2017 Fiscal Year Final Research Report
Study of organic reaction mechanism in consideration of asynchronous solvation dynamics
| Project/Area Number |
15K05434
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Nagasaki University |
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Principal Investigator |
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| Co-Investigator(Kenkyū-buntansha) |
大賀 恭 大分大学, 理工学部, 教授 (60252508)
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| Project Period (FY) |
2015-04-01 – 2018-03-31
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| Keywords | 反応速度理論 / 溶媒効果 / 非平衡状態 / 分子動力学法 / 分子軌道法 / 自由エネルギー面 |
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| Outline of Final Research Achievements |
Solute-solvent interactions often play essential roles in solution reaction kinetics not only statistically but dynamically. Under extremely high pressure, reaction rate constants does not obey Transition State Theory invoked by strong solute-solvent friction in viscous solvent; for example, Z/E isomerization reaction of nitoroazobenzene and benzylideneanilines or thermally backward cyclization reaction of hexadienone to naphthopyran. Although this pressure-dependent rate anomaly has been phenomenology interpreted by macroscopic models, the detailed mechanism at molecular level remain unresolved. In this study, the anomaly were computationally studied by means of experimental evaluation of reaction rate constant under high pressure and molecular dynamics simulations.
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| Free Research Field |
物理有機化学
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