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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-C5H8O)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-C5H8 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-state α-cyclohex-anedione(α-CHD)to cyclopentanone(c-C5H8O)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 the α-CHD→c-C5 H8 O+CO is deter-mined 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 experi-mental data.It provides a new optimal dissociation path,and enriches the spectra information of cyclic isomers for α-CHD.