Multi-state and Multi-mode Vibronic Coupling Effects in the Photoionization Spectroscopy of Acetaldehyde.

Abstract

Multi-state and multi-mode vibronic dynamics in the seven energetically low-lying (, , , , , , and ) electronic states of the acetaldehyde radical cation is theoretically studied in this article. Adiabatic energies of these electronic states are calculated by ab initio quantum chemistry methods. A vibronic coupling model of seven electronic states is constructed in a diabatic electronic basis to carry out the first-principles nuclear dynamics study. The vibronic spectrum is calculated and compared with the experimental findings reported in the literature. The progressions of vibrational modes found in the spectrum are assigned. The findings reveal that the and electronic states are energetically well-separated from the other electronic states and the remaining states ( to ) are energetically very close or even quasi-degenerate at the equilibrium geometry of the reference electronic ground state of acetaldehyde. The energetic proximity of to electronic states results in multiple multi-state conical intersections. The impact of electronic nonadiabatic interactions due to conical intersections on the vibronic structure of the photoionization band and nonradiative internal conversion dynamics is discussed.