These effects of spin-orbit coupling, core-valence correlation and scalar relativistic correction on spectroscopic calculations for PN+ cation

The potential energy curves (PECs) of 9 Λ-S states (X2Σ+, 14Σ+, 16Σ+, 12Π, 14Π, 16Π, 14Δ, 14Σ−, 24Π) and corresponding 28 Ω states of PN+ cation are calculated by the complete active space self-consistent field (CASSCF), which is followed by the internally contracted multireference configuration interaction (icMRCI) with the Davidson modification. The calculation is taken into account these effects of spin-orbit coupling, core-valence correlation and scalar relativistic correction. All the Λ-S states are found to be the bound states. The 24Π, 16Π and 14Σ− states possess double wells. Basis on the PECs, the spectroscopic parameters are evaluated. Excellent agreement is found between the present spectroscopic parameters and available measurements. In particular, dissociation energy De in the X2Σ+ Λ-S state is determined to be 5.0505 eV, which agrees well with the measurements of 5.0410 eV, the deviations of present De from the experiment values is only 0.0095 eV (0.18%). Finally, the transitions (transition dipole moments, Franck-Condon Factors and radiative lifetimes) from 16Π−1/2 and 24Π−1/2 (the first well of the two states) to the ground state 12Σ+1/2 are obtained in this paper. These results reported here could be expected to be helpful for the experiment in the future.110