Joint Theoretical Study on Quantum Rate Processes

量子速率过程联合理论研究

• 批准号: 11694060
• 负责人: YAMASHITA Koichi
• 金额: $ 2.69万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11694060/
• 关键词: quantum rate constant; flux correlation function; potential surface; dividing surface; reaction channel; diffusion process; reaction rate; time-development; 量子トンネル; 量子非断熱; 量子波束法; 経路積分法; オゾン分解反応; 大気光反応; 量子速度過程; 反応速度素過程; オゾン分解過程

We have employed a flux-flux cross-correlation function approach (CCFA) to calculate the quantum thermal rate constants of reactions for which an auto-correlation function, approach (ACFA) is not adequate. In the former approach, two dividing surfaces partition a system into three regions, while in the latter approach, two channels are defined by a dividing surface. Therefore, the CCFA method is appropriate for multi-channel reactions. In this paper, we show the efficiency of the CCFA to multi-channel reactions, and extend it to surface reactions, where there are an infinite number of localized channels. For example, we have adapted a model that forms a stable complex in a well between two barriers, and have investigated the self-diffusion of a hydrogen atom on a Cu(111) surface. In the former reaction, in addition to defining the complex channel, the cross-correlation function can avoid the oscillations seen in the ACFA. In the latter reaction, we introduce closed dividing surfaces that subdivide the potential energy surface for each channel. The combination of closed dividing surfaces and the CCFA provides well-defined rate constants for both single and multi-hopping rates.

我们采用通量-通量互相关函数方法（CCFA）来计算自相关函数方法（ACFA）不足以计算的反应的量子热速率常数。在前一种方法中，两个分割表面将系统划分为三个区域，而在后一种方法中，两个通道由分割表面定义。因此，CCFA方法适用于多通道反应。在本文中，我们展示了 CCFA 对多通道反应的效率，并将其扩展到有无限数量局部通道的表面反应。例如，我们采用了一个在两个势垒之间的井中形成稳定复合物的模型，并研究了氢原子在 Cu(111) 表面上的自扩散。在前一个反应中，除了定义复杂的通道之外，互相关函数还可以避免 ACFA 中出现的振荡。在后一个反应中，我们引入了封闭的分割表面，该分割表面可以细分每个通道的势能表面。封闭分割表面和 CCFA 的组合为单跳和多跳速率提供了明确定义的速率常数。

项目成果

K. Mishima and K. Yamashita: "A Theoretical Study on quantum Control of Photodissociation and Photodesorption Dynamics by Femtosecond Chirped Laser Pulses"J. Chem. Phys.. 110. 7756-7769 (1999)

K. Mishima 和 K. Yamashita：“飞秒啁啾激光脉冲对光解离和光解吸动力学的量子控制的理论研究”J。

中島,田中,山下: "A theoretical study of aluminium chemical vapour deposition using dimethylaluminium hydride"Surface Science. 444. 99-112 (2000)

Nakajima、Tanaka、Yamashita：“使用二甲基氢化铝进行铝化学气相沉积的理论研究”表面科学 444. 99-112 (2000)。

大脇,山下: "A DFT study of Electric Field Effects in Proton Transfer Reactions at H^+(H_2O)_2/Pt (111) and Ag (111)"Journal of Electroanalytical Chemistry. (印刷中). (2001)

Owaki, Yamashita：“H^+(H_2O)_2/Pt (111) 和 Ag (111) 中质子转移反应电场效应的 DFT 研究”电分析化学杂志（2001 年出版）。

Nakayama, Yamashita: "Path Integral Monte Carlo Study on the Structure and Absorption Spectra of Alkali Atoms(Li, Na, K)Attached to Superfluid Helium Cluster"J. Chem. Phys.. 114. 780-791 (2000)

Nakayama，Yamashita：“超流氦团簇碱原子（Li、Na、K）结构和吸收光谱的路径积分蒙特卡罗研究”J。

Mishima, Yamashita: "A Theoretical Study on Chirped Coherent Raman Spectroscopy"J. Phys. Chem.. A105. 2867-2878 (2001)

三岛山下：“啁啾相干拉曼光谱的理论研究”J。