The electronic structure of WS molecule below 21,500 cm−1

Abstract

The low-lying electronic states of the tungsten monosulfide (WS) molecule have been investigated using laser-induced fluorescence excitation spectra and high-level ab initio calculations. 29 vibronic bands in total are experimentally observed in the range of 13,100 – 21,500 cm−1 and grouped into 8 electronic transition systems. The spectroscopic constants including the vibrational frequency, rotational constant and radiative lifetime in the low-lying excited electronic state are obtained by analysis of the rovibrational-resolved spectra. Seven lowest Ω sub-states that belong to the lowest three Λ-S states considering the spin-orbit effect, i.e. the ground state 3Σ−, first and second excited states 5Π and 3Φ, are identified through single-vibrational-level emission spectra. In addition, seven Ω = 1 excited sub-states in the visible energy range are identified, which are consecutively consistent with the ab initio calculation results of the sixth to twelfth Ω = 1 sub-states. The experimental and theoretical results on WS molecule may provide a benchmark to study the electronic structure of those molecules with strong spin-orbit coupling and electron-electron correlation.