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The anharmonic force fields of HOF and F2O

J. Chem. Phys. 89, 4965 (1988); doi:10.1063/1.455639

Issue Date: 15 October 1988

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Walter Thiel
Theoretische Chemie, Universität Wuppertal, 5600 Wuppertal 1, West Germany

Gustavo Scuseria and Henry F. Schaefer III
Center for Computational Quantum Chemistry, School of Chemical Sciences, University of Georgia, Athens, Georgia 30602

Wesley D. Allen
Combustion Research Facility, Sandia National Laboratories, Livermore, California 94551
Ab initio predictions at the SCF, CISD, and CCSD levels are reported for the title compounds using DZP and TZP basis sets. The calculated geometries, rotational constants, dipole moments, fundamental frequencies, isotopic frequency shifts, vibration–rotation interaction constants, centrifugal distortion constants, Coriolis coupling constants, and infrared band intensities are compared with experimental data (if available). The best agreement is usually found for the CCSD results. The experimentally derived cubic force field of F2O is reproduced well by our results so that the predicted cubic and quartic force fields of HOF and the predicted quartic force field of F2O are also expected to be realistic. On the basis of our theoretical anharmonic constants, a new interpretation is suggested for the anomalous isotopic frequency shift of nu3 in HOF and DOF. Finally, an experimentally derived re structure with R(O–F)=1.4356 Å, r(O–H)=0.9664 Å, and alpha(H–O–F)=97.72° is proposed for HOF on the basis of the TZP CCSD vibration–rotation interaction constants. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 17 March 1988; accepted 7 June 1988
Permalink: http://link.aip.org/link/?JCPSA6/89/4965/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.20.Ea
    Molecular spectra and interactions of molecules with photons Molecular spectra, grouped by wavelength ranges Infrared spectra
  • 33.10.Gx
    Molecular spectra and interactions of molecules with photons Calculation of molecular spectra Vibrational analysis
  • 35.20.Pa
    Experimentally derived information on atoms and molecules; instrumentation and techniques Molecules Rotation, vibration, and vibrationrotation constants
  • 35.20.Dp
    Experimentally derived information on atoms and molecules; instrumentation and techniques Molecules Interatomic distances and angles
  • YEAR: 1988

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PUBLICATION DATA

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