Systematic GVB study of harmonic vibrational frequencies and dipole moment derivatives; the vinyl radical C2H3 and other simple molecules

Michel Dupuis, J. J. Wendoloski

Research output: Contribution to journalArticle

56 Citations (Scopus)

Abstract

Structure, harmonic vibrational frequencies, and dipole moment derivatives of methane, ethylene, and acetylene have been obtained from generalized valence bond (GVB) wave function calculations. The results are compared to Hartree-Fock (HF) data, and other correlated wave function data. It is found that the GVB method consistently overemphasizes left-right electron correlation effects, and predicts bond lengths ∼0.01-0.02 Å longer than experiment. However, the calculated harmonic frequencies are within 4.2% of the observed fundamentals and within 3.5% of the experimental harmonic frequencies. Dipole moment derivatives are in semi-quantitative agreement with experiment. The method is used to predict the IR spectrum of the vinyl radical, including a very intense out of plane bending mode with frequency near 1000 cm-1.

Original languageEnglish
Pages (from-to)5696-5702
Number of pages7
JournalJournal of Chemical Physics
Volume80
Issue number11
Publication statusPublished - 1984

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vinyl radical
Dipole moment
Vibrational spectra
Wave functions
dipole moments
Derivatives
valence
moments
harmonics
Electron correlations
Acetylene
Molecules
Methane
Bond length
molecules
Experiments
wave functions
acetylene
ethylene
methane

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

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abstract = "Structure, harmonic vibrational frequencies, and dipole moment derivatives of methane, ethylene, and acetylene have been obtained from generalized valence bond (GVB) wave function calculations. The results are compared to Hartree-Fock (HF) data, and other correlated wave function data. It is found that the GVB method consistently overemphasizes left-right electron correlation effects, and predicts bond lengths ∼0.01-0.02 {\AA} longer than experiment. However, the calculated harmonic frequencies are within 4.2{\%} of the observed fundamentals and within 3.5{\%} of the experimental harmonic frequencies. Dipole moment derivatives are in semi-quantitative agreement with experiment. The method is used to predict the IR spectrum of the vinyl radical, including a very intense out of plane bending mode with frequency near 1000 cm-1.",
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N2 - Structure, harmonic vibrational frequencies, and dipole moment derivatives of methane, ethylene, and acetylene have been obtained from generalized valence bond (GVB) wave function calculations. The results are compared to Hartree-Fock (HF) data, and other correlated wave function data. It is found that the GVB method consistently overemphasizes left-right electron correlation effects, and predicts bond lengths ∼0.01-0.02 Å longer than experiment. However, the calculated harmonic frequencies are within 4.2% of the observed fundamentals and within 3.5% of the experimental harmonic frequencies. Dipole moment derivatives are in semi-quantitative agreement with experiment. The method is used to predict the IR spectrum of the vinyl radical, including a very intense out of plane bending mode with frequency near 1000 cm-1.

AB - Structure, harmonic vibrational frequencies, and dipole moment derivatives of methane, ethylene, and acetylene have been obtained from generalized valence bond (GVB) wave function calculations. The results are compared to Hartree-Fock (HF) data, and other correlated wave function data. It is found that the GVB method consistently overemphasizes left-right electron correlation effects, and predicts bond lengths ∼0.01-0.02 Å longer than experiment. However, the calculated harmonic frequencies are within 4.2% of the observed fundamentals and within 3.5% of the experimental harmonic frequencies. Dipole moment derivatives are in semi-quantitative agreement with experiment. The method is used to predict the IR spectrum of the vinyl radical, including a very intense out of plane bending mode with frequency near 1000 cm-1.

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