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

✍ Scribed by L.D. Barron; L. Hecht; P.L. Polavarapu


Publisher
Elsevier Science
Year
1989
Tongue
English
Weight
380 KB
Volume
154
Category
Article
ISSN
0009-2614

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✦ Synopsis


Large deviations from the factor of 2 in the ratio of polarized to depolarized Raman optical activity intensities in methyl antisymmetric deformations in I-phenylethanol and I-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.