密度泛函交换关联势与过渡金属化合物光学非线性的计算研究

在优化几何构型的基础上，对一系列强关联过渡金属化合物，采用密度泛函理论方法中各种 交换关联势计算了电子偶极矩、一阶光学极化率和一阶光学超极化率.考虑基组和频率影响 ，对比从头算MP2，HF方法及实验值，评价了各种交换关联势的计算表现.在此基础上，讨论 新的混合密度泛函交换关联势，以提高密度泛函理论方法计算含有过渡金属体系非线性光学 性质的精度. 关键词： 密度泛函方法 过渡金属化合物 非线性光学

Computational study on the exchange-correlation function in density functional theory and optical nonlinearity of transition-metal complexes

Dipole moments, polarizabilities and first hyperpolarizabilities of a series of transition metal complexes have been studied by employing various exchange-correlated potentials within the density functional theory (DFT). Taking into consideration the basis set and frequency-dispersion effects, the efficiencies of these potentials have been calibrated by comparing with the ab initio results of MP2, HF and experimental measurements. The effect of different portion of exchanged-correlated functional of hybrid-DFT on dipole moment, polarizability and first hyperpolarizability has been discussed as well.