 is crucial. The generated hydride complex is binding to the Fe, and not binding both
Ni and Fe which has been observed in the Ni-R state of hydrogenase. From the hydride complex, the hydride
transfer process by is low barrier process and the proton transfer process from acid is barrierless process.
Following one-electron oxidation of NiFe hydride complex by ferrocene, the hydrogen atom transfer (HAT)
process or proton coupled electron transfer process (PECT) is favored, and the both proton transfer (PT)/electrontransfer (ET) and ET/PT are less likely. Our study in the hydrogen activation process give the chemical insights
to understand the function and reaction mechanism of hydrogenase and to create more efficient H2 activation
catalyst.

Figure 6. Three pathways from
[NiFe] hydride complex to [NiFe]
core. (1) PECT/HAT following
electrontransfer,(2)

hydridetransfer, and (3) generation of H2
with proton transfer.

Figure 7. Three pathways following
electron transfer; (i) PT  ET (ii)
PCET/HAT and (iii) ET  PT.

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Ⅳ 研究業績 (2016)

2. Presentation at academic conferences(1) Miho Isegawa, W. M. C. Sameera, Akhilesh K. Sharma, Taku Kitanosono, Shū Kobayashi, Keiji
Morokuma “Copper-catalyzed Enantioselective Boron Conjugate Addition: DFT and AFIR Studyon Different Selectivities of Cu(I) and Cu(II) Catalysts”
Japan-France-Spain Joint-Symposium on Theoretical and Computational Science of Complex
Systems, Oct. 26 to 28, 2016, Kyoto(2) Miho Isegawa, W. M. C. Sameera, Akhilesh K. Sharma, Taku Kitanosono, Shū Kobayashi, Keiji
Morokuma “Copper-catalyzed Enantioselective Boron Conjugate Addition: DFT and AFIR Studyon Different Selectivities of Cu(I) and Cu(II) Catalysts” The 10th Annual Meeting of Japan Society
for Molecular Science, Sept. 13 to 15, 2016, Kobe.
(3) Miho Isegawa, W. M. C. Sameera, Akhilesh K. Sharma, Seiji Ogo, Keiji Morokuma, “Hydride
Attack in Dioxygen Activation by a Biomimetic Model for Oxygen-Tolerant [NiFe] Hydrogenase: A
Density Functional Study for the Reaction Mechanism”, FIFC annual meeting, Jan. 27, 2017, Kyoto(4) Miho Isegawa, W. M. C. Sameera, Akhilesh K. Sharma, Taku Kitanosono, Shū Kobayashi, Keiji
Morokuma “Copper-catalyzed Enantioselective Boron Conjugate Addition: DFT and AFIR Studyon Different Selectivities of Cu(I) and Cu(II) Catalysts”, stimuli-responsive chemical species for thecreation of functional molecules, Mar. 6-7, 2017, Hiroshima.

－ 110 －

Ⅳ 研究業績 (2016)

Satoshi Suzuki
Satoshi Suzuki

Research Fellow

1. Summary of the research of the year
1.1 ビスジアルキルアミノアントラセン類における凝集誘起発光(AIE)の起源
9,10-bis(N,N-dialkylamino)anthracene(BDAA) はアルキルアミノ基で置換されたアントラ
あ り 、 そ のシン プル な分子構造にな分子構 造に もかもかかわ らず凝集誘起発光 (aggregation-induced
セ ン で ありかわemission:AIE) を起こす。多くの蛍光分子では凝集により発光性は低下する。AIE は非蛍光性の分子が凝集により蛍光性を持つようになる。一連の BDAA において、大きなストークスシフトが観測され、自己吸収が起こりにくいことが AIE の一因であると実験的に示唆された。
まず、大きなストークスシフトがどのような構造変化によって起こるのかを計算によって確認した。
また、BDAA が溶液中で光りにくい原因は溶液中では内部転換による失活が起こりやすいのではないかという過程のもと、（気相中での）円錐交差を計算した。内部転換は円錐交差周辺で起こりやすく、もし円錐交差がエネルギー的に到達不可能であれば内部転換が起こりにくく、溶液中でも光りやすいと考えられる。さらに、液相と固相での発光性の差を議論するために ONIOM法を用いた円錐交差探索を行った。
ストークスシフトの原因
9,10-bis(N,N-dimethylamino)anthracene(BDAA-methyl)の基底状態での安定構造と励起状態での安定構造を計算した。基底状態ではアミノ基がアントラセンに直交する構造が安定であり、syn 体と anti 体が存在する。励起状態では syn 体 anti 体どちらから構造最適化をスタートしても、一つのアミノ基が平面になる共通の Local Minimum に落ち込むことが示唆された。この構造ではアミノ基はアントラセンに直交している。また、二つのアミノ基が平面になるが、アントラセン部分に対して直交していない構造も励起状態の Local Minimum として存在することがわかった。この二種類の Local Minimum はエネルギー的にはほぼ同程度で、間にあるバリアーも低いため、共存しうる。いずれの Local Minimum からの発光だとしても蛍光波長は実験値を再現するため、これらの構造のいずれかからの起こると考えられる。
気相中での円錐交差
BDAA-methyl の円錐交差を CASSCF/6-31G(d)レベルで計算した。この系では芳香環の大きな歪みを含む円錐交差が存在し、そのエネルギーはフランクコンドン状態に比べて 50ｋJ/mol 程度
安定である。つまり、フランクコンドン状態からエネルギー的には MECI へは到達であり、それがこの分子が内部転換しやすいことを示唆している。一方で、芳香環の折れ曲がりがあることから
このような構造は凝集時には周辺からの立体制約を強く受けると予想される。円錐交差が立体制約を受けることで凝集時に内部転換しづらくなり結果的に発光しやすくなるものと考えられる。

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Ⅳ 研究業績 (2016)

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

BDAA-piperidyl の気相中での円錐交差構造－ 112 －

Ⅳ 研究業績 (2016)

一方、変位の比較的小さい、アントラセン部分の面外変角による円錐交差も存在するが、こちらは気相中でも固相中でもエネルギーが高く内部転換には関わらないと考えられる。以上のこと
からこの分子における固相での発光しやすさについて、定性的には説明ができた。
1.2 ビスジアルキルアミノアレーン類における凝集誘起発光(AIE)の起源
ピレン骨格の特定の位置にアルキルアミノ基を導入した分子 1 は AIE 特性を示すのに対し、2は溶液中でも発光し AIE 特性を持たないことが実験グループにより明らかにされた。このことか
ら、適当な芳香族炭化水素の適当な位置をアルキルアミノ基で置換すれば AIE 特性を示すのではないかと予想される。そこで、モデル化合物としてアルキルアミノ基で二置換されたベンゼ
ン、ナフタレン(1a,1b と呼ぶ)と、アルキルアミノ基とメチル基を持つベンゼン、ナフタレン(2a,2b と呼ぶ)を考え、失活過程を議論する。モデル化合物の失活過程から重要な反応座標がわかれば一般の芳香族化合物への応用は容易に可能であると期待できる。

1

2

1a

2a

1a,2a の MECI を(10e,8o)CASSCF/6-31G で最適化した。得られた MECI と S1 フランクコンドン
状態の間に遷移状態があることが示唆されたので、S1 面上での極小点と遷移状態の探索を
TD-B3LYP/6-31G(d) レ ベ ル で 行 っ た 。 CASSCF の 計 算 は GAMESS, TDDFT 計 算 はGaussian16 を用いて行った。1a,2a の PES は似通っており、どちらもフランクコンドン状態からア
ルキルアミノ基に置換された炭素位置における ring-puckering mode に沿って MECI に到達するということがわかった。図 1 に 1a,1b,2a,2b の基底状態の安定構造を 0kJ/mol とした、S1 状態のポテンシャル面を示す。違いとして、2a の場合に比べて 1a の方が遷移状態が低い。このことから 1a の方が 2a よりも溶液中で失活しやすく光りにくいと考えられる。これは変位するアルキルア
ミノ基の隣のもう一つのアルキルアミノ基が遷移状態を安定化しているからだとわかった。同様に 1b と 2b の比較からも 1b の方が光りにくいと考えられる。実際の分子 1,2 において 2 が発光性であり 1 は溶液中では非発光性である理由はモデル分子からの演繹で概ね説明できることがわかった。

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Ⅳ 研究業績 (2016)

図 1 1a,1b,2a,2b の S1 状態ポテンシャルエネルギー面

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
3. Presentation at academic conferences(1) ビスアルキルアミノアントラセンの凝集誘起発光◯鈴木聡 諸熊奎治 理論化学討論会 2016 東京

4. Others－ 114 －

Ⅳ 研究業績 (2016)

Akhilesh Kumar Sharma

Akhilesh
Kumar
SharmaPostdoctoral
Fellow
Postdoctoral Fellow
1. Summary of the Research of FY2016
Transition metals are being used in homogenous catalysis for variety cross-coupling reactions andformation of asymmetric compounds. The most popular coupling reactions are Pd-catalyzed, as evident
from the 2010 noble prize in Chemistry for developing these reactions. The efforts for development of
new methods involving non-toxic and readily available metals for coupling reactions are increasing
nowadays. The Fe can be very important in this regard, as it is non-toxic, readily available and is known
to catalyze many enzymatic processes. The mechanistic understanding of Fe–catalyzed reactions isimportant for further development in this field. M. Nakamura and coworkers have been developing
variety of Fe-phosphine catalyzed coupling reaction. The mechanism of these reactions is not establishedand there is no clear understanding on the origin of enantioselectivity. We have studied the mechanism ofreactions using DFT methods. The AFIR method as implemented in GRRM program is used to explore
potential energy surface of the important steps in the reaction.

Computational Insights on the Origin of Enantioselectivity in Fe-Catalyzed Cross-Coupling
Reaction

In current study we have studied the mechanism of chiral Fe-Phosphine catalyzed cross-coupling
reaction (Scheme 1). The favorable mechanism involves first formation C-Cl activation by Fe(I) species(1X), followed by transmetalation. The Fe(II) species (2PX) then undergo Fe(III) formation by coordinationof radical (S2) to Fe-center. The resultant species (4PXR) undergo reductive elimination leading to theformation of coupling product.

(a)(b)
Scheme 1. (a) Fe-catalyzed enantioselective cross-coupling reaction. (b) The lowest energy pathway basedon computational results.
Among different steps, the formation of 4PXR or C–C coupling can be stereoselectivity
determining. We have studied these two steps systematically through Multi Component Artificial Force
Induced Reaction (MC-AFIR) method. More than 50 distinct TSs were optimized for these two steps.
These two steps occurs in quartet spin state, with Fe quintet for Fe(II) and quartet in Fe(III) spin state.
The radical coordination to Fe-center is not enantioselectivity determining, as the activation free energy
barrier for lowest diastereomeric TSs is very small (0.3 kcal/mol). The C–C bond formation isstereoselectivity determining. In the lower energy TSs methyl and bulky phenyl groups of substrate areaway from phosphine and chloride ligand. Further carbonyl group of substrate interacts with C–Hhydrogens of phosphine ligands (Figure 1). Such interaction are absent in higher energy TSs.

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Ⅳ 研究業績 (2016)

The computed enantiomeric ratio determined by Boltzmann distribution of TSs is 92:8, which isin good agreement with experimentally reported ratio (90:10). The lowest energy diastereomeric TSs
differ by 1.5 kcal/mol free energy (Figure 1). From EDA (energy decomposition analysis) it is clear that
the TS2 is higher in energy due to more distortion in Fe-Phosphine-Phenyl fragment, which occur due tobulky tert-butyl fragment. Our study will be helpful in further development of asymmetric Fe-catalysts.

Figure 1. Optimized geometries of lowest energy TSs leading to S and R forms of the products.

Computational Insights on Mechanism of Iron-SciOPP-Catalyzed Alkyl–Aryl Coupling
Reaction

Fe-bisphosphine, -amine and -NHC complexes have been used extensively for cross-coupling reactions.
To gain mechanistic insight we have studied Fe-SciOPP-Catalyzed Kumada-Tamao-Corriu coupling
between alkyl-halides and aryl Grignard reagents trough DFT methods. In this study the mechanism ofcross-coupling-product and byproduct formation is explored.

(a)

(b)
Figure 2. (a) Fe(SciOPP) catalyzed coupling reaction. (b) Free energy profile for mechanism of cross-couplingproduct formation from Fe(SciOPP)Ph2.

We found that Fe(II) species (Fe(SciOPP)Ph2) helps in C–Cl activation at the start of the reaction. It will be－ 116 －

Ⅳ 研究業績 (2016)

followed by generation of Fe(I) species (41Br) by reductive elimination from 43PhPhBr (Figure 2).
Afterwards, C–Cl activation will occur by Fe(I) species, as activation barrier through it is only 4 kcal/mol.
The reaction of alkyl radical to Fe(II) species (52PhPh) is more favorable. The C–C coupling occurs
through Fe(III) intermediate (3PhPhR) (Figure 2). Formation of alkene involves hydrogen abstraction by
Fe(II) species, followed by benzene formation. Similar mechanism has been found for Fe(SciOPP)PhBr.
The calculation for exploring missing stationary points is in progress and manuscript is in preparation.
Computational Insights on Mechanism of Iron-Catalyzed Enantioselective Carbometalation of
Azabycyclic Alkenes
Recently Prof. Nakamura and group have explored carbometalation of azabycyclic alkenes. We
have studied mechanism of carbometalation step through DFT methods. First we have studied thedifferent spin states of Fe(II) species, which is proposed to be the active species in this reaction. We foundthat Fe(II) with tetrahedral geometry is the ground state and the triplet Fe(II) species (with square-planar
geometry) is higher in energy by 2.5 kcal/mol. THF coordination slightly lower the energy of quintet
Fe(II) complex (-1.5 kcal/mol).

The azabycyclic alkenes coordinates weakly to Fe(II) in quintet spin state (Figure 3). We foundthat the carbometalation occurs in triplet spin state. Hence, this step involves two state reactivity, as bothI2 and I3 have quintet as ground state and TS have triplet spin state. For the enantioselectivity study, weare exploring different conformations of TS2 through MC-AFIR method in quintet and triplet spin state.
Till now >12 distinct TSs are optimized each for triplet and quintet spin state. Further sampling of TSs isin progress and manuscript is in preparation.

Figure 3. Free energy profile for Fe-catalyzed carbometalation and two important stationary points in thereaction.

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Ⅳ 研究業績 (2016)

2. Original papers(1) Ming-Chung Yang, Akhilesh K. Sharma, W. M. C. Sameera, Keiji Morokuma, and Ming-Der Su“Theoretical Study of Addition Reactions of L4M(M = Rh, Ir) and L2M(M = Pd, Pt) to
Li+@C60”
J. Phys. Chem. A 121(13), 2665-2673 (2017).
(2) 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. DOI: 10.1021/acscatal.7b01152.
(3) 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 Enantiose-lectivity in Iron-Catalyzed
Cross-Coupling Reactions”(Submitted)

3. Review Article(1) W. M. C. Sameera, Akhilesh K. Sharma, Satoshi Maeda, Keiji Morokuma“Artificial Force Induced Reaction Method for Systematic Determination of Complex Reaction
Mechanisms”
Chemical Record, 16 (5), 2349-2363 (2016).

4. Presentation at academic conferences(1) Akhilesh kumar Sharma, W. M. C. Sameera, Masaharu Nakamura, Keiji Morokuma“Computational insights on the mechanism and the origin of enantioselectivity in Fe-catalyzed
cross-coupling reaction”
The 10th Annual Meeting of Japan Society for Molecular Science, Sept. 13-15, 2016.
(2) Akhilesh K. Sharma, W. M. C. Sameera, Masaharu Nakamura, Keiji Morokuma“Computational Insights on the Mechanism and the Origin of Enantioselectivity in Fe-catalyzed
Cross-Coupling Reaction”
Japan-France-Spain Joint-Symposium on Theoretical and Computational Science of Complex
Systems, Kyoto, Oct. 26-28, 2016.

5. Others(1) Akhilesh K. Sharma, W. M. C. Sameera, Masaharu Nakamura, Keiji Morokuma“Computational Insights on Iron-Catalyzed enantioselective Carbometalation of Azabycyclic
Alkenes”
The 14th symposium of Fukui Institute for Fundamental Chemistry, Kyoto, Jan. 27, 2017.

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Maneeporn Puripat
Research Fellow
1. Summary of the research of the year
Theoretical Investigation of Catalytic Hydrocarboxylation of Olefins with CO2
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, themechanical understanding is indispensable. One of the effective catalytic systems is thehydrocarboxylation of olefin with CO2 catalyzed by the Rhodium complex.[1] (See Scheme 1)
Though the reaction mechanism was partly investigated by the experimental measurements, there
are still remaining questions.
Rh 2Cl2(CO)4 , PPh3
H2

CO2

MeI, acidic additivein AcOH, 180°C, 16h

OOH

Scheme 1 Catalytic Hydrocarboxylation of Olefins with CO2
To understand the catalytic reaction mechanism, one of the methods in the Global Reaction
Route Mapping (GRRM) strategy, called the artificial force induced reaction (AFIR) method,[2]was employed to search systematically all possible pathways for the reaction of catalytichydrocarboxylation of cyclohexene with CO2.
Herein, the mechanism of the Rh complex-catalyzed Hydrocarboxylation will be studied
systematically using the AFIR method. A preliminary search for the Wilkinson catalyst showed thatit required the high barrier; we did not pursue this approach further.
In this research, we looked for all possible pathways including the oxidative addition,
carbonylation step, reductive elimination, and final transformation step into Cyclohexanecarboxylic
acid (CA). The Rh complexes with different coordination number of the phosphine ligand are used
to model the catalysts of this reaction. These complexes is used to interact with the simple starting
reagents; olefin, H2, and CO2, leading to the CA as the final product. The detailed multi-component(MC)-AFIR calculation is as follows. Firstly, approximate local minimums (LMs) and transition
states (TSs) between each catalyst and a hydrogen molecule were explored by the MC-AFIR
method. The AFIR functions were minimized with γ = 300 KJ mol-1. At this stage,
M06-L/Def2SVP/Def2SVP level of theory was used to speed up the calculation. We found that
M06-L reproduced the results of hybrid functional since all of them provided the same trend. In all
calculations, the solvation Gibbs free energy was included by the polarized continuum model(PCM). For the initial AFIR search with M06-L/Def2SVP/Def2SVP, a PCM model using the－ 119 －

Ⅳ 研究業績 (2016)

dielectric constant of 6.3 for acetic acid was employed. Then, all the approximate LMs and TSs
obtained by the initial MC-AFIR search were re-optimized without artificial force at theB3LYP-D3/SDD (Rh & I); 6-31g(d) (for other atoms) level using the same PCM model. We reportin the results section the Gibbs free energy at (453.15 K, 69.085 atm), and the electronic energy
with zero-point correction (ZPE, in parentheses). After optimization of a TS, the intrinsic reaction
coordinate (IRC) was calculated to confirm the reaction pathway. All these AFIR search,
optimizations and IRC calculations were performed with the Global Reaction Route Mapping(GRRM) program using energies, first, and second energy derivatives computed with theGaussian09 program.
The reaction was determined into two cycles separately as shown in Figure 1: Cycle B starts
the reaction with the oxidative addition of H2 and Rh complex, and Cycle A with the oxidative
addition of Iodocyclohexane (CI) and Rh complex. In each cycle, we followed the oxidative
addition, carbonylation step, reductive elimination, dehydration step, and final transformation step
into Cyclohexanecarboxylic acid (CA). It is important to emphasize that for Rh complex, we
considered the types of ligands coordinated to Rh atom carefully to examine their effect.

OC
H2

STEP I
OC
H

Rh
H

Rh

PPh 3
Cl

STEP IV
H 3O +
O
H C
H
O

CO2

OC

H 2O

Rh

I

CO

OC

Cl

I

Rh

[MePPh3+---I-]Cl

STEP II
OC

PPh3
Cl

CYCLE B

Rh
O
H C
H
O

CO2
STEP II
RDS
OC
31.9 kcal mol-1 O
C O
H

STEP III
Rh
H

PPh3

PPh3

OC

Cl

I

Rh
O

MeI

OC
Cl

I

CYCLE A

Rh

PPh3
Cl

STEP I[MePPh3+---I-]
MeI

Cl

OC
I

Rh
O

PPh 3
Cl

STEP III

OC

Rh

PPh 3
Cl

O
OH

I
MeOH

HI
MeI+H 2 O

Figure 1 Catalytic Hydrocarboxylation of Olefins with CO2

In Cycle B, firstly, the reaction pathways of the oxidative addition of H2 to the Rh
complexes were examined and it was found that the coordination number of the phosphine ligand
affects the reaction barriers. The most favorable pathway starts from the dissociation one of thephosphine ligands of the Rh catalyst, followed by the oxidative addition of H2, and the formation of
the formic acid. The decomposition of the formic acid can provide CO and H2O, which will beutilized with olefin in Cycle A to form carboxylic acid.
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In Cycle A, we purposed that the cyclohexyl iodide was simply formed from the coupling
among I- and cyclohexene. In this step, the cyclohexyl iodide and MeOH will be formed. In thiscycle, the reaction started with the oxidative addition between the cyclohexyl iodide and the Rh
complex. This was consistent with the experimental result that carboxylic acid will be formed after
the cyclohexyl iodide existence. Then, the PPh3 ligand was removed due to steric effect. This will
provide the vacant site for CO to adduct. Then, the carbonylation step took place. After that, thePPh3 ligand interacts to the Rh complex again to stabilize the intermediate. At this stage, the watermolecule directly activated to the cyclohexanecarbonyl ligand to form the carboxylic acid and HI.
In this case, HI will be consumed with MeOH to give MeI and H2O.
From calculation, the active species was found to be the monomeric Rh complex. Thisconsistent with the single-crystal X-ray diffraction, which the monomeric complex and MePPh3+
were detected. The task of MeI and PPh3 help to stabilize the intermediates and transition statesalong the reaction. The purposed mechanism is consistent with the result of NMR spectroscopy,
which observed that the carbonyl group of the carboxylic acid functionality was caused by CO,
while the –OH group was resulted from water molecule. The rate-determining step (RDS) of theprocess is the carbonylation step (step II) in Cycle B, whose reaction barrier is 31.9 kcal mol-1.
References[1] Ostapowicz, T. G.; Schmitz, M.; Krystof, M.; Klankermayer, J.; Leitner, W., Angew. Chemie Int. Ed. 52 (2013) page 12119–12123.
[2] Maeda, S.; Ohno, K.; Morokuma, K., Phys. Chem. Chem. Phys. 15 (2013) page 3683-3701.

