Rayleigh and Raman optical activity from chiral surfaces

Circular and linear polarization Rayleigh and Raman optical activity observables from chiral molecules on isotropic surfaces under resonance or preresonance conditions are predicted to be three orders of magnitude larger than those from bulk chiral media since the requirement for magnetic dipole and electric quadrupole contributions is removed. Explicit expressions for these observables are presented for the simple case of light scattered at an arbitrary angle in incident light perpendicular to the surface with the molecules restricted to a unique orientation relative to the surface normal but with free rotation about the normal in the plane of the surface. Similar non-linear effects in second harmonic and sum frequency generation and in hyper-Rayleigh and hyper-Raman scattering are discussed.