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.
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