Accurate spectroscopic calculations of the 22 Λ-S states and 60Ω states of the PS+cation.
This work studied the potential energy curves of 22 Λ-S states, which were yielded from the first two dissociation limits, P(4Su)+S+(4Su) and P+(3Pg)+S(3Pg), of the PS+cation. The potential energy curves were calculated employing the CASSCF method, which was followed by the internally contracted MRCI approach with Davidson correction. Core- valence correlation and scalar relativistic corrections as well as basis set extrapolation were included. Of these 22 Λ-S states, only the 35Σ+state was repluse without the spin-orbit coupling effect, whereas the 35Σ+, 15Δ, 25Σ+, and 15Σ-states were repulse with the spin-orbit coupling effect accounted for. The 21Π and 23Π states had double wells, but the first well of the 23Π state had no vibrational levels and the first well of 21Π state had only one vibrational state. The avoided crossings were found between the 11Π and 21Π states and between the d3Π and 23Π states. The 25Σ+, 15Π, 15Δ, b3Δ, and c3Σ-states were inverted with the spin-orbit coupling effect taken into account. The 15Δ, 25Σ+, 15Σ-, and 21Π states were weakly bound. The spectroscopic properties were evaluated and compared with the experimental and other theoretical results. The Franck-Condon factors of some electronic transitions between different Λ-S states were determined. The vibrational levels of several states were predicted. The spin-orbit coupling effect on the spectroscopic parameters was discussed. Analyses show that the spectroscopic results obtained here can be expected to be reliably predicted ones.
College of Physics and Material Science, Henan Normal University, Xinxiang 453007, China; College of Physics and Electronic Engineering, Xinyang Normal University, Xinyang 464000, China.
Hui
H
Liu
College of Physics and Material Science, Henan Normal University, Xinxiang 453007, China. Electronic address: scattering@sina.com.cn.
Deheng
D
Shi
College of Physics and Material Science, Henan Normal University, Xinxiang 453007, China.
Jinfeng
J
Sun
College of Physics and Material Science, Henan Normal University, Xinxiang 453007, China.
Zunlue
Z
Zhu
Avoided crossing; Potential energy curve; Spectroscopic parameter; Spin-orbit coupling; Vibrational property