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Updated: Feb 24, 2026

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Time-Dependent Coupled Perturbed Hartree-Fock and Density-Functional-Theory Approach for Calculating
Daoling Peng1, Shaopeng Li1, Liang Peng1
1Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education; School of Chemistry and Environment, South China Normal University , Guangzhou 510006, China.
Abstract:
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 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.
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