Ab initio investigation of Br-3d core-excited states in HBr and HBr+ toward XUV probing of photochemical dynamics

Ultrafast X-ray/XUV transient absorption spectroscopy is a powerful tool for real-time probing of chemical dynamics. Interpretation of the transient absorption spectra requires knowledge of core-excited potentials, which necessitates assistance from high-level electronic-structure computations. In this study, we investigate Br-3d core-excited electronic structures of hydrogen bromide (HBr) using spin-orbit general multiconfigurational quasidegenerate perturbation theory (SO-GMC-QDPT). Potential energy curves and transition dipole moments are calculated from the Franck-Condon region to the asymptotic limit and used to construct core-to-valence absorption strengths for five electronic states of HBr ((1)Sigma(0+); (3)Pi(1); (1)Pi(1); (3)Pi(0+); (3)Sigma(1)) and two electronic states of HBr+ ((2)Pi(3/2), (2)Sigma(1/2)). The results illustrate the capabilities of Br-3d edge probing to capture transitions of the electronic-state symmetry as well as nonadiabatic dissociation processes that evolve across avoided crossings. Furthermore, core-to-valence absorption spectra are simulated from the neutral (1)Sigma(0+) state and the ionic (2)Pi(1/2,3/2) states by numerically solving the time-dependent Schrodinger equation and exhibit excellent agreement with the experimental spectrum. The comprehensive and quantitative picture of the core-excited states obtained in this work allows for transparent analysis of the core-to-valence absorption signals, filling gaps in the theoretical understanding of the Br-3d transient absorption spectra. (C) 2019 Author(s).