2. Original papers(1) 3. Presentation at academic conferences(1) Maneeporn Puripat, Miho Hatanaka, and Keiji Morokuma, “Theoretical Investigation of
Catalytic Hydrocarboxylation of Olefins with CO2” Second Circular of Computational
Sciences and Workshop 2017 (CSW2017), Kanagawa, March 6-8, 2017(2) Maneeporn Puripat, Romain Ramozzi, Miho Hatanaka, Waraporn Parasuk, Vudhichai
Parasuk, and Keiji Morokuma, “The Biginelli reaction is a urea-catalyzed organocatalytic
multicomponent reaction” The 14th symposium of Fukui Institute for Fundamental
Chemistry, Kyoto, Jan. 27, 2017.

4. Others(1) － 121 －Ⅳ 研究業績 (2016)

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
今年度は金(I)-イソシアニド錯体によって構成される多型結晶の相対安定性および吸収・発光スペクトルの研究を行った。
【序】 金(I)-イソシアニド錯体は複数の単結晶構造を持ち、熱や光照射でなく機械的刺激によって相転移を起こし、各々の単結晶構造で異なる発光色を示す事から分子科学的にも、また材料化学的にも興味深い系である。 phenyl(phenyl-isocyanide) Gold(I)錯体 1 は、溶媒中から高速で結晶化させると単結晶構造 1b が、ゆっくり結晶化させると単結晶構造 1y が生成する事が実験的に報告されている（Scheme 1）1。1b では最小単位格子が２個の分子から構成されているのに対して、1y では１６個の分子（Scheme 1b において c 軸方向に更に３層が方向性を各々90 度変えて存在する。）から構成されている。特に 1b では PhNC 基と Ph
基の平面角が 70 度ほど捻じれた単量体から構成されるのに対し、1y では PhNC 基と Ph基がほぼ並行な単量体から構成されている。また 1b では隣り合う分子間の Au-Au 距離は
4.7～5.7Å と長く、PhNC 基と Ph 基は CH-相互作用しているのに対し、1y では隣り合う分
子間の Au-Au 距離は 3.2～3.7Å と短く、PhNC 基と Ph 基の CH-相互作用に加えて、PhNC
基の-相互作用も存在している。
吸収・発光スペクトルのピーク位置は、これらの単結晶構造の間で大きく異なり、吸収スペクトルにおいて 1y は 1b より
も 1.0 eV、発光スペクトルにおいて
1y は 1b よりも 0.3 eV 以上低エネル
ギー側へのシフトが観測されている 1。本研究では、QM/MM 法で結晶効果を考慮し、気相、溶液、結晶中での比較・検討を行い、この原因
Scheme 1: 金(I)-イソシアニド錯体の構造の究明を試みた。
【方法】構造最適化には B3LYP-D3 汎関数による DFT 法を用い、吸収エネルギーは B3LYP
汎関数による TDDFT 法で求め、発光エネルギーは B3LYP-D3 汎関数を用いた３重項-１重項のエネルギー差で求めた。Au の原子価電子には(2111111/411/2111/1)基底を用い、内殻電子は Stuttgart グループの ECP で置き換え、f 軌道の分極関数を１つ加えた。他の原子については 6-31++G**基底を用いた。CHCl3 中の溶媒効果は 3D-RISM 法、結晶効果は周期境界条件に基づく QM/MM 法によって考慮した 2。
本研究の QM/MM 法に基づく結晶中の構造決定は、次のように構築されている（Scheme2）。まず、基底状態結晶を点電荷と LJ パラメータを用いてモデル化した。ここで、対称操－ 122 －

Ⅳ 研究業績 (2016)

作と格子ベクトルによる並進操作を用いる事で全結晶部分を再構成できる領域を QM 領域に選び、計算された RESP 電荷を
MM 領域に再分布させる事で自己無撞着的に MM 領域の点電荷と構造を決めた 2。これによって得られた基底状態結晶中での吸収エネル
ギーを求めた。
基底状態結晶の MM モデルは固定 し た ま ま 、 式(1) の エ ネ ル ギ ーEcrystal が最少となるように反応中心部分の３重項状態の構造を決定し Scheme 2: QM/MM 法による結晶中３重項構造の決定て、発光エネルギーを求めた。
E crystal 
E QM  E QM/MM  QM Hˆ gas  QM  E ES  E LJ 

(1)

本研究では、格子ベクトルと基底状態結晶の Au 原子の位置を実験結果に固定した。
またスペクトルに対する結晶内部と結晶表面の結果を調べるため、結晶内部で定めた構造について、スラブモデルを適用し、結晶表面での吸収・発光スペクトルを求めた。
【結果と考察】 基底状態の単量体では、Ph 基と PhNC 基の分子内平面角 に対する気相中のエネルギー、CHCl3 中の自由エネルギーは B3LYP-D3 汎関数を用いた DFT 計算レベルでほぼ一定であり、CCSD(T)計算レベルでも平面角＝度のねじれ構造が＝度の平行構造に比べて 0.5 kcal/mol だけ安定であるという結果から、常温では自由回転していると考えられる。（図１）

図１：分子内平面角 に対するエネルギー安定性
そこで、吸収スペクトルと平面角の関係性をみる為、＝、、、度の構造について TDDFT 計算を行った結果、Ph 基の軌道から PhNC 基の*軌道への LLCT 励起が最低励起状態となるが、その振動子強度は平面角に強く依存する事が分かった（図２）。また最低励起エネルギーは気相中で 3.2-3.3 eV、CHCl3 中で 3.7-3.8 eV と後者の方が 0.5 eV 高い。
また、第二ピークは Ph 基の軌道から PhNC 基の面内in*軌道への LLCT 励起であり、第一ピークが平面角=0 度で大きな強度を持つのに対して、第二ピークは平面角=90 度で大きな強度を持つ。この第二ピークについても、気相中で 4.2 eV、CHCl3 中で 4.6 eV と後者の－ 123 －

Ⅳ 研究業績 (2016)

方が 0.4 eV 高い。この溶媒中における励起エネルギーの増加は、錯体 1 の PhNC 基は中性であるのに対して Ph 基はアニオン性であるので、より強い CH-相互作用の溶媒和が Ph基に生じ、この溶媒和によって Ph 基の軌道が相対的に安定化するため、Ph 基の軌道から PhNC 基の*軌道への LLCT 励起などの励起エネルギーは CHCl3 中でより高くなる事が原因である。

図２：気相、液相の励起エネルギーと振動子強度
結晶中の 1b と 1y についても、四量体を QM 領域に選び、自己無撞着点電荷を用いた
QM/MM 計算によって構造を決定した。計算された単量体当りの結晶エネルギーは 1b よりも 1y の方が約 1 kcal/mol ほど安定であり、この傾向は実験において 1b から 1y への単結晶-単結晶相転移を不可逆的に起こす事が出来る事に合致する。また、得られた結晶構造における四量体について TDDFT 計算を行う事で吸収スペクトルを計算した（図３）。

図３：結晶中の励起エネルギーと振動子強度
1b で計算された 4.1 eV の第一ピークは Ph 基の軌道から PhNC 基の*軌道への分子内および分子間 LLCT 励起であり、気相中の分子内 LLCT 励起に比べて 0.8 eV ほど高く、また
4.5 eV の第二ピークは Ph 基の軌道から PhNC 基の面内in*軌道への LLCT 励起であり、起草中の分子内 LLCT 励起に比べて 0.3 eV ほど高い。これらの増加は、Ph 基が隣り合う２つの分子の PhNC 基と CH-相互作用している事が原因である。実際、CH-相互作用が１つ－ 124 －

Ⅳ 研究業績 (2016)

しかない結晶表面の場合は、特にこの前者の LLCT 励起は 3.7 eV に計算される。実験結果
では 3.9 eV に大きなピークがある他、3.5 eV にショルダーと 3.2 eV に小さな吸収が観測されているが、これらは各々、結晶内分子の Ph 基の軌道から PhNC 基の面内in*軌道への
LLCT 励起、結晶内分子の Ph 基の軌道から PhNC 基の*軌道への LLCT 励起、結晶表面の分子の Ph 基の軌道から PhNC 基の*軌道への LLCT 励起に対応すると帰属できる。
一方、1y での結晶中と結晶表面で計算された 3.2 eV、3.1 eV の第一ピークは Au の d 軌
道から PhNC 基の*軌道への MLCT 励起であり、実験値 2.9 eV のピークに対応している。
1y では隣り合う分子の Au-Au 距離が短いので、anti-bonding combination 型の d 軌道が生じ、そのエネルギーが相対的に高くなるため、-型 LLCT 励起よりも MLCT 励起が低く、1bの第一ピークとは異なる励起状態となる。1b から 1y への単結晶-単結晶相転移による吸収スペクトルのレッドシフトについて、実験値 1.0 eV に対して計算値 1.4 eV であり、傾向を再現している。
また、気相、CHCl3 中の単量体の３重項状態は、PhNC 基の-*局所的励起構造が求まった。この-*局所的励起は基底状態と電荷分布が大きく変化しておらず、発光エネルギーは気相、CHCl3 中ともに 2.72 eV であり、環境の影響を受けない。二量体も検証したが、-*
局所的励起よりも anti-bonding combination 型 Au の d 軌道から bonding combination 型 PhNC
基の*軌道への MLCT 励起構造が安定であった（図４）。-相互作用構造は、CH-相互作
用構造よりも気相中で 3 kcal/mol 安定であり、発光エネルギーも前者が 1.95 eV、後者が 2.45
eV となり、発光エネルギーは Au-Au 距離だけでなく、２つの PhNC 基の向きにも大きく依存する。

図４：MLCT 型３重項の２つの安定構造
1b では、周囲の分子の配向性のため MLCT 型３重項構造を二量体間で作る事ができず、
PhNC 基の-*局所的励起構造からの発光エネルギーが 2.72 eV に求まった。一方、1y では
MLCT 型３重項の CH-相互作用構造を二量体間で作り、両側の隣り合う二量体も近付く事で、その発光は 2.38 eV に求まった。これは実験値 2.19 eV に比べて高い結果になっているが、1b から 1y への単結晶-単結晶相転移による発光スペクトルのレッドシフトについて、実験値 0.34 eV に対して計算値 0.35 eV であり、良い一致を与えている。
【引用文献】[1] H. Ito et al., Nat. Commun. 2013, 4, 2009; T. Seki, K. Sakurada, H. Ito, Angew.

Chem. Int. Ed. 2013, 52, 12828. [2] S. Aono and S. Sakaki, Chem. Phys. Lett. 2012, 544, 77.

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2. 論文(1) Shinji Aono, Toshifumi Mori, and Shigeyoshi Sakaki,“3D-RISM-MP2 Approach to Hydration Structure of Pt(II) and Pd(II) Complexes:
Unusual H‑Ahead Mode vs Usual O‑Ahead One”
J. Chem. Theory Comput. 12 (3), 1189-1206, (2016).
(2) 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) Shinji Aono, Shigeyoshi Sakaki,“Effects of molecular crystal on absorption and emission spectra of gold(I)isocyanide complex: Theoretical study with QM/MM approach”
錯体化学会第 66 回討論会 福岡 2016/9/10 1B09
(2) 青野信治、榊茂好「QM/MM 法による金(I)-イソシアニド錯体の吸収・発光に対する結晶効果の研究」
第 10 回分子科学討論会 神戸 2016/9/15 3F11
(3) Shinji Aono, Shigeyoshi Sakaki,“QM/MM study of phenyl(phenyl-isocyanide) Gold(I) complex: Effects ofmolecular crystal on absorption and emission spectra”
Japn・France・Spain-Joint Symposium on Theoretical and Computational Scienceof Complex System 京都 2016/10/26 P37
4. その他(1) 青野 信治、榊 茂好「金(I)-イソシアニド錯体の吸収・発光スペクトル：QM/MM法による分子結晶効果の研究」福井謙一京都大学第１４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 2017/1/27 P16－ 126 －

Ⅳ 研究業績 (2016)

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】遷移金属と典型元素の結合を含む化合物は錯体、有機・無機金属化合物など多岐に渡り、其々に異なった結合の性質を有する。シラノンはケイ素－酸素二重結合を持つ化合物であるが、高い分極や弱いπ結合性のため、かさ高い置換基やルイス酸・塩基の配位による安定化を必要とする(スキーム１)。
近年、村岡らによってモリブデン及びタングステン原子にシラノンが配位した錯体(スキーム 2)が合成された。1 この錯体は水分子との反応によって複数の生成物が生じるが、金属原子や用いる溶媒の種類によってその生成比が大きく変化する(スキーム 2)。これらの結果は選択的反応やその制御の観点から非常に興味深いが、その違いを生む要因だけでなく、それぞれの生成物に至る反応機構も明らかにされていない。また水分子との反応機構を理解することは安定な Si-O 二重結合を生成する上で極めて重要である。本研究では、電子状態計算を用いてシラノン-金属錯体の水分子との反応機構を明らかにし、反応を制御する支配的要因の解明を試みた。

スキーム 2スキーム１【計算方法】構造最適化には DFT(B3PW91)法を用い、エネルギー計算には SCS-MP2 法を用いた。
また、PCM 法を用い溶媒効果を取り入れた。基底関数は、構造最適化及び振動数計算には遷移金属に LANL2DZ その他の原子には 6-31G*を用い、エネルギー計算には遷移金属の内殻電子はStuttgart-Dresden-Bonn の ECP で置き換え原子価軌道には triple zeta 基底関数を用い、その他の原子には 6-311G*を用いた。

－ 127 －

Ⅳ 研究業績 (2016)【結果及び考察】構造最適化の結果、生成物 1 及び生成物 2 を生じるそれぞれの反応経路が得られた(スキーム３)。反応経路１では水分子の OH 及び H がシリレンの Si 及び O に反応し生成物１を生じる。一方、反応経路 2 では水の H 原子はシリレンではなく金属原子に配位する。配位構造の異なるいくつかの中間体を経由した後に反応物 2 を生じる。ルイス塩基であるジメチルアミノピリジン(DMAP)がシリレンに配位していない場合、反応経路１の遷移状態 TS1 は、反応経路 2 の初めの遷移状態である TS2 よりも 10kcal/mol 以上不安定である。

スキーム 3２つの反応経路

DMAP が配位することで２つの反応経路の相対安定性は大きく変化する。反応経路１では水分子と反応した後も DMAP はシラレンケイ素原子上に配位しているが、反応経路２では TS2 において既に DMAP が解離している(図１)。そのため、DMAP 配位による安定化のため反応経路１と２の遷移表１. 水分子数と Gibbs エネルギー変化(kcal/mol)

状態のエネルギー差は小さくなる。
また図１に示すような、H 原子と OH 基を供給

Int1

TS1

R

TS2

Int2

する水分子が異なる水２分子による橋かけ構造

M=Mo, (H2O)1

−0.9

+15.0

0.0

+14.6

+4.2

を考えることで遷移状態の高さは大きく減少す

M=Mo, (H2O)2

−3.5

+8.9

0.0

+7.6

+4.3

る（表１）
。

M=W, (H2O)1

+1.4

+15.7

0.0

+12.2

+0.0

M=W, (H2O)2

−0.3

+10.2

0.0

+8.2

+1.7

図１DMAP 配位した Mo 錯体と水２分子の反応－ 128 －

Ⅳ 研究業績 (2016)

中間体２以降の反応経路２の最適化構造を図２に示す。立体障害の小さい H 原子が動くことにより配位構造が変化し、SiMe3 基が一旦金属原子から解離し H 原子と結合した(Int4)後に、金属原子との再結合を経由してシラレンと反応する(Int6)。中間体２以降の反応においては Si-Mo 結合が切断される TS4 の反応障壁が最も高い。

図２

反応経路２の中間体２以降の最適化構造

溶媒効果を取り入れた２つの反応経路の Gibbs エネルギー変化を図３に示す。ベンゼン溶液中では Mo 錯体は TS4 が最も高く(15.3 kcal/mol)、反応は経路１が有利である。一方、W 錯体では TS1が最も高く(16.1 kcal/mol)、経路 2 が有利である。一方、アセトニトリル溶液中では Mo 錯体 W 錯
体共に TS4 が最も高く(26.3, 25.6 kcal/mol)、経路１が有利である。これらの結果は金属原子や溶媒の種類による主生成物の変化をよく再現している。
a) In C6H6b) In CH3CN

図３ 溶媒中での Gibbs エネルギー変化 (SCS-MP2 法, kcal/mol)－ 129 －

Ⅳ 研究業績 (2016)

２つの金属錯体を比較すると、反応経路１では Mo 錯体が W 錯体よりも有利である。反応経路１では水分子の H 及び OH 共にシラノンに結合することから金属原子は直接は関与しない。Si=O π軌道のエネル
ギーは Mo 錯体で−8.86 eV と W 錯体の-8.89eV よりも高い。従って、Mo 錯体のシラノンの方がプロトンラ
イクな水素原子の求電子攻撃を受けやすいと考えられる。シラノンの配位を取り除いた金属錯体のHOMO 及び LUMO を図４に示す。HOMO は dπ軌道であり、LUMO は dσ軌道であり、その軌道エネルギーは、W 錯体の方が HOMO は高く LUMO は低い。そのためシラノンから金属へのσ供与は W 錯体で大きい、その結果
π軌道エネルギーが下がる。そのため、水との反応は Mo
錯体の方が有利であると考えられる。一方、反応経路２では Mo 錯体よりも W 錯体が有利である。経路２では金属原子に H 原子が結合することから TS2 の反応は水分子による金属-シラノン錯体への酸化付加反応とみることができる。
HOMO の軌道エネルギーは W 錯体の方が高いことから酸
図４ Mo, W 錯体の HOMO と LUMO

化付加反応が起こりやすいと考えられる。

本研究により、シラノン-金属錯体と水との複数の反応機構が明らかになった。シラレンと水の付加反応と金属錯体への酸化付加反応は競争的に起こり、金属錯体の軌道エネルギーが反応の進行方向に大きく寄与していることから配位子を化学的に修飾し軌道エネルギーを変化させることで反応を制御できると考えられる。
【文献】[1] T. Muraoka et al., Organometallics, 2017, 36, 1009−1018.

2. 論文(1) Masayuki Nakagaki, Shigeyoshi Sakaki“Hetero-dinuclear complexes of 3d metals with a bridging dinitrogen ligand: theoreticalprediction of the characteristic features of geometry and spin multiplicity”
Phys. Chem. Chem. Phys., 2016, 18, 26365-26375(2) 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, 2017, 36, 1009−1018－ 130 －

Ⅳ 研究業績 (2016)

3. 学会発表(1) 藤本和士 服部智成 Rajdeep Singh Payal 中垣雅之 榊茂好 篠田渉 岡崎進「新規ポテンシャルモデルを用いた、非晶高分子の衝撃破壊シミュレーション」
第１９回理論化学討論会, 東京, 2016/5/23-25, 2B14 口頭(2) 服部智成 藤本和士 Rajdeep Singh Payal 中垣雅之 榊茂好 篠田渉 岡崎進「高分子破壊シミュレーョンに向けた、新規ポテンシャルモデルの開発」
第１９回理論化学討論会, 東京, 2016/5/23-25, 1P30 ポスター
(3) 中垣雅之, 中谷直輝, 長谷川淳也, 榊茂好“Theoretical Investigation of Trinuclear Cr(II) Complex: Characteristic Features ofBridged Metal-metal Multiple Bonds”
錯体化学会第 66 回討論会, 福岡, 2016/9/10-12 2B-07 口頭(4) 中垣雅之, 中谷直輝, 長谷川淳也, 榊茂好「三中心多重金属結合を持つクロム(II)三核錯体の構造と電子状態」
第 10 回分子科学討論会 2016 神戸, 神戸, 2016/9/13-15 3F17 口頭
4. その他(1) Masayuki Nakagaki, Naoki Nakatani, Jun-ya Hasegawa, Shigeyoshi Sakaki“Electronic Structure and Bonding Nature of Trinuclear Cr(II) Complex: Remarkably Small
Cr-Cr Bond Order and Large Spin Polarization”
Japan-France-Spain Joint-Symposium on Theoretical and Computational Science ofComplex Systems, Kyoto, 2016/10/26-28(1) 中垣雅之, 中谷直輝, 長谷川淳也, 榊茂好「三中心多重金属結合を持つクロム(II)三核錯体の構造と電子状態」
第14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, 2017/1/27－ 131 －

Ⅳ 研究業績 (2016)

Hong
HongZHENG
Zheng
SPR Fellow
1. Summary of the research of the year
Why can Rhodium-Aluminum Bonded Complex Cleave very Strong C-O Bond?
Theoretical Study
X-type ligands with a lone pair of electrons and a formally vacant π-orbital can coordinate with atransition metal via a -bond between low-valent group 13 element and transition metal atom and have been
investigated well, with the expectation that they have unique bifunctional nucleophilic/electrophilic
properties. In previous reports the multidentate supporting X-type ligands such as X-type boryl donor (PBP)
ligand have been synthesized. Though the boryl ligands have been studied well, the X-type alumanyl ligands
have been rear with only two examples coordinated with FeCp(CO)2.

(a)

(b)
Scheme 1. (a) C-O activation catalyzed by Rh-(PAlP) complex followed by hydrogenation. (b) Proposed reaction
mechanism.

