Franck–Condon simulation of photoelectron spectroscopy of HOO −: Including Duschinsky effects

Abstract

Geometry optimization and harmonic vibrational frequency calculations were performed on the X ∼ 2 A ″ and A ∼ 2 A ′ states of HOO and X ∼ 1 A ′ state of HOO −. The electron affinity and the term energy ( X ∼ 2 A ″ – A ∼ 2 A ′ ) of HOO were calculated at various theory levels. Franck–Condon analyses and spectral simulations were carried out on the X ∼ 2 A ″ – X ∼ 1 A ′ and A ∼ 2 A ′ – X ∼ 1 A ′ photodetachment processes. The spectral simulations of vibrational structures based on the computed Franck–Condon factors are in excellent agreement with the observed spectra. In addition, the equilibrium geometrical parameters of the X ∼ 1 A ′ state of HOO − and A ∼ 2 A ′ state of HOO were obtained in the spectral simulations.