Promoting-mode free formalism for excited state radiationless decay process with Duschinsky rotation effect  

作　　者：NIU YingLi PENG Qian SHUAI ZhiGang 

机构地区：[1]Key Laboratory of Organic Solids,Beijing National Laboratory for Molecular Sciences(BNLMS),Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China [2]Department of Chemistry,Tsinghua University,Beijing 100084,China

出　　处：《Science China Chemistry》2008年第12期1153-1158,共6页中国科学（化学英文版）

基　　金：Supported by the National Natural Science Foundation of China (Grant Nos. 10425420, 20433070 and 90503013)

摘　　要：In the present work, through the path integral of Gaussian type correlation function, a new formalism based on Fermi-Golden Rule for calculating the rate constant of nonradiative decay process with Duschinsky rotation effect in polyatomic molecules is developed. The advantage of the present path-integral formalism is promoting-mode free. In order to get the rate constant, a "transition rate matrix" needs to be calculated. The rate constant calculated previously is only an approximation of diagonal elements of our "transition rate matrix " . The total rate should be the summation over all the matrix elements.In the present work, through the path integral of Gaussian type correlation function, a new formalism based on Fermi-Golden Rule for calculating the rate constant of nonradiative decay process with Duschinsky rotation effect in polyatomic molecules is developed. The advantage of the present path-integral formalism is promoting-mode free. In order to get the rate constant, a “transition rate matrix” needs to be calculated. The rate constant calculated previously is only an approximation of diagonal elements of our “transition rate matrix”. The total rate should be the summation over all the matrix elements.

关 键 词：Duschinsky ROTATION radiationless DECAY correlation function path integral promoting-mode free 

分 类 号：O561[理学—原子与分子物理]