Zhang Lei, Zou Wenli, Yu Yao, Yang Jie
School of Mathematics and Physics, Lanzhou Jiaotong University, Lanzhou 730070, China.
Institute of Modern Physics, Northwest University, Xi'an 710127, Shaanxi, China.
J Chem Phys. 2023 Nov 28;159(20). doi: 10.1063/5.0179596.
The optical spectra of the palladium monosulfide (PdS) molecule in gas phase have been investigated for the first time through laser-induced fluorescence (LIF) and single-vibronic-level (SVL) emission spectroscopies. The I3Σ- - X3Σ- transition system containing 16 vibronic bands was identified in the LIF spectra, covering the energy range of 22 030-23 400 cm-1. The spectra with rotational resolution allowed for the determination of the molecular constants in both the ground X and excited I electronic states, involving the spin-orbit splitting, rotational constant, vibrational frequency, and isotope shift. Isotopically resolved SVL emission spectra permitted the observation of the spin-orbit splitting, vibrational frequency, and vibrational isotope shift of the X3Σ-0+,1 and A3Π2,1,0-,0+ states as they transitioned from the excited I state to the vibrational levels of the X and A states. Ab initio calculations presented plenty of the Λ-S and Ω states of PdS below 28 000 cm-1 and provided strong support for the assignments of the experimental observation.
首次通过激光诱导荧光（LIF）和单振子能级（SVL）发射光谱研究了气相中单硫化钯（PdS）分子的光谱。在LIF光谱中识别出包含16个振转带的I3Σ- - X3Σ-跃迁系统，覆盖22 030 - 23 400 cm-1的能量范围。具有转动分辨率的光谱能够确定基态X和激发态I电子态中的分子常数，包括自旋轨道分裂、转动常数、振动频率和同位素位移。同位素分辨的SVL发射光谱使得在X3Σ-0 +,1和A3Π2,1,0 -,0 +态从激发态I跃迁到X和A态的振动能级时，能够观察到自旋轨道分裂、振动频率和振动同位素位移。从头算计算给出了低于28 000 cm-1的大量PdS的Λ-S和Ω态，并为实验观测的归属提供了有力支持。
