Time-Dependent Coupled Perturbed Hartree Fock and Density-Functional-Theory Approach for Calculating Frequency-Dependent (Hyper)Polarizabilities with Nonorthogonal Localized Molecular Orbitals

摘要

The time-dependent coupled perturbed Hartree Fock/density-functional-theory (TDHF/TDDFT) approach has been reformulated based on nonorthogonal localized molecular orbitals (NOLMOs). Based on the NOLMO Fock equation, we have derived the corresponding NOLMO-TDHF/TDDFT equations up to the third order, and the formula for the frequency-dependent (hyper)polarizabilities has been given. Our approach has been applied to calculate both static and dynamic (hyper)polarizabilities of molecules varying from small molecules to large molecules. The NOLMO-TDHF/TDDFT approach can reproduce the 2 5 reference canonical molecular orbital (CMO) results for all of our testing calculations. With the help of ongoing development of optimized local virtual molecular orbitals, the NOLMO-TDHF/TDDFT approach would be a very efficient method for large system calculations and tp achieve linear scaling.