2001 Fiscal Year Final Research Report Summary
Potentiai Energy Surfaces and Dynamics of Chemical Reactions in Solution
| Project/Area Number |
10206205
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas (B)
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| Allocation Type | Single-year Grants |
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| Research Institution | Kyoto University |
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Principal Investigator |
KATO Shigeki Kyoto University, Chemistry Department, Professor, 大学院・理学研究科, 教授 (20113425)
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| Co-Investigator(Kenkyū-buntansha) |
MORITA Akihiro Kyoto University, Chemistry Department, Research Associate, 大学院・理学研究科, 助手 (70252418)
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| Project Period (FY) |
1998 – 2000
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| Keywords | Potential Surface / Chemical Reaction / Dynamics / Reaction Path / Hamiltonian / Charge Polarization / Vibrationa Spectra / Water |
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| Research Abstract |
We have developed a method to construct a reaction path Hamiltonian for chemical reactions in solution based on the reference interaction site self-consistent field (RISM-SCF) electronic structure calculations of reacting solute molecule combined with molecular dynamic (MD) simulation calculations for bulk solvent. We applied this method to the S_N2 reaction CH_3Cl + Cl^- and the Menshutkin type reactions NH_3+CH_3X (X=Cl, Br, I) and examined the effect of solvent dynamics on the reaction rates. The transmission coefficient for the former was 0.71, which was consistent with the previous simulation calculations. We have also investigated the electronic polarization effect on the dynamics of molecules in solution with the use of charge response kernel (CRK) model, which was proposed previously by us. Three and frve site CRK models for water molecule were developed and the infrared and Raman spectra for bulk water were calculated. The five site model was shown to well reproduce the experimental spectral features. The present five site model was further applied to calculate the infrared spectrum of N-Methylacetamide (NMA) in aqueous solution. Finally, we proposed a new method to define the CRK which avoid the ambiguity in determining the effective charges at atomic sites.
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