Multireference configuration interaction study of the 27 low-lying states of the PF+ cation

This paper investigated the spectroscopic parameters and vibrational properties of 27 Λ-S and 60 Ω states of PF+ cation. All the PECs were calculated with the CASSCF method, which was followed by the icMRCI + Q approach. The a4Σ−, b4Π, and D2Δ states were inverted with the SOC effect accounted for. The 24Π, 24Σ−, 22Δ, 32Δ, 32Σ+, 42Σ+, 12Φ, and 22Σ− states were repulsive whether the SOC effect was included or not, but the 52Π and D2Δ states became repulsive only with the SOC effect included. The C2Σ− state was very weakly bound. The a4Σ− state had one barrier. The avoided crossings existed between the a4Σ− and 24Σ− states, the 22Σ+ and 32Σ+ states as well as the D2Δ and 22Δ states. The spectroscopic and vibrational properties were determined. The TDMs between two Λ-S states were calculated and the FC factors of some transitions were evaluated. The SOC effect on the spectroscopic and vibrational properties was discussed. Analyses show that the spectroscopic results obtained in this paper can be expected to be reliably predicted ones.184