Geometric phase effects in the resonance spectrum, state-to-state transition probabilities and bound state spectrum of HO2

Abstract

The general vector potential (gauge theory) approach for including geometric phase effects in accurate 3D quantum scattering calculations in hyperspherical coordinates is applied to low-energy H+O2 collisions using our new more accurate DIM (Diatomics In Molecules) potential energy surface. The newly developed hybrid DVR/FBR (Discrete Variable Representation/Finite Basis Representation) numerical technique is used to include geometric phase effects due to the C2v conical intersection in HO2. The scattering results for zero total angular momentum (J=0) computed both with and without the geometric phase show significant differences in the resonance energies and lifetimes. Significant differences in the state-to-state transition probabilities are also observed. The results indicate that geometric phase effects must be included for H+O2 scattering even at low energies. All 249 vibrational energies of HO2(2A′′) (J=0) are computed both with and without the geometric phase. Due to the localized nature of the bound state wavefunctions, no geometric phase effects are observed in the vibrational energies even in the high-lying states near dissociation.