Quantum Dynamics of Vinylidene Photodetachment on an Accurate Global Acetylene-Vinylidene Potential Energy Surface.
Quantum Dynamics of Vinylidene Photodetachment on an Accurate Global Acetylene-Vinylidene Potential Energy Surface.
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DOI：
10.1021/acs.jpca.5b05061
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发表时间：
2015-07
期刊：
影响因子：
--
通讯作者：
Lifen Guo;Huixian Han;Jianyi Ma;Hua Guo
中科院分区：
文献类型：
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作者：
Lifen Guo;Huixian Han;Jianyi Ma;Hua Guo
亚乙烯是乙炔的一种高能异构体，这两种异构体中的键重排是异构化反应的原型。在这里，通过模拟亚乙叉阴离子的光剥离动力学，在最近发展起来的全局乙炔-亚乙烯势能面上对亚乙烯振动进行了全维量子力学研究。首先在一个新的从头算势能面上测定了阴离子的几个低激发态振动能级，并在Condon近似下得到了它们的光电子能谱。亚乙叉异构体的振动特征在位置和强度上都与实验相符，验证了乙炔-亚乙叉的整体势能面。
Vinylidene is a high-energy isomer of acetylene, and the rearrangement of bonds in the two species serves as a prototype for isomerization reactions. Here, a full-dimensional quantum mechanical study of the vinylidene vibration is carried out on a recently developed global acetylene-vinylidene potential energy surface by simulating the photodetachment dynamics of the vinylidene anion. Several low-lying vibrational levels of the anion were first determined on a new ab initio based potential energy surface, and their photoelectron spectra were obtained within the Condon approximation. The vibrational features of the vinylidene isomer are found to agree well with the experiment in both positions and intensities, validating the global acetylene-vinylidene potential energy surface.