Theoretical study on excited states of ICl+ molecular ion considering spin-orbit coupling

TL;DR

This study provides a detailed theoretical analysis of the excited states of the ICl+ molecular ion, incorporating spin-orbit coupling and other effects to accurately predict electronic structure, spectroscopic constants, and transition properties.

Contribution

The paper introduces a comprehensive high-level computational approach including SOC effects to analyze ICl+ electronic states, which enhances the accuracy of spectroscopic and transition property predictions.

Findings

Spin-orbit coupling significantly affects low-lying states' properties.

Potential energy curves reveal possible predissociation channels.

Computed radiative lifetimes aid in spectroscopic identification.

Abstract

The electronic structure of the ICl+ molecular ion is investigated by using high-level multireference configuration interaction (MRCI) method. To improve computational accuracy, Davidson corrections, spin-orbit coupling (SOC), and core-valence electron correlations effects are incorporated into the calculations. The potential energy curves (PECs) of 21 electronic states associated with the two lowest dissociation limits are obtained. The dipole moments (DMs) of the 21 electronic states of ICl+ are systematically studied, and the variations of DMs of the identical symmetry state in the avoided crossing regions are elucidated by analyzing the dominant electronic configuration. With the help of the calculated SOC matrix element, the interaction between crossing states can be elucidated. Spin-orbit coupling matrix elements involving the several states are calculated. By analyzing potential energy curves of these states and the nearby electronic states, the possible predissociation channels are provided. Based on the computed PECs, the spectroscopic constants of bound states are determined. The comparison of the spectroscopic constants including and excluding SOC effect indicates that the SOC effect has an obvious correction to the spectroscopic properties of low-lying states. Finally, the transition properties between excited states and the ground state are studied. Based on the computed transition dipole moments and Franck-Condon Factors, radiative lifetimes for the low-lying vibrational levels of excited states are evaluated.