Benchmark studies for explicitly correlated perturbation- and coupled cluster theories

Hans Joachim Werner, Gerald Knizia, Thomas B. Adler, Oliver Marchetti

Research output: Contribution to journalArticle

52 Citations (Scopus)

Abstract

The recently developed explicitly correlated MP2-F12 and CCSDM-F12x (x = a,b) methods are reviewed. The explicit correlation treatment leads to a dramatic improvement of the basis set convergence. Extensive benchmarks for reaction energies, atomization energies, electron affinities, ionization potentials, equilibrium structures, vibrational frequencies, and intermolecular interaction energies are presented which show that for many molecular properties the intrinsic accuracy of the CCSD(T) method is already reached with double-zeta (VDZ-F12) basis sets, while triple-zeta (VTZ-F12) basis sets yield results that are very close to the complete basis set limit. The steep scaling of the MP2-F12 method with molecular size can be reduced by local approximations. This has made it possible to carry out MP2-F12 calculations for molecules with up to 100 atoms. The errors caused by the local domain approximation are largely removed by the explicitly correlated terms, which account for the neglected configurations in an approximate way. Extensions to LCCSD(T)-F12 are discussed and preliminary results for LCCSD-F12 are presented.

Original languageEnglish (US)
Pages (from-to)493-511
Number of pages19
JournalZeitschrift fur Physikalische Chemie
Volume224
Issue number3-4
DOIs
StatePublished - Jun 15 2010

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Electron affinity
Ionization potential
Atomization
Vibrational spectra
perturbation
Atoms
Molecules
molecular properties
atomizing
electron affinity
approximation
ionization potentials
energy
scaling
configurations
atoms
molecules
interactions

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Werner, Hans Joachim ; Knizia, Gerald ; Adler, Thomas B. ; Marchetti, Oliver. / Benchmark studies for explicitly correlated perturbation- and coupled cluster theories. In: Zeitschrift fur Physikalische Chemie. 2010 ; Vol. 224, No. 3-4. pp. 493-511.
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Benchmark studies for explicitly correlated perturbation- and coupled cluster theories. / Werner, Hans Joachim; Knizia, Gerald; Adler, Thomas B.; Marchetti, Oliver.

In: Zeitschrift fur Physikalische Chemie, Vol. 224, No. 3-4, 15.06.2010, p. 493-511.

Research output: Contribution to journalArticle

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