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Vibrational optical activity in deuteriated phenylethanes

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100322a045· OSTI ID:6478633

Infrared, Raman, and vibrational circular dichroism (VCD) spectra have been recorded in the region 3100-2000 cm/sup -1/ for (S)-(+)-1-phenylethane-1-d/sub 1/, (S)-(+)-1-phenylethane-1,2-d/sub 2/, (S)-(+)-1-phenylethane-1,2,2-d/sub 3/, and (S)-(+)-1-phenylethane-1,2,2,2-d/sub 4/. From these spectra the authors have been able to assign fully the aliphatic CD and CH stretching vibrations in all four molecules. Using a harmonic force field which fits the observed frequencies, they have calculated the dipole and rotational strengths of these modes on the basis of the charge flow model. These calculations show that this model underestimates the VCD intensities of these stretching modes. However, the model can be improved through the introduction of polarization terms. Generally applicable analytical expressions for such terms are derived. When applied to the phenylethanes, they lead to the correct orders of magnitude for the rotational strengths.

Research Organization:
Univ. of Minnesota, Minneapolis (USA)
OSTI ID:
6478633
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:11; ISSN JPCHA
Country of Publication:
United States
Language:
English