Nonadiabatic fragmentation of H2O+ and isotopomers. Wave packet propagation using ab initio wavefunctions

Abstract

The fragmentation of the water cation from its ²B₂ electronic state, allowing the participation of the ²B₁, Ã ²A₁ and ²B₁ states in the process, is simulated using the extended capabilities of the collocation GridTDSE code to account for the nonadiabatic propagation of wave packets in several potential energy surfaces connected by nonadiabatic couplings. Molecular data are calculated ab initio. Two initial wave packets are considered to reproduce two different experiments. The isotopic effect in the fragmentation of D₂O⁺ and HDO⁺ is also studied and the results show very good agreement with the experimental cleavage preference in the fragmentation of HDO⁺.