Theoretical prediction of vibrational spectra. Scaled quantum mechanical (SQM) force field for fluorobenzene

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Abstract

The complete harmonic force field of fluorobenzene has been determined from ab initio Hartree-Fock calculations using the 4-21 Gaussian basis set. As force constants are systematically overestimated at this level of theory, the directly calculated force field was scaled by empirical factors taken over from benzene and methylfluoride. Except for a slight overestimation of the CF stretching frequency, the scaled quantum mechanical (SQM) force field obtained in this way reproduces the experimental fundamental frequencies of the parent molecule and two deuterated isotopomers within 20 cm-1 (with mean deviations below 12 cm-1), and experimental assignments are analyzed on this basis. Theoretical i.r. intensities reproduce the main features of the spectra fairly well.

Original languageEnglish
Pages (from-to)1067-1077
Number of pages11
JournalSpectrochimica Acta Part A: Molecular Spectroscopy
Volume44
Issue number11
DOIs
Publication statusPublished - 1988

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Vibrational spectra
Stretching
Benzene
Molecules

ASJC Scopus subject areas

  • Engineering(all)

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abstract = "The complete harmonic force field of fluorobenzene has been determined from ab initio Hartree-Fock calculations using the 4-21 Gaussian basis set. As force constants are systematically overestimated at this level of theory, the directly calculated force field was scaled by empirical factors taken over from benzene and methylfluoride. Except for a slight overestimation of the CF stretching frequency, the scaled quantum mechanical (SQM) force field obtained in this way reproduces the experimental fundamental frequencies of the parent molecule and two deuterated isotopomers within 20 cm-1 (with mean deviations below 12 cm-1), and experimental assignments are analyzed on this basis. Theoretical i.r. intensities reproduce the main features of the spectra fairly well.",
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AU - Fogarasi, G.

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N2 - The complete harmonic force field of fluorobenzene has been determined from ab initio Hartree-Fock calculations using the 4-21 Gaussian basis set. As force constants are systematically overestimated at this level of theory, the directly calculated force field was scaled by empirical factors taken over from benzene and methylfluoride. Except for a slight overestimation of the CF stretching frequency, the scaled quantum mechanical (SQM) force field obtained in this way reproduces the experimental fundamental frequencies of the parent molecule and two deuterated isotopomers within 20 cm-1 (with mean deviations below 12 cm-1), and experimental assignments are analyzed on this basis. Theoretical i.r. intensities reproduce the main features of the spectra fairly well.

AB - The complete harmonic force field of fluorobenzene has been determined from ab initio Hartree-Fock calculations using the 4-21 Gaussian basis set. As force constants are systematically overestimated at this level of theory, the directly calculated force field was scaled by empirical factors taken over from benzene and methylfluoride. Except for a slight overestimation of the CF stretching frequency, the scaled quantum mechanical (SQM) force field obtained in this way reproduces the experimental fundamental frequencies of the parent molecule and two deuterated isotopomers within 20 cm-1 (with mean deviations below 12 cm-1), and experimental assignments are analyzed on this basis. Theoretical i.r. intensities reproduce the main features of the spectra fairly well.

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