提高DV－X＿αSCC方法总能量精度及用于分子几何与振动力常数计算

On Improvement of Accuracy of the Total Energy Calculated by DV-Xα SCC Method and Its Application to Calculate the Molecular Geometry and Vibrational Force Constants

采取用解析方法计算重叠矩元和Ｆｏｃｋ矩阵元中的单中心积分、对用数值方法计算的原子间的Ｆｏｃｋ矩阵元进行校正的方法，结合过渡态技术，可以大幅度地提高用ＤＶ－Ｘ＿αＳＣＣ方法计算体系总能量的精度，从而可以用该方法计算分子几何结构和振动力常数。对Ｆ＿２，ＣＯ＿２，ＢＦ＿３，ＣＦ＿４，等１０个不同类型分子（离子）的计算结果与实验符合良好。

Calculating the overlap matrix elements and the single centered integrals of the Fock matrix elements analytically,calibrating the interatomic Fock matrix elements calculated numerically with the accurate overlap matrix elements,and adopting the transition state technique,the accuracy of the total energy calculated by DV-Xα SCC method can be improved considerably,which makes it possible to calculate the molecullar geometry and the vibrational force constants.The calcula-tion results for ten molecues such as CO_2, BF_3, CF_4,etc are in good agree-ment with experiments.