Quasi-degenerate perturbation theory with general multiconfiguration self-consistent field reference functions

Haruyuki Nakano, Ryuma Uchiyama, Kimihiko Hirao

Research output: Contribution to journalArticle

93 Citations (Scopus)

Abstract

The quasi-degenerate perturbation theory (QDPT) with complete active space (CAS) self-consistent field (SCF) reference functions is extended to the general multiconfiguration (MC) SCF references functions case. A computational scheme that utilizes both diagrammatic and sum-over-states approaches is presented. The second-order effective Hamiltonian is computed for the external intermediate configurations (including virtual or/and core orbitals) by the diagrammatic approach and for internal intermediate configurations (including only active orbitals) by the configuration interaction matrix-based sum-over-states approach. The method is tested on the calculations of excitation energies of H2O, potential energy curves of LiF, and valence excitation energies of H2CO. The results show that the present method yields very close results to the corresponding CAS-SCF reference QDPT results and the available experimental values. The deviations from CAS-SCF reference QDPT values are less than 0.1 eV on the average for the excitation energies of H2O and less than 1 kcal/mol for the potential energy curves of LiF. In the calculation of the valence excited energies of H2CO, the maximum deviation from available experimental values is 0.28 eV.

Original languageEnglish
Pages (from-to)1166-1175
Number of pages10
JournalJournal of Computational Chemistry
Volume23
Issue number12
DOIs
Publication statusPublished - Sep 1 2002
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Computational Mathematics

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