Accurate calculation of vibrational frequencies using explicitly correlated coupled-cluster theory

Guntram Rauhut, Gerald Knizia, Hans Joachim Werner

Research output: Contribution to journalArticle

139 Citations (Scopus)

Abstract

The recently proposed explicitly correlated CCSD (T) -F12x (x=a,b) approximations [T. B. Adler, G. Knizia, and H.-J. Werner, J. Chem. Phys. 127, 221106 (2007)] are applied to compute equilibrium structures and harmonic as well as anharmonic vibrational frequencies for H2 O, HCN, CO2, CH2 O, H2 O2, C2 H2, CH2 NH, C2 H2 O, and the trans-isomer of 1,2- C2 H2 F2. Using aug-cc-pVTZ basis sets, the CCSD(T)-F12a equilibrium geometries and harmonic vibrational frequencies are in very close agreement with CCSD(T)/aug-cc-pV5Z values. The anharmonic frequencies are evaluated using vibrational self-consistent field and vibrational configuration interaction methods based on automatically generated potential energy surfaces. The mean absolute deviation of the CCSD(T)-F12a/aug-cc-pVTZ anharmonic frequencies from experimental values amounts to only 4.0 cm-1.

Original languageEnglish (US)
Article number054105
JournalJournal of Chemical Physics
Volume130
Issue number5
DOIs
StatePublished - Feb 17 2009

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Vibrational spectra
Potential energy surfaces
Isomers
harmonics
Geometry
configuration interaction
self consistent fields
isomers
potential energy
deviation
geometry
approximation

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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Accurate calculation of vibrational frequencies using explicitly correlated coupled-cluster theory. / Rauhut, Guntram; Knizia, Gerald; Werner, Hans Joachim.

In: Journal of Chemical Physics, Vol. 130, No. 5, 054105, 17.02.2009.

Research output: Contribution to journalArticle

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