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Basis set limit CCSD(T) harmonic vibrational frequencies.

David P Tew1, Wim Klopper, Miriam Heckert

  • 1Lehrstuhl für Theoretische Chemie, Institut für Physikalische Chemie, Universität Karlsruhe (TH), D-76128 Karlsruhe, Germany.

The Journal of Physical Chemistry. A
|May 22, 2007
PubMed
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High-accuracy molecular vibrational frequencies were computed using coupled-cluster methods. Explicitly correlated coupled-cluster with singles and doubles, and triples (CCSD(T)-R12) achieved benchmark accuracy, outperforming standard CCSD(T) convergence.

Area of Science:

  • Quantum chemistry
  • Computational spectroscopy
  • Molecular modeling

Background:

  • Accurate prediction of molecular vibrational frequencies is crucial for understanding chemical structure and reactivity.
  • Standard computational methods often struggle to reach chemical accuracy for vibrational frequencies due to slow basis set convergence.

Purpose of the Study:

  • To compute benchmark, frozen-core coupled-cluster with singles, doubles, and triples (CCSD(T)) equilibrium harmonic vibrational frequencies for multiple molecules.
  • To assess the convergence of standard CCSD(T) with Dunning's basis sets and compare it with explicitly correlated methods.

Main Methods:

  • Utilized the explicitly correlated coupled-cluster with singles, doubles, and triples-R12 (CCSD(T)-R12) method for high-accuracy frequency calculations.
  • Examined the convergence behavior of the standard CCSD(T) method with various one-particle basis sets.

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Main Results:

  • CCSD(T)-R12 method achieved benchmark accuracy (within 1 cm-1 of the basis set limit) for vibrational frequencies.
  • Standard CCSD(T) showed slow convergence, with residual errors even at the cc-pV6Z basis set level.
  • Inclusion of scalar relativistic effects and higher-order correlation corrections improved agreement with experimental frequencies for HF, N2, and CO.

Conclusions:

  • Explicitly correlated CCSD(T)-R12 is a reliable method for obtaining benchmark vibrational frequencies.
  • Standard CCSD(T) requires very large basis sets for high accuracy, and convergence can be slow.
  • Accurate prediction of F2 vibrational frequencies remains a challenge due to the significant contribution of quadruple excitations.