 Raman vibrational activity

The simplest off-resonant explanation is a vibrating polarizability. Let $Q(t)=Q_0\cos (2\pi {\nu }_{v}t)$ be a small normal mode coordinate of molecular vibration, and use one scalar component of polarizability, $\alpha (Q)\simeq {\alpha }_0+{\alpha }_0^{\prime }Q$. For incident electric field $E(t)=E_0\cos (2\pi {\nu }_{0}t)$, the induced electric dipole moment isThe product-to-sum formula produces the two displaced frequencies. A nonzero derivative ${\alpha }_0^{\prime }$ gives vibrational Raman scattering in this linear model. Real polarizability is generally a tensor, and the selected components depend on incident and observed wave polarization. This condition differs from vibrational infrared activity, which requires a changing molecular electric dipole moment without an applied optical electric field. A vibration can therefore appear in one measurement and be absent in the other.

This classical modulation argument explains line locations but supplies equal sideband wave amplitudes; it does not explain their thermal asymmetry or the nonzero Stokes Raman scattering from a vibrational ground state. Those require the quantum harmonic oscillator population and transition strengths. The far-off-resonance drawing uses dashed virtual intermediate levels: they represent terms in a scattering probability amplitude, not a long-lived occupied electronic energy eigenstate. Near an electronic resonance, a more detailed treatment of the intermediate response is needed.