Recently a series of Rhodium complex with X-type alumanyl ligand (Rh-(PAlP)) were synthesized by
Nakao and coworkers. The alumanyl ligands were expected to activate and/or functionalize organic
compounds due to their σ-donation and the high Lewis acidity. Actually, the conventionally difficult C-O
activation was experimentally succeeded by the Rh-(PAlP) complex, as shown in Scheme 1. In this reaction,－ 132 －

Ⅳ 研究業績 (2016)

the C-O bond in Ar-OMe compound is activated in the presence of hydrosilanes and Ar-H compound isafforded. However, the reaction mechanism is not clear and thus theoretical investigation is indispensable.
In this work, we firstly investigated the reaction mechanism of the reaction cycle with Rh-(PAlP)
complexes by means of DFT calculations. The purposes here are to elucidate the characteristic features of
C-O activation and the following Si-H activation. Also, to clarify what is important factor for the C-O
activation and to increase the field of application of Rh-(PAlP), we focus on the first step of the reaction
cycle and predicted a series of C-X (X = OMe, F, NMe2) activation by Rh-(PAlP).
Reaction mechanism of the reaction cycle.
As shown in Figure 1, in the first step of catalytic cycle via C-O bond cleavage by Rh-Al, the
Rh-(PAlP) complex firstly form an adduct complex AD1a with anisole, in which the O atom and the phenylgroup weakly coordinates with the Al and Rh atoms, respectively. The O-Ph distance increases by 0.105 Å in
AD1a compared to free PhOMe compound, indicating strong interaction occurs between the Rh-Al and C-Obonds. Then, the C-O bond between the Ph and OMe groups is cleaved through one transition state TS1a. In
TS1a, the O-Ph distance increases by 0.348 Å but the Al-O and Rh-Ph distances decrease by 0.226 Å and
0.111 Å, respectively, meaning the O-Ph bond is broken and Al-O and Rh-Ph bonds are somehow formed.
Hence, TS1a is the transition state of C-O bond activation. Moreover, the Rh-Al bond becomes longer by
0.222 Å as going from AD1a to TS1a, implying the Rh-Al bond is weakened due to formation of Al-O and
Rh-Ph bonds. The O-Ph bond cleavage is completed in P1a, in which O-Ph distance increases to 3.560 Å,
whereas Rh-Al bond is almost broken due to a large distance of 2.595 Å.
In the second step, one HSiMe3 compound approaches P1a to afford an adduct AD2, in which
Rh(Ph)-Al(OMe) complex is distant from hydrosilane. Then, the Rh-H and Rh-Si distances decreases
dramatically but the H-Si bond increases by 0.073 Å in TS2. The Rh-Al further increases by 0.446 Å
because of the oxidative addition on Rh. The Si-H bond is completely cleaved in P2, in which Rh atom has
Ph, H, and SiMe3 groups. Hence TS2 is the transition state of Si-H activation. The H starts to bond with Ph
in TS3, in which the Ph-H distance decreases by 0.687 Å but the Rh-Ph distance increases by 0.082 Å asgoing from P2 to TS3. The Ph is changing its orientation to interact with the H in TS3. One benzene
compound is formed in P3. The Rh-Al distance decreases to 2.600 Å and the C6H6 species detaches from theRh center in P3. Herein, a Rh(SiMe3)-Al(OMe) complex P4 is formed. However, reductive elimination of
Si-O bond can not occur in P4 directly and the Rh-SiMe3 bond must rotates by nearly 180, leading toanother geometry P5. The reductive elimination of Si-O bond occurs through TS4. In TS4, the Si-O distancedecreases by 1.619 Å but Rh-Si increases by 1.035 Å. The Al-O bond changes little in TS4. Finally, the Si-O
bond is formed in P6. The Rh-Al bond is formed in P6 and hence the reaction cycle is completed.

－ 133 －

Ⅳ 研究業績 (2016)

Fig 1. Geometrical parameters of complexes in the C-O activation followed by Si-H activation by Rh-(PAlP). The
bond distances are represented in Angstrom.

The AD1a is moderately higher than reactant, as shown in Figure 2. The activation energy of TS1a is
9.9 kcal/mol, implying that C-O activation is easy. The P1a complexes is much more stable than reactant by-26.5 kcal/mol, suggesting that the Al-O and Rh-Ph bonds are strong. In Si-H activation, the activationenergy of TS2 is 23.2 kcal/mol relative to AD2. The product of Si-H activation P2 is only 1.1 kcal/mol lower
than TS2 due to steric repulsion and geometry distortion around the Rh atom. The activation energy of TS3
is 31.5 kcal/mol but P3 is 10.0 kcal/mol more stable than AD2. Considering that the activation energy of
Si-O reductive elimination TS is 22.4 kcal/mol relative to P3, the benzene formation step is therate-determining step in this reaction cycle. In general, C-O activation can easily occur by employing the
Rh-Al complex, which is consistant with the experimental observation.

－ 134 －

Ⅳ 研究業績 (2016)

Fig 2. Energy changes (in kcal/mol) of the reaction cycle.
C-X activations by Rh-(PAlP). It is very special that the strong C-O bond can be cleaved by the
Rh-(PAlP) complex with small activation energy and the product is very stable. To understand why C-O
activation is easy and what factor is important for this reaction, we performed investigations of C-F and C-N
activations with Ph-F and Ph-NMe2 compounds. Also, since C-O activation in Cy-OMe is useful forsynthesis of sugar, the Cy-O activation of Cy-OMe by Rh-(PAlP) was predicted.

Fig 3. Energy changes (in kcal/mol) of C-F, C-N, and Cy-O activations.
－ 135 －

Ⅳ 研究業績 (2016)

As shown in figure 3, in the C-F activation, the adduct complex AD1b is 1.8 kcal/mol higher thanreactant, whereas the transition state TS1b is 1.1 kcal/mol lower than AD1b. These results indicate that theC-F activation is much easier than the C-O activation of anisole without an activation barrier from adduct.
The C-F activation product P1b is 24.1 kcal/mol more stable than P1a, suggesting Al-F bond is muchstronger than Al-O bond. In contrast, the activation energy of TS1c in C-N activation is 13.0 kcal/mol higher
than TS1a and the product P1c is 18.9 kcal/mol less stable than P1a. These results imply that Al-N bond is
weak and therefore C-N activation can hardly occur. In the Cy-O activation, very weak interaction occurs
between Cy-OMe and Rh-Al complexes in the adduct AD1d since the Cy group does not coordinate with the
Rh. In the Cy-O activation transition state TS1d, the Cy-Rh distance is still large and its activation energy is41.3 kcal/mol, meaning this reaction can hardly occur. Herein, Rh-(PAlP) is useful for C-F activation but can
not be used for C-N and Cy-O activations.
Several important factors for C-X (X=F, OMe, NMe2) and Cy-O activations. Here we firstly
analysed the C-X (X = F, OMe, NMe2) bond energies (BE). The calculation mode is shown in Scheme 2a.
The BE values of C-X and Cy-O bonds decreases in the order C-F > C-OMe > C-NMe2 > Cy-OMe, meaningbondcleavage

becomeseasier

as

going

from

C-F

to

Cy-OMe.

However,thelowest-unoccupied-molecular-orbital (LUMO) level becomes higher in the order C-F < C-OMe < C-NMe2 <Cy-OMe. In the reaction with σ-donating alumanyl ligand, a lower LUMO level is good for the reaction andhence C-F is can easily react with the Rh-Al bond.

(a)

(b)

－ 136 －

Ⅳ 研究業績 (2016)(c)

Scheme 2. Bond energy (in kcal/mol) calculation modes: (a) Calculation mode and bond energies of C-X(X=F, OMe, NMe2) bonds and LUMO energies of Ph-X and Cy-OMe species;a (b) Calculation mode andbond energies of Al-X (X=F, OMe, NMe2) bonds; (C) Calculation mode and bond energies of Rh-Ph and
Rh-Cy bonds.ba

The bond energy of Cy-O bond was calculated with the same mode as that of C-X bonds.

b

The bond energy of Rh-Cy bond was calculated with the same mode as that of Rh-Ph bond.
The BE values of Al-X bonds decrease in the order Al-F > Al-OMe > Al-NMe2, as shown in Scheme

1b, which agree with the order of LUMO in Scheme 1a. The difference between Al-X and C-X bonds
BE(X) (BE(X) = BE(Al-X) – BE(C-X)) decreases in the order BE(F) >BE(OMe) > BE(NMe2),
indicating that the large Al-F bond energy is an important factor for the smooth C-F activation.
The BE of Rh-Cy bond is 21.0 kcal/mol smaller than that of Rh-Ph bond, as depicted in Scheme 1c,
implying that weak Rh-Cy bond is one factor for the instability of TS1d.
Based on these results, it is concluded that the LUMO of Ph-X compounds and the BE of Al-X bonds
are important factors for the C-X activations. The high LUMO of Cy-OMe and small BE of Rh-Cy bond are
the reasons why Cy-O activation is difficult.
In conclusion, C-O activation can occur easily with a small activation energy (9.9 kcal/mol) by using
Rh-(PAlP) complex. The rate-determining step in the whole reaction cycle is the formation of C6H6 species
with an activation energy of 31.5 kcal/mol. The C-F activation can easily occur but C-N and Cy-O
activations are difficult with large activation energies. The Lower LUMO of Ph-F and strong Al-F bond are
the main reasons of stable TS1b. The high LUMO of Ph-NMe2 and weak Al-N bond are the reasons of
unstable TS1c. The instability of TS1d is assigned to the high LUMO of Cy-OMe and weak Rh-Cy bond.

2. Original papers(1) Hong Zheng, Yoshiaki Nakao, Shigeyoshi Sakaki,“Why can Rhodium-Aluminum Bonded Complex Cleave very Strong C-O Bond?
Theoretical Study” In preperation.
3. Others(1) Teruhiko Saito, Hong Zheng, Naofumi Hara, Nishamol Kuriakose, Shigeyoshi Sakaki,
Yoshiaki Nakao,“Rhodium Complexes Bearing PAlP Pincer Ligands” In preparation.

－ 137 －

Ⅳ 研究業績 (2016)

Lu Jing
Research
Fellow
Research Fellow
1. Summary of the research of the year
DFT insight into core-shell preferences for bimetallic Pt42M13 (M=Mo, Tc, Ru, Rh, Pd, W, Re,
Os, and Ir) clusters
Platinum (Pt)-based clusters/particles have been playing a major role in many industrial application,such as catalyzing the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. Greatefforts are being made to decrease Pt content with increasing Pt dispersion and enhancing catalytic activity.
One approach is based on the core−shell structure consisting of a thin layer of Pt deposited on the surface of
nanoparticles made of a less expensive and/or a more abundant metal. Currently, bimetallic Fe-Pt, Co-Pt,
Ni-Pt, Cu-Pt, and Ru-Pt with core-shell structure have been reported as good catalytic candidates bothexperimentally and theoretically. However, the systematically study about the determining factors
influencing core-shell structure for bimetallic alloyed cluster/particle and their electronic structure have beenrarely presented.
For the icosahedral bimetallic Pt42M13 (M = Mo, Tc, Ru, Rh, Pd, W, Re, Os, and Ir) clusters, acomprehensive analysis of the determining factors influencing core-shell structure, such as cohesive energy,
stability of the core and shell, together with charge transfer, are elucidated. Also, the electronic structures of theinvestigated bimetallic core-shell M13@Pt42 clusters are clarified.

Scheme 1. Model systems of icosahedral 55-atom clusters with corresponding M13 core and M42 shell.

Relative energy. For the icosahedral Pt42M13 (M = Ru and Os) clusters, the most stable structure is thecore-shell structural M13@Pt42 cluster, the next stable one is Pt42M12coreMvertex cluster, and the least stable one
is Pt42M12coreMedge cluster. Similarly, the icosahedral core-shell structural Rh13@Pt42 cluster is the most stable
among these three isomers. The energies difference between the Pt42Rh12coreRhedge (Pt42Rh12coreRhvertex) andRh13@Pt42 is 11.42 kcal/mol (6.88 kcal/mol). For the icosahedral Pt-Ir combination, the stability decreases in
the order of Ir13@Pt42 (0.00 kcal/mol) > Pt42Ir12coreIredge (+41.45 kcal/mol) > Pt42Ir12coreIrvertex (+48.59
kcal/mol). In a word, the icosahedral core-shell structural M13@Pt42 (M = Ru, Rh, Os, and Ir) clusters arefavorable. However, in the cases of M = Mo, Tc, Pd, Re, and W, the icosahedral core-shell structural
M13@Pt42 clusters are not stable. For the combinations of Pt-Mo, Pt-W, and Pt-Re, the Pt42M12coreMedge
isomer have the lowest energy, which are lower by 47.76 kcal/mol, 25.02 kcal/mol, and 10.53 kcal/mol than
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M13@Pt42, respectively. For the Pt42Tc13 and Pt42Pd13 clusters, the stability decreases in the order of
Pt42M12coreMvertex > Pt42M12coreMedge > M13@Pt42 (see Table 1).
Table 1. Relative energy (in kcal/mol) of three isomers in the most stable spin states.
M
Mo
Tc
Ru
Rh
Pd
W
Re
Os
Ir

M13@Pt42
0.00 (Singlet)
0.00 (Octet)
0.00 (Septet)
0.00 (20et)0.00 (23et)0.00 (Singlet)
0.00 (Doublet)
0.00 (Septet)
0.00 (Dectet)

Pt42M12coreMedge-47.76 (Singlet)-18.38 (Doublet)+37.96 (Septet)+11.42 (20et)-31.07 (15et)-25.02 (Singlet)-10.53 (Doublet)+65.64 (Triplet)+41.45 (Quartet)

Pt42M12coreMvertex-36.53 (Quintet)-18.59 (Octet)+31.03 (Septet)+6.88 (20et)-31.37 (15et)-8.49 (Triplet)+3.24 (Dectet)+61.16 (Septet)+48.59 (12et)

Segregation energy. The calculated segregation energies are positive in the cases of M = Ru, Rh, Os,
and Ir, showing that M-core and Pt-shell structure is preferred (see in Figure 1). The minimum segregationenergies for the Ru-Pt, Rh-Pt, Os-Pt, and Ir-Pt are 1.35 eV, 0.30 eV, 2.65 eV, and 1.80 eV, respectively. For
the combinations of Mo-Pt, Tc-Pt, Pd-Pt, W-Pt, and Re-Pt, however, the segregation energies are -2.07 eV,-0.81 eV, -1.35 eV, -1.09 eV, and -0.46 eV, respectively. The negative segregation energy indicates that
M13@Pt42 (M = Mo, Tc, Pd, W, and Re) structure is not stable. For the 4d metals, the segregation energy
increases as going from Mo to Ru and then decreases as going from Ru to Pd. Though the same trend isfound for the 5d metals, the value shifts to more positive (or less negative).

Figure 1. Calculated segregation energy (in eV) for icosahedral Pt42M13 (M = Mo, Tc, Ru, Rh, Pd, W, Re, Os, andIr) clusters.

Cohesive energy. The cohesive energy of icosahedral Ru13, Rh13, Os13, and Ir13 are 4.86 eV, 4.28 eV,
5.41 eV, and 5.29 eV, respectively, which are larger than that of Pt13 (3.95 eV). It means that the M (M = Ru,
Rh, Os, and Ir) prefers to occupy the core positions to achieve the greater binding energies. Also, 5d metal(Os or Ir) has larger cohesive energy than 4d metal (Ru or Rh) in the same group. On the other hand, thecohesive energy of Pd13 (2.43 eV) is smaller than that of Pt13. It means that Pd is unfavorable to reside in thecore position for the combination of Pd and Pt.
M13 core and Pt42 shell. For the icosahedral M13 (M = Ru, Rh, Os, and Ir) core, the RMSD values for
the Ru13, Rh13, Os13, and Ir13 are 0.023 Å, 0.045 Å, 0.002 Å, and 0.006 Å, respectively. Meanwhile, thecalculated distortion energies of Ru13, Rh13, Os13, and Ir13 using the B3LYP functional are 0.52 eV, 1.08 eV,-0.05 eV, and 0.28 eV, respectively. The smallest distortion energy is observed in the Os13, verifying that theOs13 core is the most stable. The next stable core is Ir13, and the least stable cores are Ru13 and Rh13. It is－ 139 －

Ⅳ 研究業績 (2016)

reasonable to infer that, smaller RMSD and distortion energy of M13 core will result in the stabilization of
M13 core, which is beneficial to form the core-shell structure.
In the cases of metals in group VI and VII, the optimized structure of isolate M13 is significantly
different from icosahedral structure, indicating that the icosahedral M13 (M = Mo, Tc, W, and Re) is
unfavorable. The instability of icosahedral M13 core is the major reason why these metals do not have
M13@Pt42 structure. It suggests that the M13 cluster in the core positions must have the same structure as thetotal M13@Pt42 cluster.
Also, the distortion energy of the icosahedral Pt42 surface in the M13@Pt42 cluster is lower than that in
the Pt55 cluster, which also contributes to the stability of Pt42 shell. These factors are important for stabilizing
the M13@Pt42 core-shell structure.
Charge transfer. Charge distribution and d-orbital population are also important factors influencing
core-shell structure. NBO charge distributions for the icosahedral M13@Pt42 and Pt55 clusters are given in
Table 2. The NBO charge of Pt atom in the core1 position for the pure Pt55 cluster is +0.638 e. However, thecharges of Ru, Rh, Os, and Ir atoms in the core1 position of the stable core-shell structural M13@Pt42 clusters
are -3.246 e, -1.575 e, -1.467 e, and -0.619 e, respectively, indicating that the charge transfer (CT) is
occurred from Pt to M (M = Ru, Rh, Os, and Ir) metals with incompletely occupied d orbital. Similarly, thecharges of M atom in the core2 position are also negative (-2.946 e, -2.515 e, -1.577 e, and -0.220 e,
respectively). On the other hand, the NBO charge of Pt in the edge position of the Pt55 cluster is -0.122 e.
The charges of M in the same position are much more negative, and the most negative charge is found in the
Os. For the position of vertex, the Pt has a positive charge. On the contrary, the Ru, Rh, Os, and Ir havenegative charges.
The d-orbital population of Pt atom, which is located in the core1 position of Pt55 cluster, decreases by
0.21 e compared to d9 electron configuration in the atomic ground state. However, the d-orbital populationsof Ru, Rh, Os, and Ir in the stable icosahedral core-shell structural Ru13@Pt42, Rh13@Pt42, Os13@Pt42, andIr13@Pt42 clusters increase by 2.49 e, 1.75 e, 3.19 e, and 1.94 e, respectively, compared with the atomic
electron configurations. The difference of d-orbital population for the 5d metal (Os or Ir) is larger than thatfor the 4d metal (Ru or Rh) in the same group. The large difference of d-orbital population between M in the
M13@Pt42 cluster and M in the atomic ground state is benefit to obtain large segregation energy, and thenincrease the tendency of core-shell structure.
Table 2. NBO charge (q), s, p, and d orbital populations of M, and difference in electron population from theatomic ground states.
core1

q(M

)

M13@Pt42

core2

q(M

)

-3.246
5s: 0.24 [-0.76]
4d: 9.49 [+2.49]
5p: 1.73 [+1.73]-2.9460.41 [-0.59]
9.09 [+2.09]
1.74 [+1.74]-1.5755s: 0.33 [-0.67]
4d: 9.75 [+1.75]
5p: 2.40 [+2.40]-2.5150.41 [-0.59]
9.51 [+1.51]
1.90 [+1.90]

Ru

5s14d7Rh

5s14d8－ 140 －

Pt42M12coreMedgeq(Medge)

Pt42M12coreMvertex
q(Mvertex)-1.7775s: 0.60 [-0.40]
4d: 8.26 [+1.26]
5p: 1.41 [+1.41]-1.3645s: 0.62 [-0.38]
4d: 7.65 [+0.65]
5p: 1.77 [+1.77]-1.281
5s: 0.56 [-0.44]
4d: 8.89 [+0.89]
5p: 1.35 [+1.35]-0.9935s: 0.61 [-0.39]
4d: 8.63 [+0.63]
5p: 1.44 [+1.44]

Ⅳ 研究業績 (2016)-1.467
6s: 0.58 [-1.42]5d: 9.19 [+3.19]
6p: 2.42 [+2.42]-1.5770.50 [-0.50]
8.85 [+2.85]
1.76 [+1.76]-0.6196s: 0.55 [-1.45]
5d: 8.94 [+1.94]
6p: 2.21 [+2.21]-0.2200.47 [-1.53]
9.07 [+2.07]
1.52 [+1.52]+0.6386s: 0.48 [-0.52]
5d: 8.79 [-0.21]
6p: 1.29 [+1.29]-0.1700.48 [-0.52]
9.10 [+0.10]
1.49 [+1.49]Os

6s25d6Ir 6s25d7

Pt

6s15d9-2.0136s: 0.63 [-1.37]
5d: 8.29 [+2.29]
6p: 1.40 [+1.40]-2.496
6s: 0.73 [-1.27]
5d: 8.13 [+2.13]
6p: 2.03 [+2.03]-1.326
6s: 0.73 [-1.27]
5d: 8.99 [+1.99]
6p: 1.22 [+1.22]-1.1236s: 0.81 [-1.19]
5d: 8.79 [+1.79]
6p: 1.12 [+1.12]-0.1226s: 0.62 [-0.38]
5d: 8.88 [-0.12]
6p: 1.31 [+1.31]+0.0836s: 0.70 [-0.30]
5d: 8.70 [-0.30]
6p: 1.22 [+1.22]

In summary, the crucial factors influencing core-shell structure, such as cohesive energy, stability of the
icosahedral M13 core and Pt42 shell, and electronic properties are systematically explored for the icosahedral
Pt42M13 (M = Mo, Tc, Ru, Rh, Pd, W, Re, Os, and Ir) clusters. The icosahedral core-shell structural M13@Pt42
clusters are stable in the case of M = Ru, Os, and Ir. However, the core-shell structural Mo13@Pt42,
Tc13@Pt42, Pd13@Pt42, W13@Pt42, and Re13@Pt42 clusters are not stable.
Our results suggest that the M with larger cohesive energy prefers to occupy the core position. The
stability of icosahedral M13 core and Pt42 shell are also important for the formation of core-shell structure. In
addition, the large difference of d-orbital population between M in the M13@Pt42 cluster and M in the atomic
ground state is benefit to obtain positive segregation energy. We expect that our study can provide useful
understanding of the core-shell preferences for the bimetallic Pt-shell clusters/particles, and then predictwhether the bimetallic Pt-M clusters have a stable core-shell structure or not.

