Investigations on transition properties of X1Σ+, A1Σ−, B1Δ, C1Π, D1Σ+, E1Π, and F1Σ+ states of PS+ cation

Abstract

Ab initio calculations have been performed to study the transition properties of the PS+ cation. Transition dipole moments of fourteen dipole-allowed transitions, between the X1Σ+, A1Σ−, B1Δ, C1Π, D1Σ+, E1Π, and F1Σ+ states, have been calculated with the aug-cc-pV6Z basis set. Transition probabilities, band origins, as well as radiative lifetimes of vibronic emissions are predicted. The vibrational radiative lifetimes are estimated to be in order of 10−8 s for the D1Σ+, F1Σ+, and first well of E1Π states; 10−7 s for the C1Π state; 10−3-10−4 s for the second well of E1Π state. Various curve crossings and avoided crossings are revealed with the help of our computed spin–orbit coupling matrix elements. The intricate couplings among different electronic states are analyzed. We propose that the curve crossing with the D1Σ+ state may be responsible for the fact that the C1Π ν' > 7 vibrational levels cannot be detected in experiment.