Ab initio determination of potential energy surfaces for the first two UV absorption bands of SO2

作者：Xie Changjian; Hu Xixi; Zhou Linsen; Xie Daiqian^*; Guo Hua

来源：Journal of Chemical Physics, 2013, 139(1): 014305.

DOI：10.1063/1.4811840

Three-dimensional potential energy surfaces for the two lowest singlet ((A) over tilde B-1(1) and (B) over tilde (1)A(2)) and two lowest triplet ((a) over tilde (3)B1 and (b) over tilde (3)A(2)) states of SO2 have been determined at the Davidson corrected internally contracted multi-reference configuration interaction level with the augmented correlationconsistent polarized triple-zeta basis set (icMRCI+ Q/AVTZ). The non-adiabatically coupled singlet states, which are responsible for the complex Clements bands of the B band, are expressed in a 2 x 2 quasi-diabatic representation. The triplet state potential energy surfaces, which are responsible for the weak A band, were constructed in the adiabatic representation. The absorption spectrum spanning both the A and B bands, which is calculated with a three-state non-adiabatic coupled Hamiltonian, is in good agreement with experiment, thus validating the potential energy surfaces and their couplings.

• 出版日期2013-7-7
• 单位南京大学