2. Original papers(1) Jing Lu, Kazuya Ishimura, and Shigeyoshi Sakaki,“DFT insight into core-shell preferences for bimetallic Pt42M13 (M = Ru, Rh, Os, and Ir)clusters”
In preparation.
3. Presentation at academic conferences(1) Jing Lu, Kazuya Ishimura, and Shigeyoshi Sakaki,“DFT insight into core-shell preferences for bimetallic Pt42M13 (M=Mo, Tc, Ru, Rh, Pd, W,
Re, Os, and Ir) clusters”
第 20 回理論化学討論会 (P24), Kyoto, May 17, 2016

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Ⅳ 研究業績 (2016)

Rong-Lin Zhong
Rong-Lin Zhong
SPR Fellow
SPR Fellow
1. Summary of the research of the year
How to Succeed Oxidative Addition of Nitrobenzene to Palladium(0) Complex: Characteristic
Features in Electronic Process

The Pd-catalyzed Suzuki-Miyaura cross-coupling reaction is one of efficient and versatilemethods for constructing carbon–carbon bonds in biaryls and substituted aromatics. In theconventional Suzuki-Miyaura cross-coupling reaction, aryl halides are employed as electrophilic
coupling reagent. Recently, substantial efforts have been devoted to the use of alternatives of aryl
halides as the electrophilic coupling reagent because aryl halides are difficult to be regioselectively
synthesized from arenes. For example, the use of aryl ethers, aryl esters, and arenols have beensucceeded in the Suzuki-Miyaura cross-coupling reaction. On the other hand, the use of nitroarenes
for the Suzuki-Miyaura cross-coupling reaction has not been succeeded for a long time despite that
nitroarenes are highly versatile aromatic building blocks in organic synthesis, and directly obtained
though nitration which is generally highly selective toward mono-functionalization. Very recently,
the Suzuki-Miyaura cross-coupling reaction of nitroarenes with phenylboronic acid has beensucceeded by Nakao group as shown in Scheme 1. The catalytic cycle of this reaction is initiated by
the concerted oxidative addition of the Ar–NO2 bond to Pd(0) complex.

Scheme 1. Suzuki-Miyaura cross-coupling reaction of 1-methoxy-4-nitrobenzene.
In the Suzuki-Miyaura cross-coupling reaction, the first step is the oxidative addition ofaryl–halide (Ar1-X) to Pd(0) complex, the second step is transmetalation between Ar1-Pd(II)-X
complex and aryl-boronic acid (Ar2-B(OH)2), and the last step is reductive elimination of Ar1-Ar2.
In previously reported Pd-catalyzed Suzuki–Miyaura cross-coupling reaction of nitro-halo arenes,
the aryl group of phenyl boronic acid was introduced at the halide site and the nitro group was notsubstituted. This suggests that the oxidative addition of the Ar-NO2 bond is difficult. Therefore, it isof considerable interests to get a fundamental understanding of the reason(s) why the Ar-NO2 bond
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Ⅳ 研究業績 (2016)activation is more difficult than the Ar-X. On the other hand, usual phosphine ligand is effective for
Ar-X bond activation and generally a bulky monophosphine ligand is more favorable for the Ar-X
(X=Cl and Br) bond activation than a bi-phosphine ligand according to previous investigations.
Another characteristic feature of the Suzuki-Miyaura cross-coupling reaction of nitroarenes is theuse of unique BrettPhos while usual phosphine ligand, such as PMe3 could not. We wonder why not
usual phosphine ligand but BrettPhos was successfully used in the Suzuki-Miyaura cross-coupling
reaction of nitroarenes.
In this work, we theoretically investigated the characteristic features of the concerted oxidative
addition of nitrobenzene to Pd(Brettphos) complex. Our purposes here are to elucidate the reasons
why the Ph-NO2 bond activation is more difficult than Ph-X bond (X=halide), why unique
BrettPhos is used as ligand, and why usual phosphine is not useful for the Ph-NO2 bond activation.
Models and Computational Details
All geometry optimizations were performed by ωB97XD functional in gas phase, using the
Stuttgart-Dresden-Bonn basis set for Pd with the effective core potentials and the 6-31G(d) basis
sets for other atoms were used. Single-point calculations were performed by the ωB97XD
functional, using a better basis set system (BS-II) to provide a better potential energy change. In
BS-II, two f polarization functions were added to Pd and 6-311G(d) basis sets were used for otheratoms, where diffuse functions were added to anionic Br atom, N and O atom of NO2 group.
Solvation effects (1,4-dioxane) were evaluated with polarizable continuum model (PCM) method,where the geometries optimized in gas phase were employed.
In this work, discussion is presented based on the Gibbs energy, where the translation entropy
in solution was corrected by the method of Whiteside et al. because the reactions occur in solution.
Thermal correction and entropy contribution to the Gibbs energy were taken from the frequency
calculation in gas phase at 298.15 K and 1 atm. In this work, the Gibbs activation energy (∆Gº‡) isdefined as a difference in Gibbs energy between the transition state (TS) and the most stableintermediate before TS.

The Gibbs reaction energy (∆Gº) is defined as a difference in Gibbs

energy between the product and the reactants. All these calculations were carried out with
Gaussian09 program.
Since the usual phosphine ligand is not useful while the unique BrettPhos was successfully
used in the Suzuki-Miyaura cross-coupling reaction of nitroarenes. The ligand effect on theoxidative addition reaction of nitrobenzene is important to be considered. In this work, we compare
BrettPhos with BrettPhos isomer and PMe3 ligands to reveal the characteristic features of BrettPhos.
The molecule structures of the three ligands are shown in Scheme 2. The BrettPhos isomer is abulky monophosphine and designed by change the position of tri-iPr-Ph group from ortho to para of－ 143 －

Ⅳ 研究業績 (2016)

the phenyl ring of BrettPhos.

Scheme 2. The molecular structure of BrettPhos, BrettPhos isomer, and phosphine (PMe3) ligand.
Results and Discussion
Thermodynamics of Oxidative Addition of Nitrobenzene and Bromobenzene Derivatives toPd(PMe3)2 and Pd(BrettPhos)
The catalytic cycle of the Suzuki-Miyaura cross-coupling reaction of nitrobenzene is initiated by theoxidative addition of Ph-NO2 bond to Pd(BrettPhos) complex. According to experiments and ourtheoretical examinations, the single electron transfer mechanism and stepwise oxidative addition via
the nucleophilic attack mechanism were unlikely. Therefore, here the concerted oxidative additionof Ph-NO2 bond to Pd(0) complex was investigated, which is an unprecedented elemental reaction
with considerable interests. To understand the oxidative addition of nitrobenzene, we firstly
evaluated the Ph-NO2 bond dissociation energy (BDE) compared with Ph-Br bond. As shown in
Scheme 3, the BDE(Ph-NO2) is 76.9 kcal/mol and the BDE(Ph-Br) is 83.1 kcal/mol. The Ph-NO2
bond is moderately weaker than the Ph-Br, which is in consistent with experiments. However, the
Ph-NO2 bond activation is more difficult than Ph-Br even though Ph-NO2 bond is weaker. To
investigate these differences between Ph-NO2 and Ph-Br bond activation, we evaluated theBDE(Pd-NO2) and BDE(Pd-Br) in the product of oxidative addition with (PMe3)2 ligands. As
shown in Scheme 3, the BDE(Pd-NO2) is 43.3 kcal/mol and the BDE(Pd-Br) is 65.2 kcal/mol.
Though the Ph-Br bond is stronger than Ph-NO2 bond by 6.2 kcal/mol, the Pd-Br bond is muchstronger than that of Pd-NO2 by 21.9 kcal/mol. This is an important reason why the oxidative
addition of bromobenzene to Pd(PMe3)2 is more exothermic than that of nitrobenzene. Furthermore,
we also evaluated the BDE(Pd-NO2) and BDE(Pd-Ph) in the product of oxidative addition with
BrettPhos. The Pd-NO2 and Pd-Ph bond with BrettPhos ligand are considerably stronger than thatwith (PMe3)2 ligand by 8.0 kcal/mol and 8.5 kcal/mol, respectively. Therefore the oxidative additionof nitrobenzene to Pd(BrettPhos) is more exothermic than to Pd(PMe3)2. On the other hand, we also
considered the para substituted effect of electron donating (OMe) and electron withdrawing group(CF3) on the oxidative addition of nitrobenzene. As shown in Scheme 3 and Scheme 4, the effect ofOMe group on Pd-Ph and Pd-NO2 is very small, while slightly strengthen the Ph-NO2 bond. On theother hand, the Ph-NO2 bond is slightly weakened together with Pd-Ph bond is moderately－ 144 －

Ⅳ 研究業績 (2016)

strengthened by substitution of the CF3 group, which is independent on the ligands. It indicates thatthe oxidative addition of nitrobenzene is more exothermic with the substitution of electron
withdrawing group.

Scheme 3. Bond dissociation energy (BDE) of Ph-NO2, Ph-Br, Pd-Ph, Pd-NO2, and Pd-Br with
(PMe3)2 ligand. The substituted effect of OMe and CF3 group on Ph-NO2 has been considered.

Scheme 4. Bond dissociation energy (BDE) of Ph-NO2, Ph-Br, Pd-Ph, Pd-NO2, and Pd-Br with
BrettPhos ligand. The substituted effect of OMe and CF3 group on Ph-NO2 has been considered.

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Geometry and Energy Changes in Oxidative Addition of 1-methoxy-4-nitrobenzene and1-methoxy-4-bromobenzene
We investigated the oxidative addition of 1-methoxy-4-nitrobenzene to Pd(BrettPhos) complex 1,
because this substrate was used in the experiment of transmetalation. 1-methoxy-4-nitrobenzene
approaches 1 to form a stable η2-coordinated adduct (AD1a), in which the meta C-C bond of thephenyl ring coordinates with the Pd atom, as shown in Figure 1. The binding energy is significantly
large (27.9 kcal/mol in the Gibbs energy). AD1a is not connected to the transition state of theoxidative addition, as will be shown below, because the C-NO2 bond is distant from the Pd. Prior tothe oxidative addition, the Pd atom moves to the ortho C-C bond of the phenyl ring to form AD2a,which is less stable than AD1a by 5.5 kcal/mol. Starting from AD2a, the oxidative addition occurs
through the three-membered transition state (TSa) to afford the four-coordinated Pd(II)(NO2)(C6H4-OMep)(Brettphos) (PRDa). In TSa, the C1-N bond is elongated to 1.784 Å from1.455 Å, indicating that the C1-N bond cleavage is in progress. Though the Pd-C1 distance becomesshorter to 2.119, which is close to that of product; the Pd-C2-C3 angle still deviates from that of the
PRDa, indicating that the orientation of the phenyl group is changing in TSa. On the other hand,
the Pd-N distances become shorter to 2.072 Å, which is close to that of PRDa, and also the NO2
group has already changed its orientation toward the Pd. This means that the Pd-NO2 bond is almost
formed in TSa. The PRDa is a pseudo-square-planar Pd(II) complex.

Figure 1. Optimized geometries in oxidative addition of 1-methoxy-4-nitrobenzene to Pd(BrettPhos)
complex (distance [Å], hydrogen atoms are omitted for clarity), Gibbs energy relative to that ofseparated reactants are provided (potential energies are in the parentheses).
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The Gibbs activation energy (∆Gº‡) of this reaction is 30.3 kcal/mol (relative to the most stable
reactant adduct AD1) and the Gibbs reaction energy (∆Gº) is -30.0 kcal/mol (relative to the sum ofreactant complex 1 and p-methoxynitrobenzene).
We investigated the oxidative addition of 1-methoxy-4-bromobenzene to Pd(BrettPhos)
complex for comparison as shown in Figure 2. This reaction proceeds through a similarη2-coordinated adducts (AD1b and AD2b) and transition state (TSb) to afford a palladium(II)complex Pd (II)(Br)(C6H4-OMep)(Brettphos) (PRDb), as shown in Figure 2. Though AD1b andAD2b are similar to AD1a and AD2a, we found some of interesting differences between TSa andTSb. In TSb, the Pd-C1 distance is longer than that in TSa by 0.118 and the Pd-Br distance issomewhat longer than in PRDb, suggesting that TSb is less product-like than TSa.
Correspondingly, the dihedral angle between plane C1BrPd and plane PC2Pd in TSb is 27.9°, while
the dihedral angle (13.1°) between plane C1NPd and plane PC2Pd in TSa is smaller (moreproduct-like). The ∆Gº‡ is 16.3 kcal/mol, which is much smaller than that for Ph-NO2 bondactivation, and the ∆Gº is -50.0 kcal/mol, which is much more negative than that for Ph-NO2 bondactivation. These results indicate clearly that the oxidative addition of nitroarene is more difficult
than that of bromoarene, which is consistent with previous experiments.

Figure 2. Optimized geometries in oxidative addition of 1-methoxy-4-bromobenzene toPd(BrettPhos) complex (distance [Å], hydrogen atoms are omitted for clarity), Gibbs energy
relative to that of separated reactants are provided (potential energies are in the parentheses).

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Characteristic Features of Oxidative Addition of 1-methoxy-4-nitrobenzene
To gain an insight into characteristic features of oxidative addition of 1-methoxy-4-nitrobenzene,
we focused on the main difference in several important bond distance, angle and potential energychanges along the intrinsic reaction coordinate (IRC) between the Ph-NO2 and Ph-Br bondactivation. As shown in Figure 3, the first stage of the reaction is the increase of Pd-C2 distance,
which means the dissociation of the η1 coordination between Pd center and the C2 atom of thetri-iPr-phenyl ring of BrettPhos ligand. The second stage is the decrease of Pd-C2 and the increaseof Pd-C1 distance, which means the re-coordination of between Pd center and the tri-iPr-phenyl ring
together with dissociation of the η2 coordination between Pd center and ortho C-C bond of
1-methoxy-4-nitrobenzene. The third stage is the decrease of Pd-C1 and the increase of C-N1
distance, which means coordination (η1) between C1 and Pd together with the dissociation of C-N1
bond to form TSa; in this stage the orientation change of phenyl and NO2 group is in progressbecause the ∠Pd-C1-C3 increase from 112° to 139° and Pd-N-X (X is the center between two O

atoms) increase from 118° to 144°, which means Pd-Ph and Pd-N bond formation is in progress.
The last stage is continuous increase of C1-N distance together with the increase of the angel

Pd-C1-C3 and Pd-N-X to form the PRDa. Compared with Ph-NO2 bond activation, two differencesin geometry change were found in the Ph-Br bond activation; 1. The C1-Br bond elongates by 0.085
Å and the ∠Pd-C1-C3 (Ph orientation) increases by 30.85° from AD2b to TSb, smaller than that of
Ph-NO2 bond activation case, in which C1-NO2 bond elongates by 0.329 Å and the ∠Pd-C1-C3 (Phorientation) increases by 46.12° together with the ∠Pd-N-X (NO2 orientation) increase 9.63°. It
shows that the distortion of 1-methoxy-4-nitrobenzene in TSa is larger than that of
1-methoxy-4-bromobenzene in TSb. 2. The Pd-C2 distance of TSb have not decreased to that of

PRDb, while in Ph-NO2 bond activation case, the re-coordinate of Pd-C2 has almost finished inTSa. In this context, the TSa is more product-like than TSb.

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Figure 3. Change in several important bond distance, angle and potential energy along the IRC ofthe oxidative addition reaction of 1-methoxy-4-nitrobenzene and 1-methoxy-4-bromobenzene.
The natural bond orbital (NBO) charge changes along IRC are obviously different in the
Ph-NO2 bond activation and Ph-Br bond activation as presented in Figure 4. In AD2a, the NBO
charge of NO2 is more negative than MeO-Ph group, while the NBO charge of Br atom is lessnegative than MeO-Ph group in AD2b, because NO2 is a strong electron withdrawing group. In the
dissociation of Pd-C2 η1 coordination stage (first stage), the charge of MeO-Ph and NO2 groupslightly increase together with that of Pd decreases; similar trend that the charge of MeO-Ph and Br
group slightly increase are also shown in the Ph-Br bond activation in this stage. However, in thesecond stage, the charge of NO2 considerably decreases together with that of the MeO-Ph groupincreases, while that of Br atom and MeO-Ph group continuously increase. It indicates that, thePhδ+-NO2δ- polarization decreases the NBO charge of NO2 while the polarization of Phδ+-Brδ- did
not occur in this stage. After that, the NBO charge of NO2 in TSa is almost close to that of PRDa
while that of Br in TSb is considerably larger than that of PRDb. On the other hand, the charge of
MeO-Ph group of TSa is 0.07, which is considerably larger than that (-0.23) of PRDa, while thecharge of MeO-Ph group of TSb is -0.11, which is almost close to that (-0.19) of PRDb. Therefore,
the charge transfer from Pd to NO2 is almost finished in TSa, while the charge transfer process to
Br occurs after TSb. On the other hand, the charge transfer from Pd to MeO-Ph group is in progressin TSa, while the charge transfer process to MeO-Ph group has already occurred in AD2b. In this－ 149 －

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context, the electronic process in the oxidative addition of 1-methoxy-4-nitrobenzene toPd(BrettPhos) exhibits a unique feature, which is significantly different with that of
1-methoxy-4-bromobenzene.

Figure 4. Change in NBO charge along the IRC of the oxidative addition reaction of
1-methoxy-4-nitrobenzene and 1-methoxy-4-bromobenzene.
The orbital interactions in the TS of the oxidative addition of 1-methoxy-4-nitrobenzene and1-methoxy-4-bromobenzene to Pd(BrettPhos) complex are shown in Figure 5. In the HOMO ofTSa, charge transfer occur from the Pd dπ orbital to the σ*+π* orbital of the Ph-NO2, which
consists the σ*-antibonding orbital of the C-NO2 bond and the π* orbital of the NO2 group (LUMO);
together with charge transfer from the Pd dπ orbital to another σ*+π* orbital of the Ph-NO2, which
consists the σ*-antibonding orbital of the C-NO2 bond and the π* orbital of the Ph group(LUMO+1). However, in the HOMO of TSb, a smaller charge transfer occur from the Pd dπ orbitalto the σ*+π* orbital of the Ph-Br, which consists the σ*-antibonding orbital of the C-Br bond andthe π* orbital of the Ph group (LUMO). Therefore, charge transfer from Pd to NO2 is earlier thanthe charge transfer from Pd to MeO-Ph group because the π* orbital of the NO2 group participatesin the charge transfer interaction of TSa, while in the Ph-Br bond activation, the charge transferfrom Pd to Br is later than the charge transfer from Pd to MeO-Ph group.

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Ⅳ 研究業績 (2016)

Figure 5. HOMO of TSa and TSb, and charge transfer interactions in TSa and TSb.
Furthermore, the potential energy (E), deformation energy (ED) of each moiety and interactionenergy (Eint) between them are listed in Table 1. The difference between the potential energy ofAD1a and AD1b is 4.5 kcal/mol. It suggests that AD1a and AD1b are similarly stable. However, inTSa, the ED of 1-methoxy-4-nitrobenzene moiety is larger than that of 1-methoxy-4-bromobenzene
moiety in TSb by 27.0 kcal/mol even though the Eint in TSa is larger than that in TSb by 17.5
kcal/mol. Therefore, the larger ED of 1-methoxy-4-nitrobenzene moiety is the origin of larger
Ph-NO2 bond activation barrier. This is because the sp2 orbital of NO2 must change its direction
toward Pd to form bonding interaction. However, Br has spherical valence orbital, which can form
the interaction with dπ of Pd by keeping the Ph-Br σ-bond.
Characteristic Feature of BrettPhos
According to previous reports, mono-phosphine ligands are generally more favorable for the Ph-Br
bond activation than bis-phosphine ligands. Therefore, we take a BrettPhos isomer by change theposition of tri-iPr-Ph group from ortho to para of the phenyl ring as an example to consider the－ 151 －

Ⅳ 研究業績 (2016)

mono-phosphine ligands for Ph-NO2 bond activation. As shown in Figure 6, the PRDc is less stable
than AD1c, which suggests that Ph-NO2 bond activation with BrettPhos isomer is an endergonic
reaction. Besides, intermediates, transition state and product of BrettPhos isomer are less stable thanthose of BrettPhos. Therefore, a mono-phosphine ligand is not favorable for the Ph-NO2 bondactivation even though it is effective for Ph-Br bond activation. As shown in Figure 7, dπ orbital of
Pd provided by Brettphos is at a higher energy than that provide by Brettphos isomer, which isfavorable for charge transfer to Ph-NO2 moiety because the π of phenyl moiety in BrettPhos
interacts with dπ of Pd in an antibonding way.

Figure 6. Optimized geometries in oxidative addition of 1-methoxy-4-nitrobenzene to Pd(BrettPhos
isomer) (distance [Å], hydrogen atoms are omitted for clarity), Gibbs energy relative to that ofseparated reactants are provided (potential energies are in the parentheses).

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Ⅳ 研究業績 (2016)

Figure 7. HOMO (dπ) orbital in Pd(BrettPhos), Pd(BrettPhos isomer), and Pd(PMe3)2 moieties inreactant and TS.
To further reveal the characteristic feature of BrettPhos ligand, we also compared BrettPhos
with(PMe3)2 ligand.

The

geometryandenergychangeinoxidative

additionof

1-methoxy-4-nitrobenzene with Pd(PMe3)2 is shown in Figure 8. Results indicate that BrettPhos ismore favorable than (PMe3)2, because the intermediates, transition state, and product of BrettPhos
are relatively more stable than those of (PMe3)2 by 20.0 kcal/mol. It is worthy of note that, fromreactant to TSd, the P-Pd-P angle decrease from 180° to 114.56°. Correspondingly, the deformationenergy of Pd(PMe3)2 moiety in TSd is 19.0 kcal/mol because of the bending, which is larger thanthat (4.7 kcal/mol) of Pd(BrettPhos) moiety in TSa. In this context, larger deformation energy ofPd(PMe3)2 is response for corresponding less stable intermediates, transition state, and product. The
dπ orbital of Pd provided by (PMe3)2 in TSd is shown in Figure 7. The dπ orbital of Pd(PMe3)2 is-7.81 eV considerably increase to -5.73 eV of TSd with a larger deformation energy (19.0 kcal/mol).
However, the dπ orbital of Pd(BrettPhos) is -5.82 eV slightly increase to -5.65 eV of TSa with asmaller deformation energy (4.7 kcal/mol). In this context, the dπ orbital of Pd(BrettPhos) is morereactive at a higher energy while the dπ orbital of Pd(PMe3)2 is more stable that need a larger
deformation energy to activate it. Therefore, the dπ orbital of Pd(BrettPhos) is more reactive thanPd(PMe3)2, which provide a better charge transfer to form a stable precursor and transition state thatis an important reason why BrettPhos is more favorable than (PMe3)2. Furthermore, the activation－ 153 －

Ⅳ 研究業績 (2016)energy of Ph-NO2 bond is 29.1 kcal/mol with (PMe3)2 ligand, which is larger than BDE(Pd-P) in
AD1d, 20.8 kcal/mol. In this context, prior to TS, PMe3 ligand might dissociate, which is anotherreason why (PMe3)2 is unfavorable for Ph-NO2 bond activation.

