Vibrational spectroscopy of buried interfaces using nonlinear optics. Final technical report, July 7, 1986--February 29, 1996

This DOE sponsored program has been dedicated to the understanding, development, and application of nontraditional methods for studying buried interfaces, particularly the electrolyte-solid system. Most of the work has dealt with optical techniques. The early research was directed toward revealing the mechanisms of surface enhanced Raman scattering (SERS). More recently the author has concentrated on surface nonlinear optical effects--second harmonic generation (SHG) and sum-frequency generation (SHG). Both of these techniques have the potential for selective interface sensitivity, and are produced through a higher order susceptibility than that which governs linear optical response. Optical SHG has the potential of providing more information about a buried interface than can be obtained by conventional optical spectroscopy. The author`s experiments have been designed to: (a) extract the second order optical susceptibility tensor associated with the surface of a metal electrode, and (b) discover how the electrochemical environment influences the nonlinear optical measurements. Recent contributions include quantitative comparison of the nonlinear response of single crystal silver to theoretical models for the effect. The author has provided the first detailed test of the time-dependent, local density functional prediction. Optical SHG bears a fundamental connection with the symmetry of the surface atoms. While investigating Ag(111) an anomalous effect was discovered that could not be explained by the known surface structure of Ag. The phenomenon was tentatively assigned to an adsorption induced surface reconstruction, since it behaved like a second order phase transition. In addition to the optical phenomena the author has designed, built, and operated an in situ quartz crystal microbalance (QCM) electrochemical cell