TY - JOUR
T1 - Systematic GVB study of harmonic vibrational frequencies and dipole moment derivatives; the vinyl radical C2H3 and other simple molecules
AU - Dupuis, Michel
AU - Wendoloski, J. J.
PY - 1984
Y1 - 1984
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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M3 - Article
AN - SCOPUS:0001584955
VL - 80
SP - 5696
EP - 5702
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 11
ER -