Figure 8. Optimized geometries in oxidative addition of 1-methoxy-4-nitrobenzene to Pd(PMe3)2
isomer (distance [Å], hydrogen atoms are omitted for clarity), Gibbs energy relative to that ofseparated reactants are provided (potential energies are in the parentheses).
Conclusions
In this work, we theoretically investigated the characteristic features of the oxidative addition of
nitrobenzene to Pd(BrettPhos) complex with the density functional theory method. The Ph-NO2
bond activation energy is 30.3 kcal/mol, which is larger than that (16.3 kcal/mol) of Ph-Br. Results
indicate that the Ph-NO2 bond activation is more difficult than Ph-Br, which is in consistent withprevious experiments. Interestingly, the electronic process of the oxidative addition of nitrobenzene
exhibits characteristic feature that is significantly different with bromobenzene. In Ph-NO2 bondactivation, charge transfer from Pd to NO2 is earlier than the charge transfer from Pd to Ph group,
while in the Ph-Br bond activation, the charge transfer from Pd to Br is later than the charge transferfrom Pd to Ph group. This is because the π* orbital of the NO2 group participates in the chargetransfer interaction of transition state. In this context, the characteristic feature in electronic processof Ph-NO2 bond activation originates from the participation of the π* orbital of the NO2 group.
Correspondingly, the distortion of nitrobenzene moiety in transition state is larger thanbromobenzene moiety because the sp2 orbital of NO2 must change its direction toward dπ orbital of
Pd to form bond interaction while Br does not change the direction of orbital, which is responsible
for the larger Ph-NO2 bond activation barrier. On the other hand, the BrettPhos isomer－ 154 －

Ⅳ 研究業績 (2016)(mono-phosphine) is unfavorable for the Ph-NO2 bond activation because dπ of Pd provided by
BrettPhos is at higher energy than that provided by BrettPhos isomer, which is more favorable forcharge transfer to Ph-NO2 moiety because the π of Ph interacts with dπ of Pd in an antibonding way.
On the other hand, the dπ orbital of Pd(PMe3)2 is more stable that need a larger distortion to activate
it. Therefore, the better dπ of Pd provided by BrettPhos effectively stabilizes intermediates,transition state, and product of Ph-NO2 bond activation that is an important reason why BrettPhos isbetter than usual phosphine ligands.
2. Original papers(1) Rong-Lin Zhong, Masahiro Nagaoka, Yoshiaki Nakao, and Shigeyoshi Sakaki,“ How to
Succeed Oxidative Addition of Nitrobenzene to Palladium(0) Complex: Characteristic Features inElectronic Process”，in preparation.
(2) Rong-Lin Zhong, Hong-Liang Xu, and Zhi-Ru Li, “The polar 2e/12c bond inphenalenyl-azaphenalenyl hetero-dimers: Stronger stacking interaction and fascinating interlayer
charge transfer”，J. Chem. Phys. 145, 054304 (2016).
(3) Rong-Lin Zhong, Hong-Liang Xu, and Zhong-Min Su, “Connecting effect on the first
hyperpolarizability of armchair carbon–boron–nitride heteronanotubes: pattern versus proportion”，
Phys. Chem. Chem. Phys., 18, 13954-13959 (2016)
3. Presentation at academic conferences
Rong-Lin Zhong, Masahiro Nagaoka, Yoshiaki Nakao, and Shigeyoshi Sakaki, “Theoretical Studyon Oxidative Addition of Nitrobenzene to Palladium(0)-Brettphos Complex” 多元素協働触媒による分子変換手法創出のための勉強会, Kyoto, March 15, 2017
4. Others－ 155 －

Ⅳ 研究業績 (2016)

Takahide Matsuoka
Research Fellow
1. Summary of the research of the year
Electron dynamics of photoionization of H2 in intense pulse laser fields
Photoionization process in intense pulse laser field, involves complex interplays among electrons,
nuclei, and laser-field. Namely, the charge resonance enhanced ionization, the interatomic Coulombic decay
and the above-threshold ionization are processes, which involves the electronic continuum states. Moreover,
the availability of X-ray laser pulse allows further investigations of auto-ionization and Auger effect, which
involves electronic correlations. Our present method effectively includes the ionization processes anddynamical correlations.
The outgoing electron flow from the molecular region per unit time is given as electron flux 𝒋𝒋𝒋𝒋⃗ atboundary surface 𝝏𝝏𝝏𝝏𝝏𝝏𝝏𝝏. The time-dependent electron wavepacket 𝚿𝚿𝚿𝚿(𝒕𝒕𝒕𝒕) is a complex wavefunction and thus
the natural orbitals 𝝓𝝓𝝓𝝓𝝀𝝀𝝀𝝀 of the wavepacket are also complex. Thereby the fluxes of the natural orbitals are
given as,𝒋𝒋𝒋𝒋⃗(𝝀𝝀𝝀𝝀) =ℏ ∗�⃗𝝓𝝓𝝓𝝓 − 𝝓𝝓𝝓𝝓𝝀𝝀𝝀𝝀 𝛁𝛁𝛁𝛁�⃗𝝓𝝓𝝓𝝓∗𝝀𝝀𝝀𝝀 �
�𝝓𝝓𝝓𝝓 𝛁𝛁𝛁𝛁𝟐𝟐𝟐𝟐i 𝝀𝝀𝝀𝝀 𝝀𝝀𝝀𝝀

The outgoing electron flux 𝒋𝒋𝒋𝒋⃗(𝝀𝝀𝝀𝝀) from each natural orbital 𝝓𝝓𝝓𝝓𝝀𝝀𝝀𝝀 reduces the occupation number 𝒏𝒏𝒏𝒏(𝝀𝝀𝝀𝝀) of thenatural orbital per unit time.

𝝏𝝏𝝏𝝏𝒏𝒏𝒏𝒏(𝝀𝝀𝝀𝝀)�⃗= � 𝒋𝒋𝒋𝒋⃗(𝝀𝝀𝝀𝝀) ∙ d𝑺𝑺𝑺𝑺
𝝏𝝏𝝏𝝏𝒕𝒕𝒕𝒕𝝏𝝏𝝏𝝏𝝏𝝏𝝏𝝏

By scaling the norm of the complex natural orbitals 𝝓𝝓𝝓𝝓𝝀𝝀𝝀𝝀 with the reduced occupation number, the outgoing

electron flow is effectively taken into account by the reduced electron density of the wavepacket 𝚿𝚿𝚿𝚿(𝒕𝒕𝒕𝒕). The

scaling of the natural orbitals is incorporated by scaling the Slater determinants of the natural orbitals, inwhich the wavepacket 𝚿𝚿𝚿𝚿(𝒕𝒕𝒕𝒕) is expanded, as follows [1],𝚿𝚿𝚿𝚿(𝒕𝒕𝒕𝒕) = � 𝑪𝑪𝑪𝑪𝑰𝑰𝑰𝑰 𝚽𝚽𝚽𝚽𝑰𝑰𝑰𝑰 → 𝚿𝚿𝚿𝚿 ′ (𝒕𝒕𝒕𝒕) = � �� �
𝑰𝑰𝑰𝑰

𝑰𝑰𝑰𝑰

𝒊𝒊𝒊𝒊

𝒏𝒏𝒏𝒏𝑰𝑰𝑰𝑰,𝒊𝒊𝒊𝒊 (𝒕𝒕𝒕𝒕𝒕𝒕)
� 𝑪𝑪𝑪𝑪𝑰𝑰𝑰𝑰 𝚽𝚽𝚽𝚽𝑰𝑰𝑰𝑰
𝒏𝒏𝒏𝒏𝑰𝑰𝑰𝑰,𝒊𝒊𝒊𝒊 (𝒕𝒕𝒕𝒕)

The continuity equation is integrated only for electron flux which is above threshold 𝒋𝒋𝒋𝒋thresh for ionization
with external field taken into consideration.

The occupation number of hydrogen molecule in 580 TW/ cm2 two-cycle laser pulse with wavelength

760 nm shows significant decrease while at the peak of the laser pulse (Fig. 1). The radiation spectra ofhydrogen molecule showed odd-order peaks (due to rapid acceleration of dipole in Fig. 2 (a)) with finestructures, which is unique in molecular systems (Fig. 2 (b)). The fine structures are also seen in the electron
flux of the time-dependent wavepacket, which reflect the recollision process between the electron and parent－ 156 －

Ⅳ 研究業績 (2016)

Figure 2. (a) Electric field (green), dipole moment of the system(blue), and dipole acceleration (red). (b) Power spectra of H2
Figure 1. Time propagation of themolecule.

natural orbital with largest occupation

ion. The rapid stroke of acceleration is seen during the second

number of H2 in intense laser field.

half cycle of the laser field, which eventually is when the first

The real part and imaginary part arerecollision of the electron and the parent ion takes place, and theshown in blue and red, respectively.

electron is accelerated. The repetitive recollision thus results in

The

in

high-order harmonic generation process in the intense laser fieldparentheses are the ones one the(Fig. 2(b)). The contribution of the nonadiabatic effect introduces

normalized wavepacket.

isotope effect to the ionization process. A significant anisotropic

occupation

numbers

behavior of the angular distribution of photoelectron of HD in
intense field is seen due to the electron flux induced by nuclear motion differs between proton and deuteron.

Photoionization of H2O in intense pulse laser fields
The photoionization process of 11B1 state H2O molecule with two 100 TW/cm2 185 nm laser pulses(FWHM being 8.27 fs) has also been calculated with the nonadiabatic electron dynamics method. HOH bondangle flips at t=20 fs and returns at t=40 fs, hence becomes linear at t=10 fs and 30 fs. The laser polarization
is fixed along the symmetry axis of H2O and the center of the laser pulse is set at t=10 fs and 30 fs. Therefore,
the laser intensity is at its maximum when H2O have a linear structure perpendicular to the laser polarization.
While the nuclear configuration is linear, the theoretical calculation counterintuitively resulted in significant
flux perpendicular to the laser polarization (Fig. 3 (a) thru (j)). Without the nonadiabatic interaction due tothe nuclear motion, the electron flux perpendicular to laser polarization is zero. Therefore, the perpendicularelectron flux arises from the bending motion of the nuclei. The angular distribution of the photoelectron flux,
which is the integrated electron flux at the boundary surface, also shows the strongest intensity at the linear
structure (Fig. 3 (k and l)).
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Ⅳ 研究業績 (2016)

Comparison between the results
with

and

interaction

withoutdue

tononadiabatic

nuclearmotionindicates strong contribution of thebending motion to the photoionization
process. The bending motion effects the
direction of the electron flux, i.e. with
the interaction, electron flows along the
OH bond, hence the angular distributionof the photoelectron is also seen along
the OH bond. Without the nonadiabatic
effect,thenegligible

electron
and

flux

thus

becomesalso

thephotoelectron cross-section. The result
implicates
nonadiabaticthesignificant

interaction

of

role

of

nuclearmotion in photoionization processes forgeneral cases of polyatomic molecules.
[1] K. Takatsuka, J. Phys. B 47, 124038(2014).

Figure 3. (a and b) Angular distribution of electron flux of
H2O. The thick solid curves indicate the polar angle of H
coordinates. (c thru j) Fluxes at selected times. Blue and red
indicate inward and outward fluxes, respectively. (k and l)
Angular distribution of photoelectron.

2. Original papers(1) Takahide Matsuoka, and Kazuo Takatsuka,“Dynamics of photoionization from molecular electronic wavepacket states in intense pulse
laser fields: A nonadiabatic electron wavepacket study”
J. Chem. Phys. 146, 134114 (2017).
3. Presentation at academic conferences(1) 松岡貴英・高塚和夫「強レーザー場中の励起分子からのイオン化過程の非断熱電子動力学」
第 19 回理論化学討論会 新宿 2016/5/25 3B19(2) 松岡貴英・高塚和夫－ 158 －

Ⅳ 研究業績 (2016)「強光子場中多原子分子の電離過程における非断熱電子動力学」
第 10 回分子科学討論会 2016 神戸 2016/9/14 2A15
(3) Takahide Matsuoka, and Kazuo Takatsuka,“Dynamics of photoionization from molecular electronic wavepacket states in intense pulse
laser fields”
77th Okazaki Conference Series: International Symposium on Ultrafast Dynamics in
Molecular and Material Sciences (P03), Okazaki, May 6, 2017

－ 159 －

Ⅳ 研究業績 (2016)

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機構の理論的研究を行った．
【序】光触媒的な電荷分離は，
光のエネルギーを別の形に変換して固定するための，鍵となる反応である．天然光合成系では，最終的に水を分解してプロトンと電子を取り出し，このような電荷分離状態を実現する．
この反応は，光化学系 II (PSII)

図 1 モデル系の概念図．EPD，EA，そして PA はそれ中の oxygen-evolving complex

ぞれ，electron-proton donor，electron acceptor，そして(OEC) に触媒される．今日では， proton acceptor を意味する． HTn (n = 1, 2) とラベルさ
OEC は Mn4CaO5 だと考えられている.[1] 我々は，この水分解サイクルの動力学的機構の解明を進めている．本講演
では，Mn クラスターによる電荷分離の基本的な機構，coupled proton-electron transfer [2]に基づいて，その初期段階であるプロトンと電子の分離について考察し，特にアクセプ
ター側の役割に注目する．
【方法論】OEC 周辺の X 線構造 [1] に基づいて，図 1a に示すようなモデル系を考える．このモデル系は，Ω－OH2 (Ω = MnOH or MnCa(OH)3)，HO－C6H4－NH3+，そして[R－C3N2H2]－ (R = H) からなり，PSII の OEC，P680 + YZ，そして D1-H190 にそれぞれ対応する．OEC による水分解にさきがけて，P680 からは電子が，D1-H190 からはプロトンが，それぞれ移動済みであると仮定し，それを正および負電荷で表現する．図 1b に示すように，HT1 は基底状態で PA 側に移動する．図 1b の構造から光励起状態を考え，全自由度の非断熱動力学を解析する．特に HT2 の運動と，それにカップルする電子の運動に注目する．

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Ⅳ 研究業績 (2016)

図 2 Ω = MnCa(OH)3 の場合の，励起状態の反応経路に沿った構造の時間変化と，それと couple する
不対電子密度の空間分布の時間変化のスナップショット．

動力学計算は，path-branching representation に基づく.[3] この理論では，電子波束
Ψ(R, r, 𝑡𝑡𝑡𝑡) = ∑𝐼𝐼𝐼𝐼 𝐶𝐶𝐶𝐶𝐼𝐼𝐼𝐼 (𝑡𝑡𝑡𝑡)Φ𝐼𝐼𝐼𝐼 (𝐫𝐫𝐫𝐫; 𝐑𝐑𝐑𝐑(𝑡𝑡𝑡𝑡)) が，反応経路に沿って時間発展する．ここで，R, r, t はそれぞれ原子核，電子，時間の座標である．Φ𝐼𝐼𝐼𝐼 (𝐫𝐫𝐫𝐫; 𝐑𝐑𝐑𝐑(𝑡𝑡𝑡𝑡))は核座標𝐑𝐑𝐑𝐑(𝑡𝑡𝑡𝑡)をパラメータとする量子化学計算によって求める．そして，電子の運動方程式は次式で表される．
(𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒)𝑖𝑖𝑖𝑖𝑖𝑖𝐶𝐶𝐶𝐶𝐼𝐼𝐼𝐼̇ = �(𝐻𝐻𝐻𝐻𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 − 𝑖𝑖𝑖𝑖𝑖𝑖 � 𝑖𝑖𝑖𝑖̇𝑘𝑘𝑘𝑘 𝑋𝑋𝑋𝑋𝐼𝐼𝐼𝐼𝑘𝑘𝑘𝑘𝐼𝐼𝐼𝐼 −𝑖𝑖2∗
�(𝑌𝑌𝑌𝑌𝐼𝐼𝐼𝐼𝑘𝑘𝑘𝑘𝐼𝐼𝐼𝐼 + 𝑌𝑌𝑌𝑌𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝑘𝑘𝑘𝑘 ))𝐶𝐶𝐶𝐶𝐼𝐼𝐼𝐼
4

𝐼𝐼𝐼𝐼
𝑘𝑘𝑘𝑘
𝑘𝑘𝑘𝑘
(𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒)
ここで，
𝐻𝐻𝐻𝐻𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 は電子の Hamiltonian で，𝑋𝑋𝑋𝑋𝐼𝐼𝐼𝐼𝑘𝑘𝑘𝑘𝐼𝐼𝐼𝐼 = 〈Φ𝐼𝐼𝐼𝐼 |𝜕𝜕𝜕𝜕Φ𝐼𝐼𝐼𝐼 /𝜕𝜕𝜕𝜕𝑖𝑖𝑖𝑖𝑘𝑘𝑘𝑘 〉, 𝑌𝑌𝑌𝑌𝐼𝐼𝐼𝐼𝑘𝑘𝑘𝑘𝐼𝐼𝐼𝐼 = 〈Φ𝐼𝐼𝐼𝐼 |𝜕𝜕𝜕𝜕 2 Φ𝐼𝐼𝐼𝐼 /𝜕𝜕𝜕𝜕𝑖𝑖𝑖𝑖𝑘𝑘𝑘𝑘2 〉である．
また，原子核は force matrix 𝐹𝐹𝐹𝐹𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 = 〈Φ𝐼𝐼𝐼𝐼 �𝜕𝜕𝜕𝜕𝐻𝐻𝐻𝐻 (𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒) /𝜕𝜕𝜕𝜕𝑖𝑖𝑖𝑖𝑘𝑘𝑘𝑘 �Φ𝐼𝐼𝐼𝐼 〉に駆動される．

【結果と考察】光励起状態の非断熱動力学の解析から，図 2 に示すような，プロトンと電子が別々の経路を通って，別々の場所に移動する機構が得られた．Ω = MnOH の場合にも，定性的に同じ機構が得られる．EPD と EA の間プロトン移動は，局所的に見れば，基底状態に類似する．一方で電子は，プロトンを迂回するように移動し，EA のRydberg-like state に至る．図 1a の状態から考えると，プロトンはリレーによって結果的に PA に移動し，電子は EA に移動する．そして，それぞれ負および正電荷をキャンセルする．プロトンと電子の分岐点は，形式的には EA の O 原子であり，その周辺の構造
が Y の字を連想させることから，この機構を Y-shaped coupled proton electron-wavepacket
transfer (Y-shaped CPEWT) と呼ぶ．基底状態では，プロトン移動は起こるものの，このような電子移動は起こらない．
アクセプターがこのように Y 字型である利点のひとつは，d-d state への非断熱遷移に伴う電荷再結合が抑制されることである．Ω = MnOH の場合，Schiff 塩基をアクセプタ
ーとした先行研究 [2] では一回で 25%程度が d-d state に非断熱遷移するが，Y 字型では3%程度になる．さらに，Ca が加わることによってそれは 0.3%程度まで抑えられる．
参考文献－ 161 －

ーとした先行研究 [2] では一回で 25%程度が d-d state に非断熱遷移するが，Y 字型では3%程度になる．さらに，Ca が加わることによってそれは 0.3%程度まで抑えられる．

Ⅳ 研究業績 (2016)

参考文献[1] Y. Umena, K. Kawakami, J.-R. Shen, and N. Kamiya, Nature 473, 55 (2011).
[2] K. Yamamoto and K. Takatsuka, Chem. Phys. 475, 39 (2016).
[3] T. Yonehara, K. Hanaksaki, and K. Takatsuka, Chem. Rev. 112, 499 (2012).

2. 論文(1) Kentaro YAMAMOTO and Kazuo TAKATSUKA,“Dynamical mechanism of charge separation by photoexcited generation of proton–
electron pairs in organic molecular systems. A nonadiabatic electron wavepacket dynamics
study”
Chem. Phys. 475, 39-53 (2016)(2) Kentaro YAMAMOTO and Kazuo TAKATSUKA,“Photoinduced Charge Separation Catalyzed by Manganese Oxides onto a Y-Shaped
Branching Acceptor Efficiently Preventing Charge Recombination”
ChemPhysChem. 18, 537-548 (2016)

3. 学会発表(1) 山本憲太郎，高塚和夫「Photochemical mechanism of charge separation taken out of water molecule」第 19 回理論化学討論会, 東京 2016/5/23-25 3B18.
(2) 山本憲太郎，高塚和夫「 光 化 学 系 II に お け る 水 分 解 の 初 期 段 階 の 機 構 に つ い て ; Y 字 型 Coupled
Proton-Electron Transfer」第 10 回分子科学討論会, 神戸 2016/9/13-15 1F13.
(3) Kentaro Yamamoto and Kazuo Takatsuka“Photoinduced Charge Separation Catalyzed by
Mn-Oxides onto a Y-shaped Branching Acceptor Efficiently Preventing Charge
Recombination”, 第 14 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 2017/1/27 P9.
(4) Kentaro Yamamoto and Kazuo Takatsuka “ Photodynamical electron-wavepacket
mechanism of water-splitting catalyzed by manganese oxides involving hydrogen-bondnetwork”, The 77th Okazaki Conference Series: International Symposium on Ultrafast
Dynamics in Molecular and Material Sciences”, Okazaki, Japan, 2017/3/6-8 P06.
－ 162 －

Ⅳ 研究業績 (2016)

７．共同研究員

Yanying
Yanying Zhao
Zhao
Visiting Scholar
Visiting Scholar
1. Summary of the research of the year
(1) Theoretical
StudyofExcitedState
Proton5-substituted-1,3,4-thiodizole-2-thione molecules by GRRM

Transferin

The photophysics and photochemistry of thiocarbonyls were reviewed by Maciejewski andSteer. Previous studies revealed that the thione forms of small thioamides were much more stable
than the thiol tautomers in the ground electronic state. The calculated energy difference between thethione and thiol forms of thioacetamide was 39.1 kJ mol, which precluded thermal population of thethiol form of thioacetamide in the ground electronic state due to a large transition energy barrier.
The UV-induced HN–C=S → N=C–SH excited state proton transfer (ESPT) reaction leading to theconversion of thione to thiol was observed for a number of matrix-isolated thioamides. The ESPT
reaction is fundamentally different from the classic excited state intramolecular proton transfer(ESIPT) process. ESIPT refers in particular to the proton transfer reaction within an intramolecularhydrogen bond (−C=O···H–NC−). This is fulfilled neither for the heterocyclic compounds nor forthioacetamide.
Here, we theoretically investigated the excited state decay mechanism of
5-substituted-1,3,4-thiadizole-2-thione molecules (Scheme 1) by GRRM method. We carried out
geometry optimization using the TD-DFT method. The excited state minima S1, S2 and T1,
minimum energy conical intersection and seam crossing points are explored using SC-AFIR method.
The results from theoretical calculation are able to interpret our resonance Raman spectroscopic
results. The excited state reaction mechanism is tentatively proposed as S0→S2→S2/S1 or
S2/Tn→S1/S0 or T1/S0→ S0'.

