Qin Yuan, Zheng Xianfeng, Song Yu, Sun Ge, Zhang Jingsong
Department of Chemistry, University of California at Riverside, Riverside, California 92521, USA.
J Chem Phys. 2023 Oct 14;159(14). doi: 10.1063/5.0176504.
Photo-predissociation of rovibrational levels of SH (A2Σ+, v' = 0-6) is studied using the high-n Rydberg atom time-of-flight technique. Spin-orbit branching fractions of the S(3PJ=2,1,0) products are measured in the product translational energy distributions. The SH A2Σ+v' = 0 state predissociates predominantly via coupling to the 4Σ- repulsive state. As the vibrational level v' increases, predissociation dynamics change drastically, with all three repulsive states (4Σ-, 2Σ-, and 4Π) involved in the dissociation. Nonadiabatic interactions and quantum interferences among these dissociation pathways affect the fine-structure state distributions of the S(3PJ=2,1,0) products.
利用高n里德堡原子飞行时间技术研究了SH（A2Σ+，v' = 0 - 6）振转能级的光预解离。在产物平动能分布中测量了S(3PJ=2,1,0)产物的自旋 - 轨道分支比。SH A2Σ+v' = 0态主要通过与4Σ-排斥态耦合而预解离。随着振动能级v'增加，预解离动力学急剧变化，解离过程涉及所有三个排斥态（4Σ-、2Σ-和4Π）。这些解离途径之间的非绝热相互作用和量子干涉影响了S(3PJ=2,1,0)产物的精细结构态分布。
