Sum Frequency Generation Spectroscopy - Theory

Theory

IR-visible sum frequency generation spectroscopy uses two laser beams that overlap at a surface of a material or the interface between two materials. An output beam is generated at a frequency of the sum of the two input beams. The two input beams have to be able to access the surface, and the output beam needs to be able to leave the surface to be picked up by a detector. One of the beams is a visible wavelength laser held at a constant frequency and the other is a tunable infrared laser. By tuning the IR laser, the system can scan over resonances and obtain the vibrational spectrum of the interfacial region.

As a nonlinear optical process, the polarization which generates the output depends on the electric fields of the two input beams.

As a second-order nonlinear process, SFG is dependent on the 2nd order susceptibility χ(2). The fact that the 2nd order susceptibility, a third rank tensor, becomes zero in centrosymmetric media, limits what samples are accessible for SFG. Centrosymmetric media include the bulk of gases, liquids, and most solids under the assumption of the electric-dipole approximation, which neglects the signal generated by multipoles and magnetic moments. At an interface between two different materials or two centrosymmetric media, the inversion symmetry is broken and an SFG signal can be generated. This suggests that the resulting spectra represent a thin layer of molecules. A signal is found when there is a net polar orientation.