S

S

2
3

N

1

5
4

R

N

S

HS
N

H

Scheme 1－ 163 －RN

Ⅳ 研究業績 (2016)(2) Exploring water micro-solvation role in Pd-Catalyzed Ring-Opening Borylation of
2-Arylaziridines(AZ) by Artificial Force-Induced Reaction method in the global
reaction route mapping (GRRM)
The active species PdL2 initiates the aziridine ring opening borylation reaction of
2-arylaziridines by experiments and calculations, which opens up and avenue to the further
development of transition metal-catalyzed ring opening C-E bond forming cross couplings ofaziridines. H2O illustrates fundamentally important role in Pd-catalyzed regioselective
borylative ring-opening rection. The multi-component artificial force-induced reaction(MC-AFIR) method in the global reaction route mapping (GRRM) strategy determines all of thelocal minima (LMs) of the hydrogen-bonding equilibrium structures of intermediates III and VI
and transition states (TSs) for subsequent reaction paths systematically. The mechanism
proposed herein indicates the amount of water does not affect the ring-opening regioselectivity
both in the experiments and calculations, however, definite

amount of H2O molecules canstabilize the reaction intermediates via hydrogen bonding chain of H2O cluster and push thesubsequent reaction. At the same time, H2O increase the barrier for the side reaction. And theimportant role of H2O are further explained in aziridine ring-opening, the proton transfer, ligand
dissociation/association and B-B bond cleavage reaction process. The revised catalytic cycle is
proposed.
The full catalytic cycle consists of a selectivity-determining aziridine ring opening(oxidative addition), a proton transfer, phosphine ligand dissociation from the catalyst,
boron–boron bond cleavage, and reductive elimination. Importantly, H2O plays an indespensible
role in the proton transfer step by H2O hydrogen bond chain, including to quench TSN- as aproton source, and form the [Pd(OH)] species as an internal base, and further stabilize thereaction intermediates and pushing subsequent reactions, such as B-B bond cleavage.

－ 164 －

Ⅳ 研究業績 (2016)

Water plays important roles in thereaction process:(1) As a proton source toe quench
TsN-.
(2) As an internal base to form the[Pd(OH)] species.
(3) Stabilize
thereactionintermediates.

Propose catalytic cycle.

Chem. Sci., 2016, 7, 6141

aechanism

H2O in solution do not play a major role on the stabilityof TSII-III and intermediate IV?

Our Objective:(1) /onfirm theimportant roleof the H2O on
the reaction
process.
(2) Explainthemechanism ofwater drivingonthephosphine
liganddissociationand .-. bondcleavage.

H2O in solution stabilizes the intermediate III

Energies are indicated in kcal/mol-1. ΔG values are in plain text, and ΔE values are in italics.

－ 165 －

Chem. Sci., 2016, 7, 6141.

Ⅳ 研究業績 (2016)

2. Original papers(1) Pang, Sumei, Zhao Yanying*, Xue Jiadan, Zheng Xuming. "Solvent-dependent dynamics ofhydrogen bonding structure 5-(methylthio)-1, 3, 4-thiadiazole-2 (3H)-thione as determined by
Raman spectroscopy and theoretical calculation." Spectrochimica Acta Part A: Molecular andBiomolecular Spectroscopy 171 (2017): 470-477.
(2) Liu, Xin, and Yanying Zhao*. "Adsorption Kinetics of Methylene Blue on Synthesized
DMF-MIL-101 (Cr), a DMF-functionalized Metal-organic Framework." Key Engineering
Materials 671 (2016).
(3) Chen Xiao, Zhao Yanying*, Zhang Haibo, Xue jiadan, Zheng Xuming* Excited state protontransfer dynamics of thioacetamide in S2(π-π*) state: resonance Raman spectroscopic andquantum mechanical calculations study. J. Phys. Chem. A 119, 832-842(2015)(4) Zhao Yanying, Xu Qiang* Chapter 15, Metal-organic frameworks as platforms for hydrogengeneration from chemical hydrides in Organometallics and Related Molecules for Energy
Conversion, Green Chemistry and Sustainable Technology. Springer-Verlag Berlin Heidelberg
421-467(2015). W.-Y. Wong (ed.),

DOI 10.1007/978-3-662-46054-2_15.

(5) Li Dan, Zhao Yanying*, Xue Jia-Dan, Zheng Xuming Structural dynamics of 4-formaldehyde
imidazole and imidazole in light absorbing S2(π-π*) state Journal of Raman Sepctroscopy 46(3),293-301(2015).
(6) Zhao Yanying*, Zhang Yuchen, Liu Xin, Zheng Xuming Formation, characterization, structure
and bonding analysis of the metal-carbon bond OM-(ŋ6-C6H6) (M = Sc, Ti) complexes in solid
matrix: Infrared spectroscopic and theoretical study. J. Orgmet. Chem. 777, 25-30(2015)
3. Presentation at academic conferences
4. Others－ 166 －

Ⅳ 研究業績 (2016)

Ming-Chung Yang
Ming-Chung Yang
Postdoctoral research fellow
Postdoctoral research fellow(National Chiayi University, Department of Applied chemistry)(National Chiayi University, Department of Applied chemistry)
1. Summary of the research of the year
The importance of Metal-Carbon Back-Bonding to the Stability of Fullerene-Transition metal
complexes and the role of Cage Sizes, Encapsulated Ions and Metal Fragments
A density functional study of {η2-(X@Cn)}ML2 complexes with various cage sizes (C60、C70、
C76、C84、C90、C96), encapsulated ions (X = F-, 0, Li+) and metal fragments (M = Pt、Pd) is performed,
using M06/LANL2DZ levels of theory. The importance of π back-bonding to the thermodynamic
stability of fullerene-transition metal complexes ({η2-(X@Cn)}ML2) and the effect of encapsulatedions, metal fragments and cage sizes on the π back-bonding are determined in this study. The
theoretical computations suggest that π back-bonding plays an essential role in the formation offullerene-transition metal complexes. The theoretical evidence also suggests that there is no linear
correlation between cage sizes and π back-bonding, but the encapsulated Li+ ion enhances πback-bonding and F- ion results in its deterioration. These computations also show that a platinum
center produces stronger π back-bonding than a palladium center. It is hoped that the conclusions
that are provided by this study can be used in the design, synthesis and growth of novel
fullerene-transition complexes.

Scheme 1. The sites of attack for addition to the fullerenes Ih-C60, D5h-C70, D2-C76, D2d(23)-C84,
D5h(1)-C90 and D5h(1)-C96. The Hückel π bond orders (B) were calculated using the freeware－ 167 －

Ⅳ 研究業績 (2016)

program, HuLiS.

Figure 1. Optimized geometries for {η2-(X@C60)}ML2 (M = Pt, Pd; X = Li+, 0 , F-)

Figure 2. The correlation between ΔE1 and cage sizes for {η2-(X@Cn)}PtL2 (n = 60, 70, 76, 84, 90
and 96) complexes. The blue, red and black lines represent the respective values for ΔE1 for X = Li+,
0 and F-.
－ 168 －

Ⅳ 研究業績 (2016)

2. Original papers(1) Ming-Chung Yang, Akhilesh K. Sharma, W. M. C. Sameera, Keiji Morokuma, and Ming-Der Su
Theoretical Study of Addition Reactions of L4M (M = Rh, Ir) and L2M (M = Pd, Pt) to Li+@C60.
The Journal of Physical Chemistry A, 2017, 121, 2665-2673.
(2) Jia-Syun Lu, Ming-Chung Yang, and Ming-Der Su Indium–Arsenic Molecules with an In≡As
Triple Bond: A Theoretical Approach. ACS Omega, 2017, 2, 1172–1179.
(3) Jia-Syun Lu, Ming-Chung Yang and Ming-Der Su. The effect of substituents on triply bonded
boron≡antimony molecules: a theoretical approach. Phys. Chem. Chem. Phys., 2017, 19,8026-8033.
(4) Jia-Syun Lu, Ming-Chung Yang and Ming-Der Su. The Effect of Substituents on the Stability of
Triply Bonded Gallium≡Antimony Molecules: A New Target for Synthesis. Dalton Transactions,2017, 46, 1848-1856.
(5) Jia-Syun Lu, Shih-Hao Su, Ming-Chung Yang, Xiang-Ting Wen, Jia-Zhen Xie, and Ming-Der
Su Substituent Effects on Boron–Bismuth Triple Bond: A New Target for Synthesis.
Organometallics, 2016, 35, 3924–3931.

－ 169 －

Ⅳ 研究業績 (2016)

８．日本学術振興会外国人特別研究員
Xue-Feng Ren
Xue-Feng
Ren
Research Fellow
Fellow
Research

1. Summary of the research of the year
Computational Insights on the Emission Decay Way of Facial and Meridional
Tris-cyclometalated Iridium(III) Complexes
Significant attractions have been focused on synthesis d6 complexes due to theirs extreme
widely used in variety photocatalysis and photoelectrochemistry. The Ir(III) chelates complexes
have been widely synthesized because of their long excited-state lifetimes and high efficiencies. In
viewing this, a series of tris-cyclometalates of Ir(III) had been reported by either facial (fac)meridional (mer) isomers. The photophysical properties of both facial and meridional complexes
have also been examined and show distinct differences between the two forms, especially for theproperties of excited state. The emission wavelengths of meridional forms are red shifted comparedwith its facial complexes. Furthermore, the luminescent quantum efficiencies (Φ) and lifetimes (t)of fac-Ir(III) complexes are ten times larger than that of mer-Ir(III) complexes. The radiative decay
rates (Kr) of these complexes under fac- and me- configurations are similar with each other, while
the nonradiative decay rates (Knr) of mer-Ir(III) complexes are ten times larger than that of
fac-Ir(III) complexes. The mechanism of emission decay is not established and there is no clear
understanding on the origin of the dramatically differences on the Knr. We have studied the emission
decay of this kind of isomers using DFT methods. The SC-AFIR method is implemented in GRRM
program is employed to locate the minimum energy seam of crossing (MESXs).
isomersC^N ligand

Figure 1. The scheme of studied molecules
The emission decay leads to distort the phenyl ring of the ppy ligand and Ir-N1 bond break.
The MESX of mer-Ir(ppy)3 is lower than T1 state at the FC region by 21.15kJ/mol, while the energy
differences between the MESX of fac-Ir(ppy)3 and T1 at the FC state is less than 1 kJ/mol. Thismeans that the quenching pathway of mer-Ir(ppy)3 is favorable compared with its facial isomer.
Furthermore, the energy barrier from the T1-m to MESX of mer-Ir(ppy)3 is found to be much lower－ 170 －

Ⅳ 研究業績 (2016)

than that of fac-Ir(ppy)3. Therefore, the calculated results can fully explain the experimental
data(Knr is 3.2×105 and 6.4×106 for fac-Ir(ppy)3 and mer-Ir(ppy)3, respectively).
300.00fac-Ir(ppy)3

T1

T1'

277.49274.66250.00273.17

TS

247.63257.42T1-m

200.00hv

150.00

MESX

152.05

0.00

N

CC
NC
1

Ir

T1' MESX
T1-m
TS
C-C-C-N 1.16 -24.28 -49.09 -50.30
Ir-N1
2.156 2.785 3.374 3.448

100.0050.00

N274.73274.65

25.13

0.00

mer-Ir(ppy)3
300.00250.00200.00150.00T1
258.90TS

MESX

242.78228.80

T1-m

hv

Ir

237.75N

141.00

0.00

CC
NC
1

MESX
T1-m
TS
C-C-C-N -5.15 -27.06 -50.6
Ir-N1
3.419
2.349 2.855

100.0050.00

N237.7544.11
0.00

Figure 2. The emission decay of fac-Ir(ppy)3 and mer-Ir(ppy)3 obtained by B3LYP method
fac-Ir(46dfppy)3
300.00250.00T1

229.90258.20T1-m

200.00150.00TS264.23

T1'

251.36
237.63N

253.08253.05

F

50.00

T1

288.03250.00200.00258.07TS

264.13

T1-m

hv

F

N

MESX

F

254.74254.68Ir
N

119.75100.00
50.00

F

F

F

150.00

0.00

F

7.60

0.00

mer-Ir(46dfppy)3
300.00CC
N1C

T1' MESX
T1-m
TS
C-C-C-N1 -1.69 -18.96 -50.15 -56.01
Ir-N1
2.193 2.667 3.382 3.457

102.25100.00350.00

N

Ir

F

hv

0.00

F

F

MESX

C-C-C-N1
Ir-N1

45.96
0.00

CC
N1C

F

F

T1-m
MESX
TS
-6.84 -20.78 -50.97
3.429
2.337 2.686

Figure 3. The emission decay of fac-Ir(46dfppy)3 and mer-Ir(46dfppy)3 obtained by B3LYP method
As depicted in Figure 3, by the introduction of the fluorine at the ppy ligand, the MESX of
fac-Ir(46dfppy)3 is 11.15kJ/mol lower than corresponding T1 state at the FC geometry, and theenergy barrier is 28.30 kJ/mol. This means the decay process of fac-Ir(46dfppy)3 from the T1 state ismore probable compared with fac-Ir(ppy)3, which is consistent with the large Knr value (3.6×105)－ 171 －

Ⅳ 研究業績 (2016)

relative to fac-Ir(ppy)3. Follow this coordinate, the mer-Ir(46dfppy)3 has much small MESX lower
than the FC state(33.28kJ/mol) and smaller energy barrier (6.06kJ/mol), thus it has efficientquenching pathway.
300.00fac-Ir(tpy)3T

1
274.54250.00247.08TS

T1-m

200.00150.00279.16hv

T

1'
274.48260.39MESX
276.72276.69

N

CC
N1C

Ir

50.00
0.00

T1' MESX
T1-m
TS
C-C-C-N1 -1.46 -23.61 -48.32 -50.22
Ir-N1
2.207 2.789 3.378 3.448

24.88

mer-Ir(tpy)3
300.00250.00230.03240.87TS

240.77

H3C

Ir
N

CC
N1C

T1-m
MESX
TS
C-C-C-N1 -5.22 -26.35 -50.54
3.421
Ir-N1
2.348 2.843

138.70

50.00

N

CH3

hv

100.000.00

MESX

243.98T1-m

200.00150.00CH3

T1

260.26CH3

CH3

153.04100.00

0.00

N
H3C

42.79
0.00

Figure 4. The emission decay of fac-Ir(tpy)3 and mer-Ir(tpy)3 obtained by B3LYP method
As depicted in Figure 4, by the introduction of the methyl at the ppy ligand, the MESX of
fac-Ir(tpy)3 is larger than corresponding T1 state at the FC geometry, and the energy barrier is
32.08kJ/mol. This means the decay process of fac-Ir(tpy)3 from the T1 state is less probablecompared with fac-Ir(ppy)3, which is consistent with the small Knr value (2.5×105) relative to
fac-Ir(ppy)3. The mer-Ir(tpy)3 has small energy lower than FC (19.39kJ/mol) and energy barrier(13.95kJ/mol) compared with fac-Ir(tpy)3, therefore the quenching pathway is more favorable
compared with that of fac-Ir(tpy)3.
2. Original papers
Xue Feng Ren and Keiji Morokumma, “Emission Decay Way of a series of Facial and
Meridional Tris-cyclometalated Iridium(III) Complexes”, In preparation.
3. Presentation at academic conferences(1) Xue Feng Ren and Keiji Morokumma“The effect of intramolecular Hydrogen Bond on the Mechanism of Exicted state Decay of
Iridium(III) Complexes”, The 10th Annual Meeting of Japan Society for Molecular Science,
2016,9,13-15, KOBE fashion mart, Poster－ 172 －

Ⅴ 資料 (2016)

Ⅴ資料

１．研究業績一覧（平成 28 年度）№

水野

Authors

Title

JournalVolume (Number),first page tolast page

year

英如

1

H. Mizuno, L. E. Silbert, and
M. Sperl

Spatial Distributions of Local Elastic
Moduli Near the Jamming Transition

Physical Review
Letters

Vol.116,
p.068302(5pages)

2016

2

K. Saitoh and H. Mizuno

Anomalous energy cascades in dense
granular materials yielding under simple
shear deformations

Soft Matter

Vol.12, p.13601367 (8pages)

2016

3

H. Mizuno, L. E. Silbert, M.
Sperl, S. Mossa, and J.-L.
BarratCut-off nonlinearities in the lowtemperature vibrations of glasses andcrystals

Physical Review
E

Vol.93,
p.043314(18pages)

2016

4

H. Mizuno, K. Saitoh, and L.
E. Silbert

Elastic moduli and vibrational modes injammed particulate packings

Physical Review
E

Vol.93,
p.062905(21pages)

2016

5

K. Saitoh and H. Mizuno

Enstrophy cascades in two-dimensional
dense granular flows

Physical Review
E

Vol.94,
p.022908(11pages)

2016

6

H. Mizuno, S. Mossa, and J.L. Barrat

Relation of vibrational excitations
and thermal conductivity to elastic
heterogeneities in disordered solids

Physical Review
B

Vol.94,
p.144303(22pages)

20167

Yoshio Nishimoto and Dmitri
G. Fedorov

The fragment molecular orbital method
combined with density-functional tightbinding and the polarizable continuum
model

Phys. Chem.
Chem. Phys.

18(32), 2199722734

2016

8

Hiroya Nakata, Yoshio
Nishimoto, and Dmitri G.
Fedorov

Analytic second derivative of the energy
for density-functional tight-binding
combined with the fragment molecularorbital method

J. Chem. Phys.

145(4), 044113

2016

9

Yoshio Nishimoto andStephan Irle

Quantum Chemical Prediction ofVibrational Spectra of Large Molecular
Systems with Radial or Metallic
Electronic Structure

Chem. Phys.
Lett.

667, 317-321

2017

10

Yoshio Nishimoto and Dmitri
G. Fedorov

Three-body expansion of the fragment
molecular orbital method combined withdensity-functional tight-binding

J. Comput.
Chem.

38(7), 406-418

2017

Yoshio Nishimoto

Analytic Hyperpolarizability andPolarizability Derivative with Fractional
Occupation Numbers for Large Extended
Systems

J. Chem. Phys.

146(8), 084101

2017

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

Chem. Rec16, 2349-2363

2016

西本

11

諸熊
12

佳央

奎治
W. M. C. Sameera, Akhilesh
Kumar Sharma, Satoshi
Maeda,Keiji Morokuma－ 173 －

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Volume (Number),first page tolast pageyear

Chem. Sci.,

7, 6141-6152

2016

Computational Catalysis Using theArtificial Force Induced Reaction Method

Acc. Chem. Res.

49 (4), 763-773

2016

Shunsuke Sasaki, Satoshi
Suzuki, W. M. C. Sameera,
Kazunobu Igawa, Keiji
Morokuma, Gen-ichi Konishi

Highly Twisted N,N-Dialkylamines as a
Design Strategy to Tune Simple Aromatic
Hydrocarbons as Steric EnvironmentSensitive Fluorophores

J. Am. Chem.
Soc.

138 (26), 81948206

2016

16

Hu-Jun Qian, Ying Wang
Keiji Morokuma

Quantum mechanical simulation
reveals the role of cold helium atoms
and the coexistence of bottom-up andtop-down formation mechanisms ofbuckminsterfullerene from carbon vapor

Carbon14, 635-641

2017

17

Ryo Nakano, Lung Wa
Chun, Yumiko Watanabe,
Yoshishige Okuno, Yoshikuni
Okumura, Shingo Ito, Keiji
Morokuma, and Kyoko
Nozaki

Elucidating the Key Role of Phosphine−
Sulfonate Ligands in Palladium-Catalyzed
Ethylene Polymerization: Effect of Ligand
Structure on the Molecular Weight andLinearity of Polyethylene

ACS Catal.,

6, 6101-6113

2016

18

Menggai Jiao, Wei Song,
Hu-Jun Qian, Ying Wang,
Zhijian Wu, Stephan Irle,
Keiji Morokuma

QM/MD studies on graphene growthfrom small islands on the Ni(111) surface

Nanoscale8, 3067-3074

2016

19

Satoshi Maeda, Yu
Harabuchi, Makito Takagi,
Tetsuya Taketsugu, Keiji
Morokuma

Artificial Force Induced Reaction (AFIR)
Method for Exploring Quantum Chemical
Potential Energy Surfaces

Chem. Rec.

