Two-photon photoemission of thiolate/Ag(111), nitrile/Ag(111), and alcohol/Ag(111) interfaces elucidates electron solvation and localization in two dimensions. For low coverages of thiolates on Ag(111), the occupied (HOMO) and unoccupied (LUMO) electronic states of the sulfer-silver bond are localized due to the lattice gas structure of the adsorbate. As the coverage saturates and the adsorbate-adsorbate nearest neighbor distance decreases, the HOMO and LUMO delocalize across many adsorbate molecules. Alcohol- and nitrile-covered Ag(111) surfaces solvate excess image potential state (IPS) electrons. In the case of alcohol-covered surfaces, this solvation is due to a shift in the local workfunction of the surface. For two-monolayer coverages of nitriles/Ag(111), localization accompanies solvation of the IPS. The size of the localized electron can be estimated by Fourier transformation of the wavefunction from momentum- to position-space. The IPS electron localizes to 15 ± 4 angstroms full-width at half maximum in the plane of the surface, i.e., to a single lattice site.
A new instrument for angle-resolved two-photon photoemission with exceptional sensitivity and energy resolution has allowed a detailed examination of the interaction of image-state electrons with adsorbates. In addition to measuring the electrostatic properties of molecular-thickness films, the technique serves as a probe of adsorbate growth modes, and provides new opportunities to explore the dynamics of electrons in well-controlled 2D systems.
We report ultrafast measurements of the dynamic thermal expansion of a surface and the temperature dependent surface thermal diffusivity using a two-color reflection transient grating technique. Studies were performed on p-type, n-type, and undoped GaAs(100) samples at several temperatures. Using a 75 fs ultraviolet probe with visible excitation beams, the electronic effects that dominate single color experiments become negligible; thus surface expansion due to heating and the subsequent contraction caused by cooling provide the dominant influence on the diffracted probe. The diffracted signal was composed of two components, thermal expansion of the surface and heat flow away from the surface, allowing the determination of the rate of expansion as well as the surface thermal diffusivity. At room temperature a signal rise due to thermal expansion was observed, corresponding to a maximum average displacement of approximately equals 1 angstroms at 32 ps. Large fringe spacings were used, thus the dominant contributions to the signal were expansion and diffusion perpendicular to the surface. Values for the surface thermal diffusivity of GaAs were measured and found to be in reasonable agreement with bulk values above 50 degree(s)K. Below 50 degree(s)K, the diffusivity at the surface was more than an order of magnitude slower than in the bulk due to increased phonon boundary scattering. Comparison of the results with a straightforward thermal model yields good agreement over a range of temperatures (12 - 300 degree(s)K). The applicability and advantages of the transient grating technique for studying photothermal and photoacoustic phenomena are discussed.