2001 Fiscal Year Final Research Report Summary
Joint Theoretical Study on Quantum Rate Processes
| Project/Area Number |
11694060
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Physical chemistry
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| Research Institution | The University of Tokyo |
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Principal Investigator |
YAMASHITA Koichi Graduate School Of Engineering, The University of Tokyo, Professor, 大学院・工学系研究科, 教授 (40175659)
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| Co-Investigator(Kenkyū-buntansha) |
NAKAJIMA Tohru Graduate School Of Engineering, The University of Tokyo, Research Associate, 大学院・工学系研究科, 助手 (70292779)
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| Project Period (FY) |
1999 – 2000
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| Keywords | quantum rate constant / flux correlation function / potential surface / dividing surface / reaction channel / diffusion process / reaction rate / time-development |
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| Research Abstract |
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.
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