Accurate Quantum Dynamics of the Simplest Isomerization System Involving Double-H Transfer  

最小双氢转移异构体系的精确量子动力学研究

作　　者：Jia Luo Jianwei Cao Hao Liu Wensheng Bian 罗佳;曹剑炜;刘昊;边文生(中国科学院化学研究所,北京分子科学国家研究中心,北京100190;中国科学院大学化学科学学院,北京100049)

机构地区：[1]Beijing National Laboratory for Molecular Sciences,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China [2]School of Chemical Sciences,University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Chinese Journal of Chemical Physics》2022年第1期185-192,I0064,共9页化学物理学报（英文）

基　　金：supported by the National Natural Science Foundation of China(No.21973098 and No.22133003);the Youth Innovation Promotion Association CAS(No.2018045);the Beijing National Laboratory for Molecular Sciences。

摘　　要：We perform accurate quantum dynamcs calculations on the isomerization of vinylidene-acetylene.Large-scale parallel computations are accomplished by an efficient theoretical scheme developed by our group,in which the basis functions are customized for the double-H transfer process.The A_(1)' and B_(2)'' vinylidene and delocalization states are obtained.The peaks recently observed in the cryo-SEVI spectra are analyzed,and very good agreement for the energy levels is achieved between theory and experiment.The discrepancies of energy levels between our calculations and recent experimental cryo-SEVI spectra are of similar magnitudes to the experimental error bars,or≤30 cm^(-1) excluding those involving the excitation of the CCH_(2) scissor mode.A kind of special state,called the isomerization state,is revealed and reported,which is characterized by large probability densities in both vinylidene and acetylene regions.In addition,several states dominated by vinylidene character are reported for the first time.The present work would contribute to the understanding of the double-H transfer.

关 键 词：Quantum dynamics Double-H transfer ISOMERIZATION Vinylidene-acetylene 

分 类 号：O621.253[理学—有机化学]