Dispersion of Complex Refractive Indices for Intense Vibrational Bands. II. Implication to Sum Frequency Generation Spectroscopy.

Abstract

Sharp and intense vibrational bands are characterized with conspicuous dispersion of complex refractive indices. Based on the quantitative data of dispersion in the preceding paper, this paper clarifies the influence of the dispersion on the sum frequency generation (SFG) spectroscopy. As a consequence of the large dispersion, the lineshapes of SFG spectra could be influenced by the frequency dependence of the Fresnel factor as well as the nonlinear susceptibility. This paper argues the relative importance of the two factors in general cases and provides a useful criterion to evaluate their importance. The effect of Fresnel dispersion becomes significant when the SFG spectrum involves a sharp and intense vibrational band as well as a large non-resonant background susceptibility, typically in some solid-liquid interfaces. A possible way to correct the effect of Fresnel dispersion is suggested using the heterodyne measurement.