title: Full-dimensional quantum dynamics of vibrationally mediated photodissociation of NH3 and ND3 on coupled ab initio potential energy surfaces: absorption spectra and NH2(Ã(2)A1)/NH2(X̃(2)B1) branching ratios.
abstract: Vibrationally mediated photodissociation of NH3 and ND3 in the A band allows the exploration of the excited-state potential energy surface in regions that are not accessible from the ground vibrational state of these polyatomic systems. Using our recently developed coupled ab initio potential energy surfaces in a quasi-diabatic representation, we report here a full-dimensional quantum characterization of the Ã ← X̃ absorption spectra for vibrationally excited NH3 and ND3 and the corresponding nonadiabatic dissociation dynamics into the NH2(Ã(2)A1) + H and NH2(X̃(2)B1) + H channels. The predissociative resonances in the absorption spectra have been assigned with appropriate quantum numbers. The NH2(Ã(2)A1)/NH2(X̃(2)B1) branching ratio was found to be mildly sensitive to the initial vibrational excitation prior to photolysis. Implications for interpreting experimental data are discussed.
authors.affiliation: Institute of Atomic and Molecular Physics, Sichuan University , Chengdu, Sichuan 610065, China.
authors.forename: Jianyi
authors.initials: J
authors.lastname: Ma
authors.forename: Changjian
authors.initials: C
authors.lastname: Xie
authors.forename: Xiaolei
authors.initials: X
authors.lastname: Zhu
authors.forename: David R
authors.initials: DR
authors.lastname: Yarkony
authors.forename: Daiqian
authors.initials: D
authors.lastname: Xie
authors.forename: Hua
authors.initials: H
authors.lastname: Guo