Journal of Chemical Physics 2006-03-14

Large Raman-scattering activities for the low-frequency modes of substituted benzenes: induced polarizability and stereo-specific ring-substituent interactions.

Yoshihiro Yamakita, Yumiko Isogai, Koichi Ohno

Index: J. Chem. Phys. 124(10) , 104301, (2006)

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Abstract

The large nonresonant Raman-scattering activities of the out-of-plane bending and torsional modes of monosubstituted benzene analogs are studied by low-frequency Raman experiments and B3LYP6-31++G(d,p) calculations. Electronic interactions between the sigma orbitals of the substituent and the pi orbitals of the ring are found to enhance the Raman activities, depending on the substituent and its conformation. In the case of tert-butylbenzene [C6H5C(CH3)3] and trimethylphenylsilane [C6H5Si(CH3)3], three single bonds which are linked to the alpha atom of the substituent have low rotational barriers around the joint bond. Nearly free rotation of the substituents leads to a significant probability for one of the single bonds to occupy a conformation close to the vertical configuration with respect to the ring at room temperature. The resultant sigma-pi electronic interaction gives rise to the large Raman activities. In contrast, those possessing a single bond in a coplanar (or nearly coplanar) configuration at the most stable equilibrium state, i.e., anisole (C6H5OCH3), thioanisole (C6H5SCH3), and N-methylaniline (C6H5NHCH3), display no prominent Raman bands for the low-frequency vibrational modes. In these molecules, the sigma-pi conjugation does not take place due to the orthogonal orientation of the orbitals. Strong conformational dependence of the sigma-pi Raman enhancement is clearly obtained for the metastable vertical conformer of thioanisole, for which Raman activities are one-order magnitude greater than those of the coplanar conformer.