Theoretical MRCI + Q study on electronic structure and spectroscopic properties of the HX⁺(X = F, Cl, Br, I) cations

Abstract

In this work, we have systematacially investigated the electronic structure and spectroscopic properties of the HX+ (X = F, Cl, Br, I) cations by using the highly correlated MRCI+Q approach. This is the first comprehensive ab initio study on the electronic states of the HX+ cations. The SOC effect is introduced with the state interaction approach. There are total 10 Λ-S and 18 Ω states obtained in the calculation. The results show that the PECs′ shapes and structure of the electronic states of different HX+ cations exhibit the significant distinction due to the X-dependent energy-level order of the unique dissociation channel H+(1Sg)+X(2Pu). From PECs, the spectroscopic constants of the bound electronic states are determined, which are in good agreement with available observed values. Regarding HBr+ and HI+, the good agreement has been achieved only when the SOC effect is considered. The predissociation for the first excited A2Σ+ state of HCl+, HBr+, and HI+ is analyzed based on computed spin-orbit matrix elements. Around the equilibrium position, the energy splittings of X2Π are calculated to be 288 cm-1, 661 cm-1, 2691 cm-1, and 5137 cm-1 for HF+, HCl+, HBr+, and HI+, respectively. It has been demonstrated that SOC is substantial for HX+, leading to significant changes in PECs′ shapes as well as in electronic structure. Finally, the transition properties are predicted, including transition dipole moments, Franck-Condon factors, and radiative lifetimes. Both the Ω transitions A2Σ+ 1/2-X2Π3/2 and A2Σ+ 1/2-X2Π1/2 of the HX+ cations are determined to possess the radiative lifetimes at the microsecond (µs) level.