Zhu-Nakamura理論に基づく非断熱化学動力学の総合的研究

2003 Fiscal Year Annual Research Report

• Project/Area Number: 15002011
• Research Institution: Okazaki National Research Institutes
• Principal Investigator: 中村 宏樹 岡崎国立共同研究機構, 分子科学研究所, 教授 (10010935)
• Co-Investigator(Kenkyū-buntansha): GENNADY Mil'nikov 岡崎国立共同研究機構, 分子科学研究所, 助手 (00370130) ; 石田 俊正 岡崎国立共同研究機構, 分子科学研究所, 助教授 (50212890) ; 鈴木 俊法 岡崎国立共同研究機構, 理化学研究所, 主任研究員 (10192618) ; 南部 伸孝 岡崎国立共同研究機構, 計算科学研究センター, 助手 (00249955)
• Keywords: Zhu-Nakamura理論 / 非断熱遷移 / 化学反応動力学 / レーザー制御 / 分子機能

Research Abstract

以下に、主要な成果を列挙するが、基礎理論の整備と応用計算、及び実験との対比を目指した準備等が順調に進んでいる。
(1)基礎理論の開発:(i)Zhu-Nakamura(ZN)理論を組み込んだ波束伝播の半古典多次元理論を構築(論文印刷中)、(ii)古典軌道とZN理論を用いて多次元系の扱いを可能とするレーザー制御理論を構築中、(iii)時間と空間に依存した非断熱遷移問題の新基本公式を導出(論文出版済)、(iv)非断熱反応の熱反応速度定数の理論を構築中、(v)エネルギー分裂及びトンネル崩壊に対する多次元トンネル理論を完成(論文出版済),(vi)多次元空間で転回点(火点)、を求める理論を完成(論文出版済)。
(2)プログラム開発:(i)ZN理論を組み込んだ一般多次元に使える軌道ホップ(TSH)法を開発中、(ii)上部(i)のプログラムを開発中。
(3)応用研究:(i)完全反射現象等を利用した分子機能開発を環状共役系分子で探索中(広範囲の量子化学計算を実行中)、(ii)O(^1D)+HCl反応系の3枚のポテンシャル曲面の電子結合を量子化学計算で求め大規模動力学計算用に準備、(iii)ZN理論と周期チャープを用いた波束運動制御の理論計算を実行、(iv)具体的分子(マロンアルデヒドやビニルラジカル等)のトンネル分裂に我々のトンネル理論を応用して解析中(一部論文出版済)。
(4)実験的研究:(i)衝突エネルギー可変交差分子線散乱画像観測装置の製作、(ii)励起酸素原子O(^1D)線の開発、(iii)交差分子線反応実験の実行(O(^1D)+H_2/D_2)、(iv)画像検出感度分布(装置関数)のシミュレーション、(v)光解離実験の実施(N_2O, OCS)(論文出版済)。