16, 2232-2248

2016

20

Yuanying Li, Fengyi Liu,
Bin Wang, Qingqing Su,
Wenliang Wang, Keiji
Morokuma

Different conical intersections control
nonadiabatic photochemistry of fluorene
light-driven molecular rotary motor: A
CASSCF and spin-flip DFT study

The Journalof Chemical
Physics

145, 244311

2016

21

Anna V. Pomogaeva, Keiji
Morokuma, and Alexey Y.
Timoshkin

Trimeric Cluster of Lithium
Amidoborane—The Smallest Unit for
the Modeling of Hydrogen Release
Mechanism

Journal ofComputational
Chemistry

37, 1259-1264

2016

22

Miho Hatanaka, Yuichi Hirai,
Yuichi Kitagawa, Takayuki
Nakanishi, Yasuchika
Hasegawa, Keiji Morokuma

Organic linkers control thethermosensitivity of the emission
intensities from Tb(III) and Eu(III) in achameleon polymer

Chem. Sci.,

8, 423-429

2017

23

Naokazu Kano, Nathan J.
O'Brien, Ryohei Uematsu,
Romain Ramozzi, Keiji
Morokuma

Trihydroborates and Dihydroboranes
Bearing a Pentacoordinated Phosphorus
Atom: Double Ring Expansion To
Balance the Coordination States

Angew. Chem.

129, 5976-5979

2017

24

Hongyan Xiao, Yusuke
Kobayashi, Yoshiji Takemoto,Keiji Morokuma

Proton Transfer Mechanism ofOrganocatalyzed Isomerizationof Alkynoates into Allenoates:
Enantioselectivity and Reversibility. A
DFT Study

ACS Catal.

6,2988-2996

2016

№

Authors

Title

13

Youhei Takeda, Akinobu
Kuroda, W. M. C. Sameera,
Keiji Morokuma, Satoshi
Minakata

Palladium-catalyzed regioselective andstereo-invertive ring-opening borylationof 2-arylaziridines with bis(pinacolato)
diboron: experimental and computational
studies

14

W. M. C. Sameera, Satoshi
Maeda, Keiji Morokuma

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Authors

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25

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

Formation Mechanisms of Graphitic-N:
Oxygen Reduction and Nitrogen Dopingof Graphene Oxides

J. Phys. Chem. C

120, 5673-5681

2016

26

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

Computed Relative Populations of
D2 (22)-C84 Endohedrals with Encapsulated
Monomeric and Dimeric Water

Chem. Phys.
Chem.

17, 1109-1111

2016

27

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

Regioselective Multistep Reconstructionof Half-Saturated Zigzag Carbon
Nanotubes

J. Comput.
Chem.

37, 1363-1366

2016

28

Y. Takano, R. Tashita,
M. Suzuki, S. Nagase, H.
Imahori, and T. Akasaka

Molecular Location Sensing by
Anisotropic Magnetism of an Endohedral
Metallofullerene

J. Am. Chem.
Soc.

138, 8000-8005

2016

29

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

Strong Electronic Coupling and ElectronTransfer in a Ce2@Ih -C80-H2P Electron
Donor Acceptor Conjugate

Nanoscale8, 13257-13262

2016

30

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

Unconventional Electronic Structure andChlorination/Dechlorination Mechanismsof #1911C64 Fullerene

Inorg. Chem.

55, 6827-6829

2016

31

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

Stabilization of a Chlorinated #4348C66:C2v
Cage by Encapsulating Monometal
Species: Coordination between Metal andDouble Hexagon-Condensed Pentalenes

Inorg. Chem.

55, 7667-7675

2016

32

W. –J. Guan, P. Zhao, Q. –Z.
Li, S. Nagase, M. Ehara, and
X. Zhao

Sc3N@Cs(39715)-C82: A Missing Isomer
Linked to Sc3N@C2v(39718)-C82 by aSingle Step Stone-Wales Transformation

RSC Adv.

6, 75588-75593

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33

C. L. Wagner, L. Tao, E. J.
Thompson, T. A. Stich, J. –D. Guo, J. C. Fettinger, L.
A. Berben, R. D. Britt, S.
Nagase, and P. P. Power

Dispersion-Force-Assisted
Disproportionation: A Stable TwoCoordinate Copper (II) Complex

Angew. Chem.
Int. Ed.

55, 1044410447

2016

34

T. Kuwabara, M. Nakada,J. Hamada, J. –D. Guo, S.
Nagase, and M. Saito(h4-Butadiene)Sn(0) Complexes: A
New Approach for Zero-Valent p-Block
Elements Utilizing a Butadiene as a
4π-Electron Donor

J. Am. Chem.
Soc.

138, 1137811382

2016

35

Y. Suzuki, T. Sasamori, J. –D. Guo, S. Nagase, and N.
Tokitoh

Isolation and Ambident Reactivity of a
Chlorogermylenoid

Chem. Eur. J.

22, 1378413788

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36

A. W. Kyri, P. K. Majhi,
T. Sasamori, T. Agou, V.
Nesterov, J. –D. Guo, S.
Nagase, N. Tokitoh, and R.
StreubelSynthesis of a 1-Aryl-2,2chlorosily(phospha)silene Coordinated byan N-Heterocyclic Carbene

Molecules

21, 1309 (10pages)

2016

37

Y. Maeda, S. Minami, Y.
Takehana, J. –S. Dang,
S. Aota, K. Matsuda, Y.
Miyauchi, M. Yamada, M.
Suzuki, R. –S. Zhao, X.
Zhao, and S. Nagase

Tuning of the Photoluminescence and UpConversion Photoluminescence Propertiesof Single-Walled Carbon Nanotubes by
Chemical Functionalization

Nanoscale8, 16916-16921

2016

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茂

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Volume (Number),first page tolast pageyear

Chem. Eur. J.

22, 1537315379

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Reaction of a Stable Digermyne
with Acetylenes: Synthesis of
a 1,2-Digermabenzene and a
1,4-Digermabarrelene

Bull. Chem. Soc.
Jpn.

89, 1375-1384

2016

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

Dispersion Forces, Disproportionation,and Stable High-Valent Late Transition
Metal Alkyls

Angew. Chem.
Int. Ed.

55, 1476614769

2016

41

S. Tsukada, N. J. O’Brien, N.
Kano, T. Kawashima, J. –D.
Guo, and S. Nagase

The Synthesis and Structure of a
Dianionic Species with a Bond between
Pentacoordinated Tin Atoms: Bonding
Property of the Tin-Tin Bond

Dalton Trans.

45, 1937419379

2016

42

M. Suzuki, M. Yamada, Y.
Maeda, S. Sato, Y. Takano,
F. Uhlík, Z. Slanina, Y. Lian,
X. Lu, S. Nagase, M. M.
Olmstead, A. L. Balch, and T.
Akasaka

The Unanticipated Dimerization of Ce@
C2v(9)-C82 upon Cocrystallization with
Ni(octaethyporphyrin) and Comparison
with Monomeric M@C2v(9)-C82 (M = La,
Sc, and Y)

Chem. Eur. J.

22, 18115-18122

2016

43

M. Yamada, Y. Tanabe, J. –S.
Dang, S. Sato, N. Mizorogi,
M. Hachiya, M. Suzuki, T.
Abe, H. Kurihara, Y. Maeda,
X. Zhao, Y. Lian, S. Nagase,and T. Akasaka

D2d(23)-C84 versus Sc2C2@D2d(23)-C84:
Impact of Endohedral Sc2C2 Doping on
Chemical Reactivity in the Photolysis of
Diazirine

J. Am. Chem.
Soc.

138, 1652316532

2016

榊

茂好

44

Shinji Aono, Toshifumi Mori,and Shigeyoshi Sakaki Shinji
Aono, Toshifumi Mori, andShigeyoshi Sakaki

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

J. Chem. Theory
Comput.

12, 1189-1206

2016

45

Tetsuya Fukuda, Hisako
Hashimoto, Shigeyoshi
Sakaki, and Hiromi Tobita

Stabilization of a Silaaldehyde by its η2
Coordination to Tungsten

Inorg. Chem.

55, 188-192

2016

46

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

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

Angew. Chem.
Int. Ed.

137, 158-161

2016

47

Yuta Takano, Tomohiro
Numata, Kazuto Fujishima,
Kazuaki Miyake, Kazuya
Nakao, Wesley David
Grove, Ryuji Inoue, Mineko
Kengaku, Shigeyoshi
Sakaki, Yasuo Mori, Tatsuya
Murakami and Hiroshi
Imahori

Optical control of neuronal firing via
photoinduced electron transfer in donor–
acceptor conjugates

Chem. Sci.

7, 3331-3337

2016

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Authors

Title

38

Y. Maeda, E. Sone, A. Nishio,
Y. Amagai, W. –W. Wang,
M. Yamada, M. Suzuki, J.
Matsui, M. Mitsuishi, T.
Okazaki, and S. Nagase

Thermal Stability of Oxidized SingleWalled Carbon Nanotubes: Competitive
Elimination and Decomposition
Reaction Depending on their Degree ofFunctionalization

39

T. Sugahara, J. –D. Guo, T.
Sasamori, Y. Karatsu, Y.
Furukawa, A. E. Ferao, S.
Nagase, and N. Tokitoh

40－ 176 －

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Authors

Title

JournalVolume (Number),first page tolast page

year

48

Hajime Kameo, Koki
Ikeda, Shigeyoshi Sakaki,
Shin Takemoto, Hiroshi
Nakazawa, Hiroyuki
Matsuzaka,

Experimental and theoretical studies of
Si-Cl and Ge-Cl sigma-bond activation
reactions by iridium-hydride

Dalton Trans.

45, 7570-7580

2016

49

Hajime Kameo, Tatsuya
Kawamoto, Shigeyoshi
Sakaki, Didir Bourissou,
Hiroshi Nakazawa

Transition-Metal-Mediated Cleavageof Fluoro-Silanes under Mild
ConditionsTransition-Metal-MediatedCleavage of Fluoro-Silanes under Mild
Conditions

Chem. A Euro. J.

22, 2370-2375

2016

50

Hajime Kameo, Koki Ikeda,
Didir Bourissou, Shgeyoshi
Sakaki, Shin Takemoto,
Hiroshi Nakazawa, Hiroyuki
Matsuzaka

Transition-Metal-Mediated GermaniumFluorine Activation: Inverse Electron
Flow in sigma-Bond Metathesis

Organometallics

35, 713-719

2016

51

Koki Kikui, S. Hayaki, K.
Kido, Daisuke Yokogawa,K. Kasahara, Y. Matsumura,
Hirofumi Sato, Shigeyoshi
Sakaki,Solvent structure of ionic liquid withcarbon dioxide

J. Mol. Liq.

217, 12-16

2016

52

Kazuhiko Semba, Kenta
Ariyama, Hong Zheng,
Ryohei Kameyama,
Shigeyoshi Sakaki, Yoshiaki
Nakao

Reductive Cross-Coupling of ConjugatedArylalkenes and Aryl Bromides with Hydrosilanes by Cooperative Palladium/
Copper Catalysis

Angew. Chem.,
Int. Ed.

55, 6275-6278

2016

53

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

Theoretical Study of Hydrogenation
Catalysis of Phosphorus Compound andPrediction of Catalyst with High Activity
and Wide Application ScopeACS Cat.

6, 4859-4870

2016

54

Masayuki Nakagaki,
Shigeyoshi Sakaki,Hetero-dinuclear complexes of 3d metals
with a bridging dinitrogen ligand:theoretical prediction of the characteristicfeatures of geometry and spin multiplicity

Phys. Chem.
Chem. Phys.

18, 2636526375

2016

55

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

Catalytic Hydrogenation of Carbon
Dioxide with Ammonia-Borane by
Pincer-Type Phosphorus Compounds:
Theoretical Prediction

J. Am. Chem.
Soc.

138, 1348113484

2016

56

Shogo Okumura, Shuwei.
Tang, Teruya Saito, K.
Semba, Shigeyoshi Sakaki,
Yoshiaki Nakao

para-Selective Alkylation of Benzamides
and Aromatic Ketones by Cooperative
Nick-el/Aluminum Catalysis

J. Am. Chem.
Soc.

138, 1469914704

2016

Wei Guan, Guixinag Zeng,
Hajime Kameo, Yoshiaki
Nakao, Shigeyoshi Sakaki

Cooperative Catalysis of Combined
Systems of Transition-Metal Complexes
with Lewis Acids: Theoretical
UnderstandingCooperative Catalysis of
Combined Systems of Transition-Metal
Complexes with Lewis Acids: Theoretical
Understanding

Chem. Rec.

16, 2405-2425

2016

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Volume (Number),first page tolast pageyear

Chem. Lett.

45(6), 634-636

2016

Thermodynamical Vibronic Coupling
Constant and Density: Chemical Potential
and Vibronic Coupling in Reactions

Chem. Phys.
Lett.

652, 157-161

2016

60

Hiroyuki Watanabe,
Masataka Hirose, Kazuyoshi
Tanaka, Kazuo Tanaka, andYoshiki Chujo

Color Tuning of Alternating
Conjugated Polymers Composed ofPentaazaphenanthrene by Modulating
Their Unique Electronic Structures
Involving Isolated-LUMOs

Polym. Chem.

7, 3674-3680

2016

61

Yoshimasa Matsumura,
Makoto Ishidoshiro,
Yasuyuki Irie, Hiroaki Imoto,Kensuke Naka, Kazuyoshi
Tanaka, Shinsuke Inagi, andIkuyoshi Tomita

Arsole-Containing p-Conjugated Polymer
by the Post-Element-Transformation
TechniqueAngew. Chem.
Int. Ed.

55(48), 1504015043

2016

62

Akihiro Ito, Ryohei Kurata,
Yusuke Noma, Yasukazu
Hirao, and Kazuyoshi Tanaka

Radical Cation of an Oligoarylamine
Having a Nitroxide Radical Substituent:
A Coexistent Molecular System ofLocalized and Delocalized Spins

J. Org. Chem.

81(22), 1141611420

2016

63

Julián Zapico, Marie Shirai,
Ryo Sugiura, Naokazu Idota,
Hiroyuki Fueno, Kazuyoshi
Tanaka, and Yoshiyuki
Sugahara

Borophosphonate Cages as ElementBlocks: Ab Initio Calculation of theElectronic Structure of a Simple
Borophosphonate, [HPO3BH]4, andSynthesis of Two Novel Borophosphonate
Cages with Polymerizable Groups

Chem. Lett.

46(2), 181-184

2017

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Authors

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58

Shun Goda, Masanori
Nikai, Mikinao Ito, Daisuke
Hashizume, Kohei Tamao,
Atsushi Okazawa, Norimichi
Kojima, Hiroyuki Fueno,
Kazuyoshi Tanaka, Yoshio
Kobayashi, and Tsukasa
MatsuoSynthesis and Magnetic Properties ofLinear Two-Coordinate Monomeric
Diaryliron (II) Complexes Bearing FusedRing Bulky “Rind” Groups

59

Tohru Sato, Naoki Haruta,
and Kazuyoshi Tanaka

田中

高塚

Journal

一義

和夫

64

Y. Arasaki, Y. Mizuno, S.
Scheit, K. Takatsuka

Stark-assisted quantum confinement of
wavepackets. A coupling of nonadiabaticinteraction and CW-laser.

J. Chem. Phys.

144, 044107 (10pages)

2016

65

K. Takatsuka, K. Matsumoto

Classical and semiclassical dynamics instatistical environments with a mixed
dynamical and statistical representation

PCCP

18, 1771-1785

2016

66

Yuta Mizuno, Yasuki
Arasaki, Kazuo Takatsuka

A perturbation theoretic approach to the
Riccati equation for the Floquet energies,
spectral intensities, and cutoff energy ofharmonic generation in photoemission
from nonadiabatic electron-transfer
dynamics driven by infrared CW laser
fieldsJ. Chem. Phys.

144, 024106 (13pages)

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67

Takehiro Yonehara, Kazuo
Takatsuka,

Nonadiabatic electron dynamics indensely quasidegenerate states in highly
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144, 164304 (15pages)

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Volume (Number),first page tolast pageyear

Chem. Phys.
(Perspective)

475, 39-53

2016

Yuta Mizuno, Yasuki
Arasaki, Kazuo Takatsuka,

Real-time observation of wavepacket
bifurcation on nonadiabatically coupledfield-dressed potential energy curves bymeans of spectrogram of induced photonemission from molecules driven by CW
laser

J. Chem. Phys.

145, 184305 (11pages)

2016

70

Hiroki Ichikawa, Kazuo
Takatsuka

Chemical modification of conicalintersections in photoisomerization
dynamics of butadiene derivatives

J. Phys. Chem. A

121, 315-325

2017

71

Kentaro Yamamoto, Kazuo
Takatsuka

Photoinduced charge separation catalyzed
by Mn-oxides onto a Y-shaped branching
acceptor efficiently preventing charge
recombination

ChemPhysChem

18, 1-13

2017

72

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

J. Chem. Phys.

146, 084312 (10pages)

2017

73

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№

Authors

Title

Kentaro Yamamoto, Kazuo
Takatsuka

Dynamical mechanism of charge
separation by photoexcited generation of
proton-electron pairs in organic molecularsystems. A nonadiabatic electron
wavepacket dynamics study

69

68

北浦

Journal

和夫

74

Tomomi Shimazaki, Kazuo
Kitaura, Dmitri G. Fedorov,Takeshi Nakajima

Gropup molecular orbital approarch tosolve Huzinaga subsystem self-consistentfield equations

J. Chem. Phys.

146(8), 084109

2017

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Dmitri G. Fedorov, Kazuo
KitauraMany-body expansion of the Fock matrix
in the fragment molecular orbital method

J. Chem. Phys.

147(10), 104106

2017

Active diffusion of model chromosomal
loci driven by athermal noise

Soft Matter

13, 812017

Reciprocating motion of active
deformable particles

Europhys. Lett.

114, 30002

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Universal Form of Stochastic Evolution
for Slow Variables in Equilibrium
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167(1), 46-63

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齋藤
76

拓也
Takahiro Sakaue and Takuya
Saito

多羅間
77

伊丹
78

充輔

M. Tarama and T. Ohta將人
Masato Itami and Shin-ichi
Sasa－ 179 －

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Volume (Number),first page tolast page

year

Current Opinion
in Collioid
Interface Science22, 59-64

2016

Collision between chemically-driven selfpropelled drops

Journal of Fluid
Mechanics

806, 205-233

2016

Dynamic heterogeneities and nonGaussian behaviour in 2D randomly
confined colloidal fluids

Phys. Rev. E

95(3), 032602

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J. Chem. Theory
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12, 2272-2284

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79

Akira Onuki, Shunsuke
Yabunaka, Takeaki Araki and
Ryuichi Okamoto

Structure formation due to antagonistic
salts

80

Shunsuke Yabunaka and
Natsuhiko Yoshinaga

藪中

俊介

Simon K. Schnyder

81

Simon K. Schnyder, Thomas
O. E. Skinner, Alice
Thorneywork, Dirk G. A. L.
Aarts, Jürgen Horbach

伊勢川

美穂

82

M. Isegawa, F. Neese, D. A.
PantazisIonization Energies and Aqueous
Redox Potentials of Organic Molecules:
Comparison of DFT, Correlated ab
Initio Theory and Pair Natural Orbital
Approaches

83

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

accepted2017

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

J. Am. Chem.
Phys.,

138, 8194-8206

2016

85

Ming-Chung Yang, Akhilesh
K. Sharma, W. M. C.
Sameera, Keiji Morokuma,
and Ming-Der Su

Theoretical Study of Addition Reactionsof L4M(M = Rh, Ir) and L2M(M = Pd, Pt)
to Li+@C60

J. Phys. Chem. A

121(13), 26652673

2017

86

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.

DOI: 10.1021/
acscatal.
7b01152.

2017

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

J. Chem. Theory
Comput.

12 (3), 11891206

2016

鈴木

84

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

Akhilesh Kumar Sharma

青野

87

信治
Shinji Aono, Toshifumi Mori,and Shigeyoshi Sakaki－ 180 －

Ⅴ 資料 (2016)

JournalVolume (Number),first page tolast page

year

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

89

Masayuki Nakagaki,
Shigeyoshi Sakaki

Hetero-dinuclear complexes of 3d metals
with a bridging dinitrogen ligand:theoretical prediction of the characteristicfeatures of geometry and spin multiplicity

Phys. Chem.
Chem. Phys.

18, 2636526375

2016

90

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

2016

Reductive Cross-Coupling of ConjugatedArylalkenes and Aryl Bromides with Hydrosilanes by Cooperative Palladium/
Copper Catalysis

Angew. Chem.,
Int. Ed.

55, 6275-6278

2016

Computational design of benzo[1,2-b:4,5-b'] dithiophene based thermally
activated delayed fluorescent materials

Dyes andpigments

127, 189-196

2016

93

Rong-Lin Zhong, Hong-Liang
Xu, and Zhi-Ru Li

The polar 2e/12c bond in phenalenylazaphenalenyl hetero-dimers: Stronger
stacking interaction and fascinatinginterlayer charge transfer

J. Chem. Phys.

145, 054304

2016

94

Rong-Lin Zhong, Hong-Liang
Xu, and Zhong-Min Su

Connecting effect on the first
hyperpolarizability of armchair carbon–boron–nitride heteronanotubes: patternversus proportion

Phys. Chem.
Chem. Phys.

18, 1395413959

2016

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

J. Chem. Phys.

146(13), 134114

2017

№

88

中垣

Authors

Shinji Aono, Nakagaki
Masayuki, and Shigeyoshi
SakakiTitle

雅之

Zheng, Hong91

Kazuhiko Semba, Kenta
Ariyama, Hong Zheng,
Ryohei Kameyama,
Shigeyoshi Sakaki, Yoshiaki
Nakao

Lu Jing
92

Jing Lu, Yiying Zheng, andJingping Zhang

Rong-Lin Zhong

松岡

95

貴英
Takahide Matsuoka, andKazuo Takatsuka－ 181 －

Ⅴ 資料 (2016)№

山本

Authors

Title

JournalVolume (Number),first page tolast page

year

憲太郎

96

Kentaro Yamamoto andKazuo Takatsuka

Dynamical mechanism of charge
separation by photoexcited generationof proton–electron pairs in organic
molecular systems. A nonadiabatic
electron wavepacket dynamics study

97

Kentaro Yamamoto andKazuo Takatsuka

Photoinduced Charge Separation
Catalyzed by Manganese Oxides onto a
Y-Shaped Branching Acceptor Efficiently
Preventing Charge Recombination

Chem. Phys.
Chem

18(5), 537-548

2017

Pang, Sumei, Zhao Yanying*,
Xue Jiadan, Zheng Xuming.

