论文部分内容阅读
根据群论及原子分子反应静力学的有关原理,推导了PS基态分子电子态及其合理的离解极限.采用Gaussian 03软件中的密度泛函理论B3LYP和B3P86结合6-311++G(3df,3pd)、6-311++G、6-311G(3df,3pd)、cc-p VTZ和D95基组,对PS分子基态平衡结构和谐振频率进行了计算.通过比较计算结果,发现B3P86方法结合cc-p VTZ基组计算所得结果与实验值最接近.在该水平下对PS分子的基态进行了单点势能扫描计算,利用正规方程组拟合三参数的Murrell-Sorbie函数和修正的Murrell-Sorbie+C6函数,得到了基态PS分子完整的势能函数与相应的光谱常数ωe、ωexe、Be和αe的值.计算结果表明,利用三参数的Murrell-Sorbie函数计算所得的光谱常数与实验数据吻合得更好.
According to the theory of group theory and atomic-molecule reaction statics, the electronic states of PS ground state and their reasonable dissociation limits were deduced.The density functional theory B3LYP and B3P86 of Gaussian 03 were used in combination with 6-311 ++ G (3df, 3pd), 6-311 ++ G, 6-311G (3df, 3pd), cc-p VTZ and D95 basis set were used to calculate the ground-state equilibrium structure and resonance frequency of PS molecule.By comparing the calculated results, The calculated results of the cc-p VTZ basis set are closest to the experimental ones, and the ground states of the PS molecules are scaled by single-point potential energy at this level. The normal equations are used to fit the three-parameter Murrell-Sorbie function and the modified Murrell- Sorbie + C6 function, the complete potential energy function and the corresponding spectral constants ωe, ωexe, Be and αe of the ground-state PS molecule are obtained.The calculated results show that the spectral constants calculated by the Murrell-Sorbie function with three parameters agree well with the experimental data Better.