Disentanglement of triplet and singlet states of azobenzene: direct EELS detection and QMC modeling

Abstract

Singlet and triplet excited states of trans-azobenzene have been measured in the gas phase by electron energy loss spectroscopy (EELS). In order to interpret the strongly overlapping singlet and triplet bands in the spectra a set of large-scale correlated quantum Monte-Carlo (QMC) simulations was performed. The EELS/QMC combination of methods yields an excellent agreement between theory and experiment and for the two low-lying excited singlet and two low-lying triplet states permitted their unambiguous assignment. In addition, EELS revealed two overlapping electronic states in the band commonly assigned as S₂, the lower one with a pronounced vibrational structure, the upper one structureless. Finally, the agreement between theory and experiment was shown to further increase by taking computationally into account the finite temperature effects.