A comparison of linear and nonlinear correlation factors for basis set limit Moller-Plesset second order binding energies and structures of He-2, Be-2, and Ne-2

David P. Tew, Wim Klopper*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

65 Citations (Scopus)

Abstract

The basis set limit Moller-Plesset second-order equilibrium bond lengths of He-2, Be-2, and Ne-2, accurate to 0.01a(0), are computed to be 5.785a(0), 5.11a(0), and 6.05a(0). The corresponding binding energies are 22.4 +/- 0.1, 2180 +/- 20, and 86 +/- 2 mu E-h, respectively. An accuracy of 95% in the binding energy requires an aug-cc-pV6Z basis or larger for conventional Moller-Plesset theory. This accuracy is obtained using an aug-cc-pV5Z basis if geminal basis functions with a linear correlation factor are included and with an aug-cc-pVQZ basis if the linear correlation factor is replaced by exp(-gamma r(12)) with gamma=1. The correlation factor r(12) exp(-gamma r(12)) does not perform as well, describing the atom more efficiently than the dimer. The geminal functions supplement the orbital basis in the description of both the short-range correlation, at electron coalescence, and the long-range dispersion correlation and the values of gamma that give the best binding energies are smaller than those that are optimum for the atom or the dimer. It is important to sufficiently reduce the error due to the resolution of the identity approximation for the three- and four-electron integrals and we recommend the complementary auxiliary basis set method. The effect of both orbital and geminal basis set superposition error must be considered to obtain accurate binding energies with small orbital basis sets. In this respect, we recommend using exp(-gamma r(12)) with localized orbitals and the original orbital-variant formalism. (c) 2006 American Institute of Physics.

Original languageEnglish
Article number094302
Number of pages15
JournalJournal of Chemical Physics
Volume125
Issue number9
DOIs
Publication statusPublished - 7 Sep 2006

Keywords

  • MOLECULAR ELECTRONIC-STRUCTURE
  • AB-INITIO THERMOCHEMISTRY
  • GAUSSIAN-BASIS SETS
  • WAVE-FUNCTIONS
  • HELIUM DIMER
  • EXTRAPOLATION TECHNIQUES
  • BENCHMARK CALCULATIONS
  • PERTURBATION-THEORY
  • CORRELATION CUSP
  • MODEL CHEMISTRY

Cite this