单分子微正则系综反应速率常数的理论研究──曲率校准和转动选态速率常数的计算

高等学校化学学报 ›› 1996, Vol. 17 ›› Issue (7): 1104.

单分子微正则系综反应速率常数的理论研究──曲率校准和转动选态速率常数的计算

李宗和, 王艳, 张绍文, 冯文林, 刘若庄

北京师范大学化学系, 北京 100875

收稿日期:1995-06-14 出版日期:1996-07-24 发布日期:1996-07-24
通讯作者: 李宗和,男,51岁,副教授.
作者简介:李宗和,男,51岁,副教授.
基金资助:
国家自然科学基金

A Theoretical Study on the Microcanonical Rate Constants of Unimolecular Rerctions──Calculation of Rate Constants Regarding to the Effect of Curvature and the Selection of Rotation States

LI Zong-He, WANG Yan, ZHANG Shao-Wen, FENG Wen-Lin, LIU Ruo-Zhuang

Department of Chemistry, Beijing Normal University, Beijing 100875

Received:1995-06-14 Online:1996-07-24 Published:1996-07-24

摘要/Abstract

摘要： 研究了微正则系综下单分子反应速率常数的理论计算公式,并将曲率因子A引入含振动和转动的隧道几率表达式中,进而得到了反应速率常数表达式。应用该式研究了F─C≡C─H反应的氢迁移过程的转动选态及曲率因子对反应速率常数的影响。结果表明:在隧道效应区域内,曲率因子对速率常数的影响比较显着,它将引起速率常数的增加;转动选态对速率的影响不太明显。

关键词: 微正则系综, 单分子反应速率, 曲率因子, 转动选态

Abstract: The curvature correction factor Ais introduced into the tunneling probability expression derived by W.H.Miller.Then the modification for the microcanonical unimolecular rate constant formula is obtained.The application of the formula to the unimolecular hydrogen transfer reaction of F─C≡C─H indicates that the rate constants have asignificant enhancement in the tunneling region when the factor Ais involved,but the selection of rotation states has little effect on the reaction rate.

Key words: Microcanonical ensemble, Unimolecular rate constant, Curvature, Selection of rotation state

TrendMD:

李宗和, 王艳, 张绍文, 冯文林, 刘若庄. 单分子微正则系综反应速率常数的理论研究──曲率校准和转动选态速率常数的计算. 高等学校化学学报, 1996, 17(7): 1104.

LI Zong-He, WANG Yan, ZHANG Shao-Wen, FENG Wen-Lin, LIU Ruo-Zhuang. A Theoretical Study on the Microcanonical Rate Constants of Unimolecular Rerctions──Calculation of Rate Constants Regarding to the Effect of Curvature and the Selection of Rotation States. Chem. J. Chinese Universities, 1996, 17(7): 1104.