Explicitly correlated plane waves: Accelerating convergence in periodic wavefunction expansions

Andreas Grueneis*, James J. Shepherd, Ali Alavi, David P. Tew, George H. Booth

*Corresponding author for this work

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

47 Citations (Scopus)

Abstract

We present an investigation into the use of an explicitly correlated plane wave basis for periodic wavefunction expansions at the level of second-order Moller-Plesset (MP2) perturbation theory. The convergence of the electronic correlation energy with respect to the one-electron basis set is investigated and compared to conventional MP2 theory in a finite homogeneous electron gas model. In addition to the widely used Slater-type geminal correlation factor, we also derive and investigate a novel correlation factor that we term Yukawa-Coulomb. The Yukawa-Coulomb correlation factor is motivated by analytic results for two electrons in a box and allows for a further improved convergence of the correlation energies with respect to the employed basis set. We find the combination of the infinitely delocalized plane waves and local short-ranged geminals provides a complementary, and rapidly convergent basis for the description of periodic wavefunctions. We hope that this approach will expand the scope of discrete wavefunction expansions in periodic systems. (C) 2013 AIP Publishing LLC.

Original languageEnglish
Article number084112
Number of pages13
JournalJournal of Chemical Physics
Volume139
Issue number8
DOIs
Publication statusPublished - 28 Aug 2013

Keywords

  • QUANTUM MONTE-CARLO
  • PLESSET PERTURBATION-THEORY
  • ELECTRONIC-STRUCTURE THEORY
  • COUPLED-CLUSTER THEORY
  • CORRELATION CUSP
  • BASIS-SETS
  • CORRELATION ENERGIES
  • GROUND-STATE
  • HARTREE-FOCK
  • TERMS

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