Quantum Dynamics of Vinylidene Photodetachment on an Accurate Global Acetylene-Vinylidene Potential Energy Surface

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• 作者：Lifen Guo ; Huixian Han ; Jianyi Ma ; Hua Guo
• 刊名：Journal of Physical Chemistry A
• 出版年：2015
• 出版时间：August 6, 2015
• 年：2015
• 卷：119
• 期：31
• 页码：8488-8496
• 全文大小：493K
• ISSN：1520-5215

文摘

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鈥搗inylidene 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鈥搗inylidene potential energy surface.