The mechanism leading to photon-stimulated desorption (PSD) of excited atoms from the surfaces of alkali halides has been a subject of controversy since it was first discussed a decade ago. We have recently carried out a systematic experimental study of PSD from alkali halides under both valence-band and core-level excitation. Our data demonstrate that the desorption yields for excited alkali atoms track the excitonic optical response of these crystals even at photon energies below the bulk band gap. Secondary electron measurements, taken simultaneously, implicate the formation of excess metal in the time and dose dependence of PSD yields. These results suggest a unified picture of PSD in which the ion motion initiating desorption is pictured as the decay of a localized, highly deformed vibrational mode of the crystal. Plausible mechanisms for creation of the excited atomic state include relaxation of excited F-centers and resonant neutralization into the excited state on metallic microclusters.

Self-Trapped Excitons discusses the structure and evolution of the self-trapped exciton (STE) in a wide range of materials. It includes a comprehensive review of experiments and extensive tables of data. Emphasis is given throughout to the unity of the basic physics underlying various manifestations of self-trapping, with the theory being developed from a localized, atomistic perspective. The topics treated in detail in relation to STE relaxation include spontaneous symmetry breaking, lattice defect formation, radiation damage, and electronic sputtering.

We describe recent measurements which have provided, in unprecedented detail, insights into the electronic mechanisms through which energy carried into a material by photon irradiation is absorbed, localized and rechanneled to produce desorption, surface modification, erosion and damage. The specific object of these studies has been desorption induced by electronic transition in alkali halide crystals, with particular emphasis on the dynamics of changes in the surface and near-surface regions. In our experiments, the irradiating ultraviolet photons are provided by a synchrotron storage ring, and the dynamical information about desorption products is obtained from optical measurements of the quantum states, yields and velocity distributions of neutral ground-state and excited-state atoms ejected from the surface of the irradiating material. These studies have shown that the dominant exit channels in photon-induced particle emission are those producing ground-state and excited-state neutral atoms. Using dynamical information about these desorbing neutral species, obtained, for example, by laser-induced fluorescence and laser Doppler spectroscopy, we are generating an increasingly comprehensive picture of the dynamics of electronic energy flow into and out of pure crystalline surfaces in these prototypical dielectrics. We are also beginning to be able to relate desorption dynamics to specific materials properties, and to discriminate between pure surface and near-surface effects in these materials. Applications of these techniques to the problem of photon-induced surface damage and to analysis of surface dynamics in dielectric materials are discussed, and the relationships between these nearly ideal model materials and the non-crystalline, covalently bonded materials more typical of real optical elements are pointed out. 19 refs., 13 figs.