Alternative wavefunction ansatz for including explicit electron-proton correlation in the nuclear-electronic orbital approach

Chaehyuk Ko, Michael V. Pak, Chet Swalina, Sharon Hammes-Schiffer

Research output: Contribution to journalArticlepeer-review

Abstract

The nuclear-electronic orbital (NEO) approach treats specified nuclei quantum mechanically on the same level as the electrons with molecular orbital techniques. The explicitly correlated Hartree-Fock (NEO-XCHF) approach was developed to incorporate electron-nucleus dynamical correlation directly into the variational optimization of the nuclear-electronic wavefunction. In the original version of this approach, the Hartree-Fock wavefunction is multiplied by (1+G), where G is a geminal operator expressed as a sum of Gaussian type geminal functions that depend on the electron-proton distance. Herein, a new wavefunction ansatz is proposed to avoid the computation of five- and six-particle integrals and to simplify the computation of the lower dimensional integrals involving the geminal functions. In the new ansatz, denoted NEO-XCHF2, the Hartree-Fock wavefunction is multiplied by 1+G rather than (1+G). Although the NEO-XCHF2 ansatz eliminates the integrals that are quadratic in the geminal functions, it introduces terms in the kinetic energy integrals with no known analytical solution. A truncated expansion scheme is devised to approximate these problematic terms. An alternative hybrid approach, in which the kinetic energy terms are calculated with the original NEO-XCHF ansatz and the potential energy terms are calculated with the NEO-XCHF2 ansatz, is also implemented. Applications to a series of model systems with up to four electrons provide validation for the NEO-XCHF2 approach and the treatments of the kinetic energy terms.

Original languageEnglish (US)
Article number054106
JournalJournal of Chemical Physics
Volume135
Issue number5
DOIs
StatePublished - Aug 7 2011

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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