基态α-环己二酮最优解离路径中环状异构体的红外光谱分析  

Infrared spectral analysis of cyclic isomers in the optimal dissociation path ofα-cyclohexanedione in ground state

作　　者：杨雪[1] 张跃 赵国明[1] 解玉鹏[1] YANG Xue;ZHANG Yue;ZHAO Guo-Ming;XIE Yu-Peng(College of Science,Jilin Institute of Chemical Technology,Jilin 132022,China)

机构地区：[1]吉林化工学院理学院,吉林132022

出　　处：《原子与分子物理学报》2021年第5期8-16,共9页Journal of Atomic and Molecular Physics

基　　金：国家自然科学基金(11904126;11447194);吉林省教育厅科技项目(JJKH20190832KJ);吉林市科技创新发展规划项目(201831777)。

摘　　要：在CCSD(T)//B3LYP/6-311++G(d,p)理论水平上研究了基态α-环己二酮(α-CHD)到环戊酮(c-C_(5)H_(8)O)和一氧化碳(CO)的光解离反应势能面(PES),并计算了沿反应路径各环状异构体的红外光谱.从过渡态的相对能量、高能势垒的数目两个方面,并结合红外光谱研究结果确定了α-CHD→c-C_(5)H_(8)O+CO的最优光解离路径.对其势能面上的环状异构体进行了红外光谱分析,给出各异构体的振动频率、振动强度和主要的振动模式,与实验结果吻合较好.计算结果为基态α-CHD提出了一条新的最优解离路径,同时丰富了其环状异构体的光谱信息.The potential energy surface(PES)of photodissociation reaction,from ground-stateα-cyclohexanedione(α-CHD)to cyclopentanone(c-C_(5)H_(8)O)and carbon monoxide(CO),has been studied at CCSD(T)//B3LYP/6-311++G(d,p)level of theory,and the infrared spectra of cyclic isomers along the reaction path have also been computed.The optimal photodissociation path of theα-CHD→c-C_(5)H_(8)O+CO is determined in two aspects,the relative energies of transition states and the number of high-energy barriers,together with the infrared spectra by comparing with other studies.The infrared vibrational analysis of the cyclic isomers on the PES is carried out.The observed frequencies are assigned to various vibration modes on the basis of the infrared intensity,and the assignment of fundamental vibration frequencies is in good agreement with the experimental data.It provides a new optimal dissociation path,and enriches the spectra information of cyclic isomers forα-CHD.

关 键 词：α-CHD 密度泛函理论 光解离 异构体 红外光谱 

分 类 号：O644[理学—物理化学]