Theoretical Studies of Nonadiabatic Transitions and Chemical Dynamical Problems

非绝热转变和化学动力学问题的理论研究

• 批准号: 10440179
• 负责人: NAKAMURA Hiroki
• 金额: $ 6.27万
• 依托单位: Institute for Molecular Science
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10440179/
• 关键词: nonadiabatic transition; Zhu-Nakamura theory; Landau-Zener model; Rosen-Zener model; Chemical reaction; laser control; Semiclassical theory; Complete reflection phenomenon; 化学反応動力学; 超球座標; 全反応確率; Landau-Zener-Stueckelberg; Rozen-Zener; ポテンシャルリ

(1) Quantum dynamics of hydrogen transfer reactionsUsing our own hyperspherical elliptic coordinates, we could conceptualize the hydrogen transfer reactions as vibrationally nonadiabatic transitions along the potential ridge line. Furthermore, it was demonstrated that these transitions can be treated by the Zhu-Nakamura theory analytically to reproduce the cumulative reaction probabilities.(2) Development of basic theories of nonadiabatic transitionsExact analytical solutions of some special exponential models and more general semiclassical solutions have successfully formulated. A new type of nonadiabatic transition has also been found. This is a transition between asymptotically degenarate states.(2) Diabatically avoided crossing (DAC) model and complete reflection phenomenonAnalytical solutions have been obtained for the DAC model and also an interesting complete reflection phenomenon has been found in this model and the case of two crossings.(4) Applications of the Zhu-Nakamura theory to electronically nonadiabatic reactionsBy incorporating the Zhu-Nakamura theory into the trajectory surface hopping method, it was shown that we can deal with electronically nonadiabatic reactions accurately.(5) Laser control of molecular processesWe have proposed a new way of controlling molecular processes by sweeping laser frequency, and successfully applied to various processes.

(1)氢转移反应的量子动力学利用我们自己的超球椭圆坐标，我们可以将氢转移反应概念化为沿势脊线沿着的振动非绝热跃迁。此外，证明了这些跃迁可以用Zhu-Nakamura理论解析地处理，以再现累积反应几率。(2)非绝热相变基本理论的发展成功地给出了一些特殊指数模型的精确解析解和更一般的半经典解。还发现了一种新的非绝热跃迁，即渐近简并态之间的跃迁。(2)非绝热避免交叉（DAC）模型和完全反射现象本文给出了DAC模型的解析解，并在此模型和两个交叉的情况下发现了一个有趣的完全反射现象。(4)Zhu-Nakamura理论在电子非绝热反应中的应用通过将Zhu-Nakamura理论结合到轨线表面跳跃方法中，表明我们可以准确地处理电子非绝热反应。(5)分子过程的激光控制我们提出了一种利用激光扫频控制分子过程的新方法，并成功地应用于各种过程。

项目成果

C.Zhu and H.Nakamura: "Improvement of the Adiabatic Phase Integral for the Landau-Zener Type Curve Crossing"J.Chem.Phys.. 109. 4689 (1998)

C.Zhu 和 H.Nakamura：“Landau-Zener 型曲线交叉的绝热相积分的改进”J.Chem.Phys.. 109. 4689 (1998)

M.Wojcik, H.Nakamura, S.Iwata, and W.Tatara: "Theoretical study of multidimensional proton tunneling in the excited state of tropolone"J.Chem.Phys.. (in press). (2000)

M.Wojcik、H.Nakamura、S.Iwata 和 W.Tatara：“托酚酮激发态多维质子隧道的理论研究”J.Chem.Phys..（出版中）。

M.Wojcik, H.Nakamura, S.Iwata, and W.Tatara: "Theoretical study of multidimensional proton tunneling in the excited state of tropolone"J. Chem. Phys.. (in press). (1999)

M.Wojcik、H.Nakamura、S.Iwata 和 W.Tatara：“托酚酮激发态多维质子隧道效应的理论研究”J。

C.Zhu and H.Nakamura: "Improvement of the Adiabatic Phase Integral for the Landau-Zener Type Curve Crossing" J.Chem.Phys.109. 4689-4689 (1998)

C.Zhu 和 H.Nakamura：“Landau-Zener 型曲线交叉的绝热相积分的改进”J.Chem.Phys.109。

H.Nakamura: "Chemical Reaction Dynamics and Potential Ridge --Beyond the Transition State in "The Transition State --A Theoretical Approach" edited by T. Fueno"Kohdansha and John Wiley & Sons. 193-215 (1999)

H.Nakamura：T. Fueno 编辑的《化学反应动力学和势岭——超越过渡态》Kohdansha 和 John Wiley