Alternative formulation of many-body perturbation theory for electron-proton correlation

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

Research output: Contribution to journalArticlepeer-review

63 Scopus citations

Abstract

We present a formulation of nuclear-electronic many-body perturbation theory for treating electron-proton correlation. Our analysis indicates that removal of the proton-proton Coulomb-exchange operator from the reference Hamiltonian can lead to a significantly lower second-order energy and potentially faster convergence of the perturbation series for many-electron systems with a single quantum nucleus and many classical nuclei. This alternative reference Hamiltonian gives negative virtual nuclear orbital energies that are related to proton ionization potentials. Our applications to the chemical systems [HeHHe]+, [FHF]-, and [ClHCl] - illustrate the substantial decrease in the second-order energy. This formulation is applicable to numerous biologically important hydrogen transfer reactions in which the transferring hydrogen nucleus is treated quantum mechanically.

Original languageEnglish (US)
Pages (from-to)394-399
Number of pages6
JournalChemical Physics Letters
Volume404
Issue number4-6
DOIs
StatePublished - Mar 21 2005
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry

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