Wang Jun, Li Jun, Ma Jianyi, Guo Hua
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, USA.
J Chem Phys. 2014 May 14;140(18):184314. doi: 10.1063/1.4874975.
The photodetachment of both the HOCO(-) and DOCO(-) anions is investigated using full-dimensional quantum wave packets on new ab initio based global potential energy surfaces for both the neutral and anionic species. The calculated electron affinities and neutral fundamental vibrational frequencies of both isotopomers are in good agreement with available experimental data. The measured photoelectron spectra are also accurately reproduced, further validating the accuracy of the potential energy surfaces. In addition, strong mode specificity is found in the lifetimes of the HOCO vibrational features and the tunneling facilitated predissociation rates to H + CO2 are rationalized using the recently proposed sudden vector projection model.
利用基于从头算的中性和阴离子物种全局势能面的全维量子波包，研究了HOCO(-)和DOCO(-)阴离子的光解离。两种同位素异构体的计算电子亲和能和中性基频与现有实验数据吻合良好。测量的光电子能谱也得到了准确再现，进一步验证了势能面的准确性。此外，在HOCO振动特征的寿命中发现了强烈的模式特异性，并使用最近提出的突然矢量投影模型对隧穿促进的H + CO2预解离速率进行了合理化解释。
