State-Resolved Quantum Dynamics of Photodetachment of HCO2(-)/DCO2(-) on an Accurate Global Potential Energy Surface.
State-Resolved Quantum Dynamics of Photodetachment of HCO2(-)/DCO2(-) on an Accurate Global Potential Energy Surface.
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DOI：
10.1021/jp512557k
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发表时间：
2015-01
期刊：
影响因子：
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通讯作者：
Lindong Zou;Jun Yu Li;Hui Wang;Jianyi Ma;Hua Guo
中科院分区：
文献类型：
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作者：
Lindong Zou;Jun Yu Li;Hui Wang;Jianyi Ma;Hua Guo
采用波包方法，在精确的中性HOCO/HCO_2体系整体势能面上，对HCO_2（-）和DCO_2（-）的光剥离过程进行了全维量子动力学研究.计算的光电子能谱再现了实验中观察到的HCO 2和DCO 2主峰的位置和宽度。具体而言，由于绝热PES捕获了（2）A1和（2）B2最小值，因此在我们的模拟中识别了中性自由基的（2）A1和（2）B2共振峰。窄的宽度和同位素效应的最低共振表明隧道促进预解离。此外，解离产物CO2被发现在其对称的拉伸和弯曲模式，这是通过一个强大的费米共振耦合，但旋转冷，在最近的光电子-光剥离符合实验的良好协议被激发。
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.