Anharmonic force fields of HOF and F/sub 2/O

Journal Article · Sat Oct 15 00:00:00 EDT 1988 · J. Chem. Phys.; (United States)

OSTI ID:6930517

Thiel, W; Scuseria, G; Schaefer, III, H F; Allen, W D

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 F/sub 2/O is reproduced well by our results so that the predicted cubic and quartic force fields of HOF and the predicted quartic force field of F/sub 2/O 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 ..nu../sub 3/ in HOF and DOF. Finally, an experimentally derived r/sub e/ structure with R(O--F) = 1.4356 A, r(O--H) = 0.9664 A, and ..cap alpha..(H--O--F) = 97.72/sup 0/ is proposed for HOF on the basis of the TZP CCSD vibration--rotation interaction constants.

• Research Organization: Theoretische Chemie, Universitaet Wuppertal, 5600 Wuppertal 1, West Germany
• OSTI ID: 6930517
• Journal Information: J. Chem. Phys.; (United States), Vol. 89:8
• Country of Publication: United States
• Language: English

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37 INORGANIC
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PHYSICAL AND ANALYTICAL CHEMISTRY
FLUORINE OXIDES
INFRARED SPECTRA
MOLECULAR STRUCTURE
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HYPOFLUOROUS ACID
CORIOLIS FORCE
GEOMETRY
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CHALCOGENIDES
ENERGY LEVELS
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FLUORINE COMPOUNDS
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400201* - Chemical & Physicochemical Properties