Electron tunneling of photochemical reactions on metal surfaces: nonequilibrium Green's function-density functional theory approach to photon energy dependence of reaction probability

We have developed a theoretical model of photoinduced reactions on metal surfaces initiated by the substrate/indirect excitation mechanism using the nonequilibrium Green's function approach. We focus on electron transfer, which consists of (1) electron-hole pair creation, (2) transport of created hot electrons, and (3) tunneling of hot electrons to form an anion resonance. We assume that steps (1), (2), and (3) are separable. By this assumption, the electron dynamics might be restated as a tunneling problem of an open system. Combining the Keldysh time-independent formalism with the simple transport theory introduced by Berglund and Spicer, we present a practical scheme for first-principle calculation of the reaction probability as a function of incident photon energy. The method is illustrated by application to the photoinduced desorption/dissociation of O2 on a Ag(110) surface by adopting density functional theory.