title: Coupled-Perturbed SCF Approach for Calculating Static Polarizabilities and Hyperpolarizabilities with Nonorthogonal Localized Molecular Orbitals.
abstract: Coupled-perturbed self-consistent-field (CPSCF) approach has been broadly used for polarizabilities and hyperpolarizabilities computation. To extend this application to large systems, we have reformulated the CPSCF equations with nonorthogonal localized molecular orbitals (NOLMOs). NOLMOs are the most localized representation of electronic degrees of freedom. Methods based on NOLMOs are potentially ideal for investigating large systems. In atomic orbital representation, with a static external electric field added, the wave function and SCF operator of unperturbed NOLMO-SCF wave function/orbitals are expanded to different orders of perturbations. We have derived the corresponding equations up to the third order, which are significantly different from those of a conventional CPSCF method because of the release of the orthogonal restrictions on MOs. The solution to these equations has been implemented. Several chemical systems are used to verify our method. This work represents the first step toward efficient calculations of molecular response and excitation properties with NOLMOs.
authors.affiliation: Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry & Environment, South China Normal University , Guangzhou 510006, China.
authors.forename: Shaopeng
authors.initials: S
authors.lastname: Li
authors.affiliation: Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry & Environment, South China Normal University , Guangzhou 510006, China.
authors.forename: Linping
authors.initials: L
authors.lastname: Hu
authors.affiliation: Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry & Environment, South China Normal University , Guangzhou 510006, China.
authors.forename: Liang
authors.initials: L
authors.lastname: Peng
authors.affiliation: Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry & Environment, South China Normal University , Guangzhou 510006, China.|Department of Chemistry and Physics, Duke University , Box 90346, Durham, North Carolina 27708-0346, United States.
authors.forename: Weitao
authors.initials: W
authors.lastname: Yang
authors.affiliation: Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry & Environment, South China Normal University , Guangzhou 510006, China.
authors.forename: Feng Long
authors.initials: FL
authors.lastname: Gu