Accurate atomization energies from combining coupled-cluster computations with interference-corrected explicitly correlated second-order perturbation theory

Konstantinos Vogiatzis, Robin Haunschild, Wim Klopper

Research output: Contribution to journalArticle

22 Scopus citations

Abstract

Interference-corrected explicitly correlated second-order perturbation theory (INT-MP2-F12) is applied to accelerate the convergence to the completebasis- set limit of coupled-cluster computations. Adding energy terms obtained from INT-MP2-F12 theory to the energies obtained from coupled-cluster singles-and-doubles (CCSD) computations yields a mean absolute deviation (MAD) from explicitly correlated CCSD results below 1 kJ/mol for a test set of 106 molecules. A composite scheme for the computation of atomization energies is assessed. This scheme is denoted as CCSD(T)+F12+INT and consists of the CCSD model with perturbative triples (CCSD(T)) supplemented with INT-MP2-F12 corrections, using a quadruple-zeta quality basis set (cc-pVQZ-F12). The composite scheme achieves chemical accuracy with respect to experimentally derived or computed reference values. Using Boys localized molecular orbitals, the MAD of the CCSD(T)+F12+INT/cc-pVQZ-F12 atomization energies from the reference values is below 1 kJ/mol for the G2/97 test set.

Original languageEnglish (US)
Pages (from-to)1-12
Number of pages12
JournalTheoretical Chemistry Accounts
Volume133
Issue number3
DOIs
StatePublished - Jan 30 2014

Keywords

  • Atomization energy
  • Coupled-cluster theory
  • Explicit correlation
  • Interference effects
  • Performance assessment
  • Test set

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