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利用耦合簇方法和Dunning等提出的系列相关一致基对PH2自由基的基态结构进行优化, 并使用优选出的cc-pV5Z基组对其进行频率计算. 结果表明,平衡核间距RP—H=0.14185 nm, 键角αHPH=91.8624°, 离解能De(HP—H)=3.483 eV, 对称伸缩振动频率ν1(a1)=2399.9781 cm-1, 弯曲振动频率ν2(a1)=1128.4213 cm-1,反对称伸缩振动频率ν3(b2)=2407.8374 cm-1. 在此基础上采用多体项展式理论导出了PH2自由基的解析势能函数, 其等值势能图准确再现了PH2自由基分子的平衡结构特征和动力学特征.The equilibrium geometries for the ground state of PH2 radical are calculated by using the coupled_cluster single_double model with a perturbative triple excitations (CCSD(T)) method in combination with the series of correlation-consistent basis sets of Dunning and co-workers. It can be found that the cc-pV5Z basis set is the most suitable basis set by comparing the calculations with the experiment. The results obtained at CCSD(T)/ cc-pV5Z level of theory are 0.14185 nm for the equilibrium bond length RP—H, 91.8624° for the bond angle αHPH, 3.483 eV for the dissociation energy De and 2399.9781, 1128.4213 and 2407.8374 cm-1 for the normal of vibrational frequencies(ν(a1), ν2(a1) and ν3(b2), respectively. The potential energy function of PH2 (C2v, X2B1) is derived using many-body expansion theory. The characters of structure and the change of energy are reflected correctly by the function.







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