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Analytic evaluation of energy gradients for the single and double excitation coupled cluster (CCSD) wave function: Theory and application

J. Chem. Phys. 87, 5361 (1987); doi:10.1063/1.453655

Issue Date: 1 November 1987

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Andrew C. Scheiner, Gustavo E. Scuseria, Julia E. Rice, Timothy J. Lee, and Henry F. Schaefer III
Department of Chemistry, University of California, Berkeley, California 94720
The theory for the analytic evaluation of energy gradients for coupled cluster (CC) wave functions is presented. In particular, explicit expressions for the analytic energy gradient of the CC singles and doubles (CCSD) wave function for a closed-shell restricted Hartree–Fock reference determinant are presented and shown to scale as N6 where N is the one-electron number of atomic basis functions for the molecular system. Thus analytic CCSD gradients are found to be of the same magnitude in computational cost as is the evaluation of analytic gradients for the configuration interaction singles and doubles (CISD) wave function. Applications of this method are presented for the water molecule and the formaldehyde molecule using a double-zeta plus polarization (DZ+P) basis set. The CCSD equilibrium geometries, dipole moments, and, via finite differences of gradients, CCSD harmonic vibrational frequencies and infrared intensities are reported. For H2O these results are compared to analogous CISD, CISDT, CISDTQ, and experimental results, and it is found that the CCSD predictions are most comparable to those of CISDTQ for this particular system. For the case of H2CO, the CCSD results are compared to CISD and experimental predictions. In general, the CCSD results and timings are encouraging. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 20 February 1987; accepted 11 June 1987
Permalink: http://link.aip.org/link/?JCPSA6/87/5361/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.20.Tz
    Electronic structure of atoms and molecules: theory Specific calculations and results Electron correlation and CI calculations
  • 33.10.Gx
    Molecular spectra and interactions of molecules with photons Calculation of molecular spectra Vibrational analysis
  • 33.20.Ea
    Molecular spectra and interactions of molecules with photons Molecular spectra, grouped by wavelength ranges Infrared spectra
  • 33.70.Fd
    Molecular spectra and interactions of molecules with photons Intensities and shapes of molecular spectral lines and bands Lifetimes, absolute and relative line and band intensities
  • YEAR: 1987

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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