Force field, dipole moment derivatives, and vibronic constants of benzene from a combination of experimental and ab initio quantum chemical information

Péter Pulay, G. Fogarasi, James E. Boggs

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Abstract

The quadratic and the most important cubic force constants of benzene have been determined from ab initio Hartree-Fock calculations with a double-zeta basis set. Some constants have also been recalculated using other basis sets, including a polarized one. A few empirical scale factors, applied to the ab initio force field, allow the reproduction of a large number of observed vibrational frequencies, isotope shifts, and Coriolis constants within the uncertainties of experiment and the harmonic model. It is shown that the simultaneous utilization of ab initio and spectroscopical information is sufficient for the conclusive resolution of the uncertainties and alternatives in previous empirical force fields. The resulting scale factors can be used directly to obtain force fields for other aromatic hydrocarbons from ab initio calculations. Reproduction of the observed infrared intensities is only moderately successful, even with the polarized basis set. The calculated vibronic coupling constants show qualitative agreement but important deviations from previous simpler calculations. The predicted vibrational patterns confirm Lindholm's assignment of the photoelectron spectrum of benzene.

Original languageEnglish
Pages (from-to)3999-4014
Number of pages16
JournalThe Journal of Chemical Physics
Volume74
Issue number7
Publication statusPublished - 1981

Fingerprint

Dipole moment
Benzene
field theory (physics)
dipole moments
benzene
Derivatives
Aromatic Hydrocarbons
Vibrational spectra
Photoelectrons
Isotopes
isotope effect
Infrared radiation
photoelectrons
hydrocarbons
deviation
harmonics
Experiments
Uncertainty

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

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abstract = "The quadratic and the most important cubic force constants of benzene have been determined from ab initio Hartree-Fock calculations with a double-zeta basis set. Some constants have also been recalculated using other basis sets, including a polarized one. A few empirical scale factors, applied to the ab initio force field, allow the reproduction of a large number of observed vibrational frequencies, isotope shifts, and Coriolis constants within the uncertainties of experiment and the harmonic model. It is shown that the simultaneous utilization of ab initio and spectroscopical information is sufficient for the conclusive resolution of the uncertainties and alternatives in previous empirical force fields. The resulting scale factors can be used directly to obtain force fields for other aromatic hydrocarbons from ab initio calculations. Reproduction of the observed infrared intensities is only moderately successful, even with the polarized basis set. The calculated vibronic coupling constants show qualitative agreement but important deviations from previous simpler calculations. The predicted vibrational patterns confirm Lindholm's assignment of the photoelectron spectrum of benzene.",
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T1 - Force field, dipole moment derivatives, and vibronic constants of benzene from a combination of experimental and ab initio quantum chemical information

AU - Pulay, Péter

AU - Fogarasi, G.

AU - Boggs, James E.

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N2 - The quadratic and the most important cubic force constants of benzene have been determined from ab initio Hartree-Fock calculations with a double-zeta basis set. Some constants have also been recalculated using other basis sets, including a polarized one. A few empirical scale factors, applied to the ab initio force field, allow the reproduction of a large number of observed vibrational frequencies, isotope shifts, and Coriolis constants within the uncertainties of experiment and the harmonic model. It is shown that the simultaneous utilization of ab initio and spectroscopical information is sufficient for the conclusive resolution of the uncertainties and alternatives in previous empirical force fields. The resulting scale factors can be used directly to obtain force fields for other aromatic hydrocarbons from ab initio calculations. Reproduction of the observed infrared intensities is only moderately successful, even with the polarized basis set. The calculated vibronic coupling constants show qualitative agreement but important deviations from previous simpler calculations. The predicted vibrational patterns confirm Lindholm's assignment of the photoelectron spectrum of benzene.

AB - The quadratic and the most important cubic force constants of benzene have been determined from ab initio Hartree-Fock calculations with a double-zeta basis set. Some constants have also been recalculated using other basis sets, including a polarized one. A few empirical scale factors, applied to the ab initio force field, allow the reproduction of a large number of observed vibrational frequencies, isotope shifts, and Coriolis constants within the uncertainties of experiment and the harmonic model. It is shown that the simultaneous utilization of ab initio and spectroscopical information is sufficient for the conclusive resolution of the uncertainties and alternatives in previous empirical force fields. The resulting scale factors can be used directly to obtain force fields for other aromatic hydrocarbons from ab initio calculations. Reproduction of the observed infrared intensities is only moderately successful, even with the polarized basis set. The calculated vibronic coupling constants show qualitative agreement but important deviations from previous simpler calculations. The predicted vibrational patterns confirm Lindholm's assignment of the photoelectron spectrum of benzene.

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