Studies of Surfaces Using Optical Second-Harmonic Generation.

The experiments reported in this thesis demonstrate the use of second-harmonic generation (SHG) and sum-frequency generation (SFG) in reflection from surfaces to study various surface properties. The experiments firmly establish SHG as a viable new surface probe that complements existing surface probes in ultrahigh vacuum environments and is in many ways unique for studying interfaces between dense media. Surface structural symmetry can be revealed through the anisotropy in the SH signal from the surface as the sample is rotated about its normal. The form of this anisotropy is derived in theory and verified with an experiment on the Si(100) and (111) surfaces. The absence of an anisotropic contribution to the SH signal from the surface layer of the (100) face enabled the first measurement of the dipole -forbidden contribution to the SH from the underlying centrosymmetric Si bulk. The SHG and SFG signals from molecules adsorbed on noninteracting substrates have a direct relationship to the number, average orientation, and spectroscopic properties of the molecules. The SH intensity was used to measure the isotherm for adsorption of p-nitrobenzoic acid from ethanolic solution to fused silica. The polarization of the SH field was used to measure the average tilt angle of PNBA to be (TURN)38(DEGREES) when adsorbed at the ethanol/silica interface and to be (TURN)70(DEGREES) at the air/silica interface. Preliminary results show that SFG combining a visible frequency and an infrared frequency can be used to obtain vibrational spectra of adsorbates on silica. Experiments performed on a strongly-interacting well-characterized Rh(111) surface in ultrahigh vacuum establish the sensitivity of the SH probe in corroboration with other surface probes. For the first time, the SH coverage-dependence was fit by theory in a quantitative way for the case of O-atom adsorption. The sensitivity of SH to adsorption at different sites was established for CO on top- and bridge-sites. SHG was shown to be surface specific in that the SHG from alkali metal surfaces originates from the first two monolayers. SH sensitivity to the adsorption of catalytically-important hydrocarbons and to chemical processes such as benzene dehydrogenation was also demonstrated.