Product fine-structure resolved photodissociation dynamics: the A band of H2O.
The photodissociation dynamics of H2O in its first absorption band is investigated on an accurate potential energy surface based on a large number of high-level ab initio points. Several ro-vibrational states of the parent molecule are considered. Different from most previous theoretical studies, the spin-orbit and Λ-doublet populations of the open-shell OH fragment are reported from full-dimensional wave packet calculations. The populations of the two spin-orbit manifolds are in most cases close to the statistical limit, but the Λ-doublet is dominated by the A(") component, thanks largely to the fast in-plane dissociation of H2O(Ã(1)A('')). Comparisons with experimental data and a Franck-Condon model are generally very good, although some discrepancies exist.
Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
Linsen
L
Zhou
Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
Daiqian
D
Xie
State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical and Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Zhigang
Z
Sun
Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.
Hua
H
Guo