Polarized Raman optical activity in methyl antisymmetric deformations: influence of heteroatom Rydberg orbitals

Barron, L.D., Hecht, L. and Polavarapu, P.L. (1989) Polarized Raman optical activity in methyl antisymmetric deformations: influence of heteroatom Rydberg orbitals. Chemical Physics Letters, 154(3), pp. 251-254. (doi:10.1016/0009-2614(89)87458-5)

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Abstract

Large deviations from the factor of 2 in the ratio of polarized to depolarized Raman optical activity intensities in methyl antisymmetric deformations in 1-phenylethanol and 1-phenylethylthiol are reported. It is suggested that these deviations might originate in large electric quadrupole contributions induced by excited-state interactions involving heteroatom Rydberg p orbitals and orbitals on other parts of the molecule. Such interactions appear to undermine the bond polarizability theory of Raman intensities.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Hecht, Dr Lutz and Barron, Professor Laurence
Authors: Barron, L.D., Hecht, L., and Polavarapu, P.L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemical Physics Letters
Publisher:Elsevier Science Publishers B.V.
ISSN:0009-2614
ISSN (Online):1873-4448

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