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An efficient ab initio method for computing infrared and Raman intensities: Application to ethylene

J. Chem. Phys. 70, 2014 (1979); doi:10.1063/1.437627

Issue Date: 15 February 1979

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Andrew Komornicki
NASA-Ames Research Center, Moffett Field, California 94035

James W. McIver, Jr.
Department of Chemistry, State University of New York, Buffalo, New York 14214
A new and very efficient method for the calculation of the infrared and Raman spectral intensities of polyatomic molecules using ab initio Hartree–Fock theory is described. The utility of the method is exemplified by an evaluation of the dipole and polarizability derivatives of the ethylene molecule employing a Gaussian basis set of double zeta quality, augmented by two sets of polarization functions. The predicted values of the vibrational intensities and the depolarization ratios are nearly within the experimental uncertainty which indicates that Hartree–Fock theory is capable of correctly describing these phenomena. The new method enables the efficient calculation of these properties by evaluating the dipole and polarizability derivatives as the first and second order contributions to the potential energy gradient of a molecule in the presence of a finite perturbing electric field. The calculations are thus performed at a single nuclear geometry and the molecular integrals are evaluated only once. The efficiency of the method shows great promise in the evaluation of reliable vibrational intensities for a wide range of polyatomic molecules. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
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PACS

  • 31.20.Gm
    Electronic structure of atoms and molecules: theory Specific calculations and results Other accurate, or nearly ab initio calculations (DIM method, SAMO method, etc.)
  • 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
  • 33.20.Fb
    Molecular spectra and interactions of molecules with photons Molecular spectra, grouped by wavelength ranges Raman and Rayleigh spectra (including optical scattering)
  • YEAR: 1979

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (22)
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