Coupled-Perturbed SCF Approach for Calculating Static Polarizabilities and Hyperpolarizabilities with Nonorthogonal Localized Molecular Orbitals.

Published

Journal Article

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.

Full Text

Duke Authors

Cited Authors

  • Li, S; Hu, L; Peng, L; Yang, W; Gu, FL

Published Date

  • March 2015

Published In

Volume / Issue

  • 11 / 3

Start / End Page

  • 923 - 931

PubMed ID

  • 26579746

Pubmed Central ID

  • 26579746

Electronic International Standard Serial Number (EISSN)

  • 1549-9626

International Standard Serial Number (ISSN)

  • 1549-9618

Digital Object Identifier (DOI)

  • 10.1021/ct500889k

Language

  • eng