Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
J Chem Phys. 2013 Jul 7;139(1):014305. doi: 10.1063/1.4811840.
Three-dimensional potential energy surfaces for the two lowest singlet (Ã(1)B1 and B̃(1)A2) and two lowest triplet (ã(3)B1 and b̃(3)A2) states of SO2 have been determined at the Davidson corrected internally contracted multi-reference configuration interaction level with the augmented correlation-consistent 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 × 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.
已经在 Davidson 修正的内收缩多参考组态相互作用水平上，使用扩充的关联一致极化三重 zeta 基组（icMRCI+Q/AVTZ），确定了 SO2 的两个最低单重态（Ã(1)B1 和 B̃(1)A2）和两个最低三重态（ã(3)B1 和 b̃(3)A2）的三维势能面。负责复杂克莱门斯带（B 带）的非绝热耦合单重态以 2×2 准非绝热表示表示。负责弱 A 带的三重态势能面是在绝热表示中构建的。用三态非绝热耦合哈密顿量计算的横跨 A 带和 B 带的吸收光谱与实验很好地吻合，从而验证了势能面及其耦合。