Research Products

• [Publications] Gennady V.Mil'nikov, Kiyoshi Yagi, Tetsuya Taketsugu, Hiroki Nakamura, Kimihiko Hirao: "Tunneling splitting in polyatomic molecules : Application to malonaldehyde"Journal of Chemical Physics. Vol 119,No 1. (2003)
• [Publications] Chaoyuan Zhu, Gennady Mil'nikov, Hiroki Nakamura: "Semiclassical Theory of Nonadiabatic Transition and Tunneling"Modern Trends in Chemical Reaction Dynamics, Advanced Series in Physical Chemistry, World Scientific edited by K.Liu & X.Yang. In Presss.
• [Publications] H Nakamura, E A Solov'ev: "Semiclassical theory for the quantum defect function of diatomic molecules"J.Phys.B : At.Mol.Opt.Phys.. 36. 3697-3705 (2003)
• [Publications] Hiroki Nakamura: "Analytic Solution to wave packet dynamics in a laser field : the case of linear chirp"Chemical Physics. 295. 269-273 (2003)
• [Publications] V.I.Osherov, V.G.Ushakov, H.Nakamura: "Semiclassical Theory of Nonadiabatic Transitions Between Asymptotically Degenerate States"Russian Chem. Phys.. Vol 22,No 10. 87-102 (2003)
• [Publications] V.I.Osherov, V.G.Ushakov, H.Nakamura: "Analytical Treatment of S-P Type Collisional Resonant Excitation Transfer"Russian Chem.Phys.. Vol22,No 10. 103-108 (2003)
• [Publications] Hiroki Nakamura: "Nonadiabatic Transition -An Origin of Mutability of This World"Russ.Acad.Sci.Publ.. In Press.
• [Publications] Ponmile Oloyede, Gennady Mil'nikov, Hiroki Nakamura: "On The Determination Of Caustics"J.Theo.Comp.Chem.. Vol.3,No 1. 1-9 (2004)
• [Publications] Gennady Mil'nikov, Kiyoshi Yagi, Tetsuya Taketsugu, Hiroki Nakamura, Kimihiko Hirao: "Simple and accurate method to evaluate tunneling splitting in polyatomic molecules"J.Chem.Phys.. In Press.
• [Publications] A.Kondorskiy, H.Nakamura: "Semiclassical Theory of Electronically Nonadiabatic Chemical Dynamics : Incorporation of the Zhu-Nakamura Theory into the Frozen Gaussian Propagation Method"J.Chem.Phys.. In Press.
• [Publications] Ikuo Tokue, Katsuyoshi Yamasaki, Shinkoh Nanbu: "He (2^3S)Penning ionization of H_2SI. Theoretical Franck-Condon factors for the H_2S (X^1A_1,V'=0) →H_2S^+ (X^2B_1,A^2A_1) ionization and the H_2S^+ (A-X) transition"J.Chem.Phys.. 119. 5874-5881 (2003)
• [Publications] Ikuo Tokue, Katsuyoshi Yamasaki, Shinkoh Nanbu: "He (2^3S) Penning ionization of H_2S II. Formation of the SH^+(A^3II) and H_2S^+ (A^2A_1) ions"J.Chem.Phys.. 119. 5882-5888 (2003)
• [Publications] Ikuo Tokue, Katsuyoshi Yamasaki, Satoshi Minamino, Shinkoh Nanbu: "Theoretical transition probabilities for the A^2A_1-X^2B_1 system of H_2O^+ and D_2O^+ and related Franck-Condon factors based on global potential energy surfaces"J.Chem.Phys.. (submitted).
• [Publications] Shinkoh Nanbu, Matthew S.Johnson: "Analysis of the Ultraviolet Absorption Cross Sections of Six Nitrous Oxide Isotopomers Using 3D Wavepacket Propagation"Memorial Festschrift for Professor Gert Billing in J. Phys. Chem.. (submitted).
• [Publications] Jong-In Choe, Suk-Kyu Chang, Satoshi Minamino, Shinkoh Nanbu: "Ab Initio Study of Complexation Behavior of Calix[5]arene Derivative toward Alkyl Ammonium Cations"Bull.Korean Chem.Soc.. 24. 75-80 (2003)
• [Publications] S.Minamino, J.-I.Choe, S-K.Chang, F.Mizutani, S.Nanbu: "Theoretical study of vibrational spectra of p-tert-butylcalix [4] crown-6-ether complexed with ethyl ammonium cation"Chem.Phys.Lett.. 374. 572-576 (2003)
• [Publications] Jong-In Choe, Sang Hyun Lee, Dong-Suk Oh, Suk-Kyu Chang, Shinkoh Nanbu: "Ab Initio Study of Complexation Behavior of p-tert-Butylcalix[5]arene Derivative toward Alkyl Ammonium Cations"Bull. Korean Chem. Soe.. (submitted).
• [Publications] H.Watanabe, S.Nanbu, J.Maki, Z.-H.Wang, T.Urisu, M.Aoyagi, K.Ooi: "Theoretical Analysis of the Oxygen Insertion Process in the Reaction of H_2O with H-terminated Si(100) Surface"Chem.Phys.Lett.. 383. 523-527 (2004)
• [Publications] Z.-H.Wang, T.Urisu, S.Nanbu, J.Maki, M.Aoyagi, H.Watanabe, K.Ooi: "Three Pairs of Doublet Bands Assigned to Scissors Modes of SiH_2 on Si(100) Surfaces Observed in Several H_2O-induced Oxidation systems"Phys.Rev.B. 69. 045309 (2004)
• [Publications] Z.-H.Wang, G.R.Rao, T.Urisu, S.Nanbu, J.Maki, M.Aoyagi, H.Watanabe, K.Ooi: "Assignment of surface IR absorption spectra observed in the oxidation reactions : 2H + H_2O/Si(100) and H_2O + H/Si(100)"Phys.Rev.B. (In Press).
• [Publications] Toshimasa Ishida, George C.Schatz: "A local interpolation scheme using no derivatives in potential sampling : Application to O(^1D)+H_2 system"J.Comput.Chem.. 24(9). 1077-1086 (2003)
• [Publications] Kyoung Hoon Kim, Yoon Sup Lee, Gwang-Hi Jeung, Toshimasa Ishida: "Potential energy surface generation using ab initio calculations and IMLS/Shepard interpolation for the LiH + H 【tautomer】Li + H_2 Reactions"J.Chem.Phys.. 119(9). 4689-4694 (2003)
• [Publications] Toshimasa Ishida, Makoto Murakami, Go Watanabe, Hirofumi, Yoshikawa, Shin-ichi Nishikiori: "Theoretical Study on Photoinduced Color Change and Charge Transfer of Methylviologen"Internet Electronic J. Mol. Design. 2(1). 14-23 (2003)
• [Publications] Mutsumi Hirama, Toshimasa Ishida, Jun-ichi Aihara: "Possible Molecular Hydrogen Formation Mediated by the Radical Cations of Anthracene and Pyrene"J.Comput.Chem.. 24(12). 1378-1382 (2003)
• [Publications] Hirofumi Yoshikawa, Shin-ichi Nlshikiori, Toshimasa Ishida: "Crystal structure and spectroscopic properties of the CT complex of methyl viologen dication and o-dimethoxybenzene included in a polycyano-polycadmate host, and theoretical study on its red shifted CT absorption"J.Phys.Chem.B. 107(35). 9261-9267 (2003)
• [Publications] Jun-ichi Aihara, Toshimasa Ishida: "Aromatic character of annelated dimethyldihydropyrenes"J.Phys.Org.Chem.. (In Press). (2004)
• [Publications] Tatsuhiro Nishide, Toshinori Suzuki: "Photodissociation of Nitrous Oxide revisited by high-resolution photofragment imaging : energy partitioning"J.Phys.Chem.A. (submitted).
• [Publications] Masaaki Tsubouchi, Toshinori Suzuki: "Femtosecond time-resolved charged particle imaging studies of the ultraviolet photodissociation of the NO dimmer"J.Chem.Phys. 119. 11728 (2003)
• [Publications] Masaaki Tsubouchi, Toshinori Suzuki: "Excitation energy dependence in the electronic dephasing time of the NO dimmer"Chem.Phys.Lett.. 382. 418 (2003)
• [Publications] Masaaki Tsubouchi, Toshinori Suzuki: "Femtosecond photoelectron imaging on Pyridine : Ultrafast electronic dephasing from the S1 state Rydberg state energetics"J.Phys.Chem.A. 107. 10897 (2003)