A multi-dimensional microcanonical Monte Carlo study of S_0→T_1 intersystem crossing of isocyanic acid  

作　　者：ZHANG Feng1,2,FANG WeiHai1,LUO Yi2 & LIU RuoZhuang1 1 College of Chemistry,Beijing Normal University,Beijing 100875,China 2 Theoretical Chemistry,School of Biotechnology,Royal Institute of Technology,S-10691 Stockholm,Sweden 

出　　处：《Science China Chemistry》2009年第11期1885-1891,共7页中国科学（化学英文版）

基　　金：Supported by the National Natural Science Foundation of China (Grant No. 20720102038)

摘　　要：A general formula for the multi-dimensional Monte Carlo microcanonical nonadiabatic rate constant expressed in configuration space is applied to calculate the rate of intersystem crossing(ISC) between the ground(S0) and first excited triplet(T1) states for isocyanic acid.One-,two-and three-dimensional potential energy surfaces are constructed by coupled-cluster single-double CCSD calculations,which are used for Monte Carlo sampling.The calculated S0→T1 ISC rate is in good agreement with experimental findings,which gives us a reason to believe that the multi-dimensional Monte Carlo microcanonical nonadiabatic rate theory is a very effective method for calculating nonadiabatic transition rate of a polyatomic molecule.A general formula for the multi-dimensional Monte Carlo microcanonical nonadiabatic rate constant expressed in configuration space is applied to calculate the rate of intersystem crossing(ISC) between the ground(S0) and first excited triplet(T1) states for isocyanic acid.One-,two-and three-dimensional potential energy surfaces are constructed by coupled-cluster single-double CCSD calculations,which are used for Monte Carlo sampling.The calculated S0→T1 ISC rate is in good agreement with experimental findings,which gives us a reason to believe that the multi-dimensional Monte Carlo microcanonical nonadiabatic rate theory is a very effective method for calculating nonadiabatic transition rate of a polyatomic molecule.

关 键 词：MULTI-DIMENSIONAL MONTE Carlo MICROCANONICAL NONADIABATIC rate theory intersystem CROSSING isocyanic ACID NONADIABATIC transition 

分 类 号：O641.1[理学—物理化学]