"Solvent-dependent dynamics
of hydrogen bonding structure5-(methylthio)-1, 3, 4-thiadiazole-2(3H)-thione as determined by Raman
spectroscopy and theoretical calculation."Spectrochimica
Acta Part A:
Molecular andBiomolecular
Spectroscopy

171, 470-477.

2017

Liu, Xin, and Yanying Zhao.*"Adsorption Kinetics of Methylene Blueon Synthesized DMF-MIL-101 (Cr),a DMF-functionalized Metal-organic
Framework."

Key Engineering
Materials

671

2016

100

Ming-Chung Yang, Akhilesh
K. Sharma, W. M. C.
Sameera, Keiji Morokuma,
and Ming-Der Su

Theoretical Study of Addition Reactionsof L4M (M = Rh, Ir) and L2M(M = Pd, Pt)
to Li+@C60.

J. Phys. Chem. A

121, 2665-2673

2017

101

Jia-Syun Lu, Ming-Chung
Yang and Ming-Der Su

Triply-bonded indium phosphorus
molecules: theoretical designs andcharacterization.

RSC Advances

7, 20597-20603

2017

102

Jia-Syun Lu, Ming-Chung
Yang and Ming-Der Su

Indium–Arsenic Molecules with an In≡As
Triple Bond: A Theoretical Approach.

ACS Omega

2, 1172–1179

2017

103

Jia-Syun Lu, Ming-Chung
Yang and Ming-Der Su

The effect of substituents on triply bonded
boron≡antimony molecules: a theoretical
approach.

Phys. Chem.
Chem. Phys.

19, 8026-8033

2017

104

Jia-Syun Lu, Ming-Chung
Yang and Ming-Der Su

The Effect of Substituents on the Stabilityof Triply Bonded Gallium≡Antimony
Molecules: A New Target for Synthesis.

DaltonTransactions

46, 1848-1856

2017

Chem. Phys.

475, 39-53

2016

Yanying Zhao

98

99

Ming-Chung Yang

－ 182 －

Ⅴ 資料 (2016)

２．共同研究者受入れ状況（平成 28 年度）

受入れ教員

諸熊奎治

共同研究者名SAMEERA,
W.M.C.

受入れ身分

受入れ期間

所属機関・職

研究内容

外国人
共同研究者

平成 26 年 9 月 16 日 ~平成 28 年 9 月 15 日

日本学術振興会・外国人特別研究員

合成キラル金属ポルフィリンの反応機構と選択性の計算化学による研究

北海道大学（日本）・
博士研究員

反応経路自動探索法を基盤とする化学反応の理論設計技術

諸熊奎治

鈴木

机倫

共同研究者

平成 27 年 3 月 1 日 ~平成 29 年 2 月 28 日

諸熊奎治

YANG MingChung

外国人
共同研究者

平成 27 年 8 月 10 日 ~平成 28 年 8 月 9 日

National Chiayi
University（台湾）・
博士研究員

複雑分子系の計算化
学的研究

諸熊奎治

ZHAO Yanying

外国人
共同研究者

平成 27 年 12 月 1 日 ~平成 28 年 11 月 30 日

Zhejiang Sci-Tech
University（中国）・准教授

複雑分子系の理論と
計算研究

榊

茂好

KWAN HUNG,
Enrique

招へい
共同研究者

平成 28 年 2 月 1 日 ~平成 29 年 1 月 31 日

中央大学（日本）
・博士研究員

アルカンの触媒的脱水素化反応の計算化
学研究

諸熊奎治

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

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

諸熊奎治
美穂

榊

茂好

永瀬

茂

ＬＩ, Qiao-Zhi

外国人
共同研究者

平成 28 年 9 月 19 日 ~平成 29 年 3 月 19 日

西安交通大学（中国）・PhD 学生

金属内包フラーレンの理論的研究諸熊奎治

PRABHAKAR,
Rajeev

招へい
外国人学者

平成 29 年 2 月 15 日 ~平成 29 年 3 月 9 日

University of Miami（アメリカ）・准教授

理論計算の基づく生体から着想を得た触媒、物質、薬の開発

榊

GUPTA, Ashutosh

招へい
外国人学者

平成 29 年 3 月 2 日 ~平成 29 年 3 月 16 日

Udai Pratap(Autonomous) College（インド）・准教授

分子間相互作用と化学反応に関する理論
計算化学研究茂好－ 183 －

Ⅴ 資料 (2016)

３．海外渡航一覧（平成 28 年度）

職

名

氏

名

期間（自）

期間（至）

員

榊

茂好

2016/6/12

2016/6/22

チェコ、ドイツ

特定研究員

多羅間

充輔

2016/7/7

2016/8/5

ドイツ、フランス

特定研究員

伊丹

将人

2016/7/17

2016/7/24

フランス

研

榊

茂好

2016/8/30

2016/9/4

中

特定研究員

多羅間

充輔

2016/9/11

2016/9/27

ドイツ、フランス

特定研究員

多羅間

充輔

2016/10/3

2016/11/4

ドイツ

研

究

員

榊

茂好

2016/10/19

2016/10/23

中

研

究

員

高塚

和夫

2017/1/14

2017/1/20

アメリカ合衆国

特定研究員

多羅間

充輔

2017/1/23

2017/2/12

オランダ、ドイツ

特定研究員

薮中

俊介

2017/3/15

2017/4/30

フランス

2017/3/15

2017/3/31

フランス

研

究

究

員

特定研究員

SCHNYDER, Simon Kaspar－ 184 －

目

的

地

国

国

Ⅴ 資料 (2016)

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－ 185 －

Ⅴ 資料 (2016)

第 14 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

2017 年 1 月 27 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]

赤木 和夫（京都大学 福井謙一記念研究センター長）

10:00 – 10:05[ご 挨 拶]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


高塚 和夫 （京都大学 福井謙一記念研究センター）

10:15 – 11:15「化学反応における電子動力学 －電子の運動が観える時代の基礎化学－」
司会：榊 茂好（福井センター）

11:25 – 12:25

八島 栄次 （名古屋大学 大学院工学研究科）「らせん構造を基本骨格とする超分子・高分子の創成、構造と機能」
司会：赤木 和夫（福井センター）

12:35 – 13:35

高田 彰二 （京都大学 大学院理学研究科）「複雑生体分子系のマルチスケールシミュレーション」
司会：林 重彦（京大院理）— 昼食 —「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

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－ 186 －

Ⅴ 資料 (2016)

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.

A computational study on luminescent [Cu(POP)(dmp)]+ and [Cu(xantphos)(dmp)]+ complexes
Sae Yanagida, 〇W. M. C. Sameera, Masaki Yoshida, Atsushi Kobayashi, and Masako Kato (Dept. of Chem.,
Faculty of Sci., Hokkaido Univ.)2.

レナードジョーンズクラスター LJ7 における固液転移とカオス〇馬場 朋広、清水 寧（立命館理工）3.

小数軌道占有数を用いた解析的微分法の開発〇西本 佳央（京大福井セ）

4.

Universal Form of Stochastic Evolution for Slow Variables in Equilibrium Systems〇伊丹 將人[1]、佐々 真一[2]（京大福井セ[1]、京大理[2]）5.

Collective Dynamics of Migrating Cells〇Simon K. Schnyder[1], John J. Molina[2], and Ryoichi Yamamoto[2] (FIFC[1], Grad. School of Eng.,
Kyoto Univ.[2])6.

化学反応で自己推進運動する液滴の衝突〇藪中 俊介[1]、義永 那津人[2]（京大福井セ[1]、東北大 AIMR[2]）7.

Aggregation-induced Emission of bis(dialkylamino)anthracene〇鈴木 聡、諸熊 奎治（京大福井セ）

8.

DFT investigations for activation process of dioxygen by a model of [NiFe] hydrogenase〇伊勢川 美穂[1]、W. M. C. Sameera[2]、A. K. Sharma[1]、小江 誠司[3]、諸熊 奎治[1]（京大福井セ[1]、北大院理[2]、九大 I2CNER[3]）9.

Theoretical study on ring opening and closing mechanism of diarylethene derivatives〇Kimichi Suzuki[1], Satoshi Maeda[1], and Keiji Morokuma[2] (Grad. School of Sci., Hokkaido Univ.[1],FIFC[2])－ 187 －

Ⅴ 資料 (2016)

10. The Biginelli reaction is a urea-catalyzed organocatalytic multicomponent reaction〇 Maneeporn Puripat[1], Romain Ramozzi[1], Miho Hatanaka[2,3], Waraporn Parasuk[4], Vudhichai
Parasuk[5], and Keiji Morokuma[1] (FIFC[1], Kindai Univ.[2], JST PRESTO[3], Kasetsart Univ.[4],Chulalongkorn Univ.[5])11. Computational Insights on Iron-Catalyzed Enantioselective Carbometalation of Azabycyclic
Alkenes〇Akhilesh K. Sharma[1], W. M. C. Sameera[1], M. Nakamura[2], and K. Morokuma[1] (FIFC[1], Dept. ofEnergy and Hydrocarbon Chem., Grad. School of Eng., Kyoto Univ.[2])12. Theoretical Study on Oxidative Addition of Nitrobenzene to Palladium(0)-Brettphos Complex〇Rong-Lin Zhong[1], Masahiro Nagaoka[2], Yoshiaki Nakao[2], and Shigeyoshi Sakaki[1] (FIFC [1], Grad.
School of Eng., Kyoto Univ.[2])13. Rational design of phenoxazine-based thermally activated delayed fluorescent materials withhigh performance〇Jing Lu[1,2], Yiying Zheng[2], and Jingping Zhang [2] (FIFC [1], Northeast Normal Univ. [2])14. Characteristic Features Transmetallation of Pd(II)–Ph Complex with Cu(I)–alkyl Complexes:
Theoretical Study〇Hong Zheng[1], Kazuhiko Semba[2], Yoshiaki Nakao[2], and Shigeyoshi Sakaki[1] (FIFC [1], Dept. of Mat.
Chem., Kyoto Univ.[2])15. 三中心多重金属結合を持つクロム(II)三核錯体の構造と電子状態〇中垣 雅之[1]、中谷 直輝[2]、長谷川 淳也[2]、榊 茂好[1]（京大福井セ[1]、北大触媒研[2]）16. 金(I)-イソシアニド錯体の吸収・発光スペクトル：QM/MM 法による分子結晶効果の研究〇青野 信治、榊 茂好（京大福井セ）
17. 高強度パルスレーザー場中のイオン化過程の非断熱電子ダイナミックス〇松岡 貴英、高塚 和夫（京大福井セ）
18. 浮動ガウシアン基底を用いた水素分子の原子核-電子波動関数における非断熱ダイナミクスの研究〇市川 雄一[1]、加藤 毅[2]、山内 薫[2]（京大福井セ[1]、東大院理[2]）19. Photoinduced Charge Separation Catalyzed by Mn-Oxides onto a Y-shaped Branching
Acceptor Efficiently Preventing Charge Recombination〇Kentaro Yamamoto and Kazuo Takatsuka (FIFC)－ 188 －

Ⅴ 資料 (2016)20. 液体の統計力学と原子間力顕微鏡で見るカルサイト上の三次元水和構造〇天野 健一[1]、宮澤 佳甫[2]、西 直哉[1]、福間 剛士[2]、作花 哲夫[1]（京大院工[1]、金大院自然[2]）
21. キラルネマチック相を示す液晶性イオン液体の合成と不斉電解重合への応用〇和田 浩平、山川 勝平、赤木 和夫（京大院工）22. キラル側鎖を有するポリジフェニルアセチレン誘導体の合成と光学特性〇松山 大起、大田 冬木、赤木 和夫（京大院工）23. –相互作用と水素結合を利用した芳香族共役系ポリマー凝集体の構築とその光学特性〇原田 恭佑、野津 賢祐、赤木 和夫（京大院工）24. メソポーラスシリカで被覆したアルミニウムナノ粒子アレイのプラズモン特性と薄膜内への光閉じ込め〇阪本 浩之[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]）25. Why Na Cannot Be Intercalated into Graphite〇大田 航[1]、Maxim Shishkin[2]、佐藤 啓文[1,2]（京大院工[1]、京大 ESICB[2]）26. HIV-1 protease に関する理論的研究〇金曽 将弘、林 重彦（京大院理）27. 液体ピレンの分子動力学シミュレーションと理論的解析〇山本 裕生[1]、Lu Fengniu[2]、中西 尚志[2]、林 重彦[1]（京大院理[1]、国際ナノアーキテクトニ
クス研究拠点[2]）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[2]、吉田 紀生[3]、林 重彦[1]（京大院理[1]、理研[2]、九大院理[3]）29. LOV 光受容タンパク質の光活性化機構の理論的研究〇田口 真彦、成 鋮、東村 智佳、林 重彦（京大院理）30. Theoretical study on molecular mechanism of a light-driven ion transport of Halorhodopsin〇小山 糧、長谷川 太祐、林 重彦（京大院理）31. 周期的静電ポテンシャルを考慮した埋め込みクラスターモデルの開発〇松井 正冬[1]、榊 茂好[1,2]（京大 ESICB[1]、京大福井セ[2]）－ 189 －

Ⅴ 資料 (2016)

32. Theoretical Study of NO–CO Reaction on Cu38 Cluster〇 Nozomi Takagi[1], Kazuya Ishimura[2], Ryoichi Fukuda[1], Masahiro Ehara[1,2], and Shigeyoshi
Sakaki[1,3] (ESICB, Kyoto Univ.[1], IMS[2], FIFC[3])33. Adsorption of CO2 and C2H2 in a Flexible Porous Coordination Polymer: QM and ClassicalMonte-Carlo Study〇 Jia-Jia Zheng[1,2], Shinpei Kusaka[1], Ryotaro Matsuda[1,3], Susumu Kitagawa[1], and Shigeyoshi
Sakaki[2] (iCeMS[1], FIFC[2], Grad. School of Eng., Nagoya Univ.[3])34. 光駆動イオン輸送型ロドプシンのイオン輸送メカニズムの解明〇宮原 友夫、中辻 博（量子化学研究協会研究所）
35. 太陽電池設計のための非断熱分子動力学シミュレーションの実装〇嶺澤 範行（理研 AICS）
36. TD-DFT 法を用いた Ir(ppy)3 錯体およびその類縁体の光吸収特性に関する理論研究〇名取 圭紀、浅岡 瑞稀、北河 康隆、中野 雅由（阪大院基礎工）
37. Theoretical study on third-order nonlinear optical property of carbon-bridged oligo
para-phenylenevinylene (COPV)〇Yusuke Nishigaki[1], Hiroshi Matsui[1], Tsuji Hayato[2], and Masayoshi Nakano[1] (Grad. School of Eng.
Sci., Osaka Univ.[1], Faculty of Sci., Kanagawa Univ.[2])38. イリジウム二核錯体を用いる第一級アルコールの酸化反応に関する理論的研究〇瀬川 実礼[1]、畑中 美穂[1,2]、中井 英隆[1]、若林 知成[1]（近大理工[1]、JST さきがけ[2]）39. 不斉亜鉛錯体を触媒とするアルドール反応の立体選択性発現機構の解明〇日下部 彩[1]、畑中 美穂[1,2]、若林 知成[1]（近大理工[1]、JST さきがけ[2]）40. P=P double bond cleavage by N-heterocyclic carbenes
Naoki Hayakawa[1], Kazuya Sadamori[1], Shota Tsujimoto[1], 〇 Miho Hatanaka[1,2], Tomonari
Wakabayashi[1], and Tsukasa Matsuo[1] (Kindai Univ.[1], JST PRESTO[2])－ 190 －

Ⅴ 資料 (2016)

５．福井センターセミナー

ポスター・プログラム

第14回
福井センターセミナー（春季）The 14th Fukui Center Seminar-Spring	
2016年4月13日(水) 13:30-17:00
April 13, 2016

〒606-8103 京都市左京区高野西開町34-4 (TEL: 075-711-7708)
京都大学福井謙一記念研究センター (１階106室）	

Fukui Institute for Fundamental Chemistry (1F, room 106)
Kyoto Univ. (http://www.fukui.kyoto-u.ac.jp/)

13:30～14:20 Takahiro Sasamori (Kyoto Univ.) 	
“What is the Difference of Multiple Bonds between
Carbon and heavier Group 14 Elements?”	
14:20～15:10 Atsushi Wakamiya (Kyoto Univ.) 	
“Materials Design for Highly Efficient
Perovskite Solar Cells”	
15:10～15:25 Break	
15:25～16:15 Hideki Yorimitsu (Kyoto Univ.) 	
“Journey from Discovery of New Pummerer Chemistry
to Catalytic C-S Bond Cleavage”	
16:15～17:00 Shigeyoshi Sakaki (Kyoto Univ.) 	
“The Present and Future of Molecular Theory
and Calculations in Transition Metal Chemistry”	
皆様のご来場を歓迎します	
We welcome all of you to join.	

－ 191 －

Ⅴ 資料 (2016)

６．複雑・複合系の理論計算科学に関する日・仏・スペイン合同シンポジウムを開催

雑・複合系の理論計算科学に関する 日・仏・スペイン合同シンポジウム日程2016 年 10 月 26 日（水）～ 28 日（金）場所

京都大学福井謙一記念研究センター（〒606-8103 京都府京都市左京区高野西開町
34-4）
趣

旨
理論計算科学は、理論的手法、計算機、計算アルゴリズムの進歩により、長足の発展を遂げ、今や化学、物理、生命科学分野の研究で欠くことの出来ない研究手法となっている。
特に、実験的な手段が限られている複雑・複合系の研究分野では、理論計算科学への期待が大きい。たとえば、化学分野では触媒が、物理分野では無限系と孤立系が相互作用している複合系、金属と複合金属クラスターの境界などがその例である。生命科学では、酵素や細胞などが化学、物理から見た場合の複雑・複合系である。これらの研究対象は、化学、物理、生命科学の中で互いに離れているが、その理論計算科学的手法には共通性も多く、理論計算を中心とした領域融合は、これらの研究に大きな成果を生み出すはずである。本学は、福井謙一博士の存在により、特に化学および生命科学分野で計算科学研究が歴史的に盛んであり、わが国はもとより世界レベルで先導的な研究を進めてきた。本シンポジウ
ムは、わが国の窓口となり、わが国の若手、中堅研究者に、フランス、スペインからの若手、中堅研究者を加え、複雑・複合系に関する理論計算科学に関する研究成果を互いに紹介しあい、理論計算科学を機軸とする融合研究の更なる展開を目指し、このシンポジウムを企画した。将来的には、より多くの国と国際連携も広げる予定である。
内容

Plenary Talk, Invited Talk, Poster Session を行います。Speaker（別ページ）と Program（PDF）はそれぞれのリンクをご参照ください（2016/10/22 更新）。

Poster Session (PDF)の発表者一覧を作成しました（2016/10/22 更新）。
ポスターセッション詳細
お申し込み期限は 9 月 23 日（金）題目、発表者氏名〔所属〕、連絡先、Poster Short Talk 希望の有無を記載し、要旨（word-fileと pdf-file 双方）と共に JFSsymp@fukui.kyoto-u.ac.jp にメールをお送りください。
要旨は例をダウンロードして、それを書きつぶして、作成ください。
Poster Short Talk は件数が限られていますので、御希望に添えない場合があります。御了承ください。

－ 192 －

Ⅴ 資料 (2016)

要旨の例は右をクリックしてください： Abstract_Example (word-file)
なお、ポスターボードのサイズは A0 縦型です（2016/10/22 更新）。
参加申し込みお名前、御所属、連絡先、懇親会参加の有無を記載したメールを

JFSsymp@fukui.kyoto-u.ac.jp にお送りください。
参加費
10,000 円 〔当日会場にてお支払いください〕
学生、博士研究員の方には免除制度(*)がございますので、申請の際はメールに「参加費免除希望」とご記入ください（2016/09/24 更新）。
(*)対象： 所属機関にて支払い可能な財源をお持ちでない方
懇親会
10 月 27 日（木）夕方を予定しています（当センターにて開催します）。
会費：5,000 円 （当日会場にてお支払いください）
組織委員会
Honorary Chair: Keiji Morokuma
International Committee Members:
Odile Eisenstein, Feliu Maseras, Koichi Yamashita, Shigeyoshi Sakaki
実行委員会 (Local Committee Members)
江原正博、榊 茂好、佐藤啓文、高塚和夫、長岡正隆、永瀬 茂、長谷川淳也、林 重彦、山下晃一、吉澤一成 （敬称略）
連絡先
京都大学福井謙一記念研究センター 榊茂好
E-Mail: JFSsymp@fukui.kyoto-u.ac.jp
Tel: 075-711-7708

Fax: 075-781-4757

Web: http://www.fukui.kyoto-u.ac.jp－ 193 －

Ⅴ 資料 (2016)

７．日本－ブラジル

理論化学 ･ 計算化学交流会を開催

日本－ブラジル趣

理論化学･計算化学交流会を開催

旨
JSPS とサンパウロ研究財団（São Paulo Research Foundation：略称 FAPESP）のサポ

ー ト に よ り 、 JSPS-FAPESP Joint Research Workshop と し て 国 際 シ ン ポ ジ ウ ム ”
Multi-scale Simulation of Condensed-phase Reacting Systems 2016″ (MSCRS2016)が名古屋大学で開催されます。
その一環として、ブラジルからの参加者が京都大学福井謙一記念研究センター（FIFC）
を訪問して当センターを見学すると共に、センター研究者と理論化学･計算化学に関する研究紹介と意見・情報交換を行います。
日時2016 年 10 月 13 日〔木〕

場

9:30 から 12:45 まで

所

京都大学福井謙一記念研究センター（〒606-8103 京都府京都市左京区高野西開町
34-4）多目的室（参加者が多い場合、３階大ホール）
プログラム
09:30

FIFC 到着;会場へ

09:40

開会挨拶（FIFC センター長代理；田中一義先生）

09:50

挨拶と講演

10:50

講演

榊

茂好 (FIFC)

11:20

講演

永瀬

茂 (FIFC)

11:50

閉会挨拶 （長岡正隆名大教授）

12:00

記念撮影

12:15

センター見学

12:45

交流会終了

Prof. Sylvio Canuto（ブラジル側代表、サンパウロ大教授）－ 194 －

京都大学福井謙一記念研究センター

年報

2016

2017 年 10 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）

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