Theoretical study on potential energy curves and spectroscopy properties of ground and low-lying excited electronic states of BrCl^+  

作　　者：WANG MingWei  WANG BingWu  CHEN ZhiDa 

机构地区：[1]Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

出　　处：《Science China Chemistry》2008年第6期521-528,共8页中国科学（化学英文版）

基　　金：the National Basic Research Program of China(Grant No.2006CB601102);the National Natural Science Foundations of China(Grant Nos.20490210 and 20503001)

摘　　要：The calculations on the potential energy curves and spectroscopic constants of the ground and low-lying excited states of BrCl^+, one of the important molecular ions in environment science, have been performed by using the multireference configuration interaction method at high level of theory in quantum chemistry. Through analyses of the effects of the spin-orbit coupling interaction on the electronic structures and spectroscopic properties, the multiconflguration characteristic of the X^2Π ground state and low-lying excited states was established. The spin-orbit coupling splitting energy of the X^2 Π ground state was calculated to be 1814 cm^(-1), close to the experimental value 2070 cm^(-1). The spin-orbit coupling splitting energy of the ~2Π(II) exited state was predicted to be 766 cm^(-1). The transition dipole moments and Frank-Condon factors of the 3/2(III)-X3/2 and 1/2(III)-1/2(I) transitions were estimated, and the radiative lifetimes of the two transitions were briefly discussed.The calculations on the potential energy curves and spectroscopic constants of the ground and low-lying excited states of BrCl+,one of the important molecular ions in environment science,have been performed by using the multireference configuration interaction method at high level of theory in quantum chemistry.Through analyses of the effects of the spin-orbit coupling interaction on the elec-tronic structures and spectroscopic properties,the multiconfiguration characteristic of the X2Π ground state and low-lying excited states was established.The spin-orbit coupling splitting energy of the X2 Π ground state was calculated to be 1814 cm-1,close to the experimental value 2070 cm-1.The spin-orbit coupling splitting energy of the 2Π(Ⅱ) exited state was predicted to be 766 cm-1.The transition dipole moments and Frank-Condon factors of the 3/2(Ⅲ)-X3/2 and 1/2(Ⅲ)-1/2(I) transitions were estimated,and the radiative lifetimes of the two transitions were briefly discussed.

关 键 词：BrCl+ ab INITIO MRCI(SD)+Q method SPIN-ORBIT coupling LOW-LYING excited state potential energy CURVES 

分 类 号：O561.3[理学—原子与分子物理]