Local explicitly correlated second- and third-order Moller-Plesset perturbation theory with pair natural orbitals

Christof Haettig*, David P. Tew, Benjamin Helmich

*Corresponding author for this work

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

69 Citations (Scopus)

Abstract

We present an algorithm for computing explicitly correlated second-and third-order Moller-Plesset energies near the basis set limit for large molecules with a cost that scales formally as N-4 with system size N. This is achieved through a hybrid approach where locality is exploited first through orbital specific virtuals (OSVs) and subsequently through pair natural orbitals (PNOs) and integrals are approximated using density fitting. Our method combines the low orbital transformation costs of the OSVs with the compactness of the PNO representation of the doubles amplitude vector. The N-4 scaling does not rely upon the a priori definition of domains, enforced truncation of pair lists, or even screening and the energies converge smoothly to the canonical values with decreasing occupation number thresholds, used in the selection of the PNO basis. For MP2.5 intermolecular interaction energies, we find that 99% of benchmark basis set limit correlation energy contributions are recovered using an aug-cc-pVTZ basis and that on average only 50 PNOs are required to correlate the significant orbital pairs. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4719981]

Original languageEnglish
Article number204105
Number of pages14
JournalJournal of Chemical Physics
Volume136
Issue number20
DOIs
Publication statusPublished - 28 May 2012

Keywords

  • COUPLED-CLUSTER THEORY
  • AUXILIARY BASIS-SETS
  • CONSISTENT BASIS-SETS
  • WAVE-FUNCTIONS
  • IDENTITY APPROXIMATION
  • ELECTRON CORRELATION
  • CORRELATION-ENERGY
  • CORE-VALENCE
  • AB-INITIO
  • RESOLUTION

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