title: State-Resolved Quantum Dynamics of Photodetachment of HCO2(-)/DCO2(-) on an Accurate Global Potential Energy Surface.
abstract: Full-dimensional quantum dynamics studies of the photodetachment of HCO2(-) and DCO2(-) are reported using a wave-packet method on an accurate global potential energy surface of the neutral HOCO/HCO2 system. The calculated photoelectron spectra reproduced both the positions and widths of the main HCO2 and DCO2 peaks observed in experiment. Specifically, both the (2)A1 and (2)B2 resonance peaks of the neutral radicals were identified in our simulations thanks to the adiabatic PES that captures both the (2)A1 and (2)B2 minima. The narrow widths and isotope effect of the lowest resonances are indicative of tunneling-facilitated predissociation. Furthermore, the dissociation product CO2 was found to be excited in both its symmetric stretching and bending modes, which are coupled via a strong Fermi resonance, but rotationally cold, in good agreement with the recent photoelectron-photodetachment coincidence experiments.
authors.affiliation: †Institute of Atomic and Molecular Physics, Sichuan University, Chengdu, Sichuan 610065, China.
authors.forename: Lindong
authors.initials: L
authors.lastname: Zou
authors.affiliation: ‡Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, United States.
authors.forename: Jun
authors.initials: J
authors.lastname: Li
authors.affiliation: §National Key Laboratory for Reactor Fuel and Materials, Nuclear Power Institute of China, Chengdu, Sichuan 610041, China.
authors.forename: Hui
authors.initials: H
authors.lastname: Wang
authors.affiliation: †Institute of Atomic and Molecular Physics, Sichuan University, Chengdu, Sichuan 610065, China.|‡Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, United States.
authors.forename: Jianyi
authors.initials: J
authors.lastname: Ma
authors.affiliation: ‡Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, United States.
authors.forename: Hua
authors.initials: H
authors.lastname: Guo