✦ LIBER ✦
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.