Vibronic Coupling Effects in the Photoelectron Spectra of LiB6-

Abstract

The present article exhibits a theoretical exploration of vibronic coupling effects in the 193 nm experimental photoelectron spectra of the LiB₆^-, focusing on its six lowest-lying electronic states. Based on adiabatic potential energy curves derived from abinitio calculations, we construct a diabatic vibronic Hamiltonian and perform nuclear dynamics by adopting TD and TI formulations of quantum mechanics, treating in adiabatic (uncoupled) and non-adiabatic (coupled) scenarios. In this study, Poisson statistics provided vibronic intensity progressions from an adiabatic perspective, and the rapid transfer of electronic population confirmed the magnitude of the non-adiabatic coupling. Our final simulated spectrum reproduces the peaks of the experimental spectra in good agreement, providing the detailed vibronic interpretation of the photoelectron spectrum of LiB₆^-