Origin of power laws for reactions at metal surfaces mediated by hot electrons

A wide range of experiments have established that certain chemical reactions at metal surfaces can be driven by multiple hot-electron-mediated excitations of adsorbates. A high transient density of hot electrons is obtained by means of femtosecond laser pulses and a characteristic feature of such experiments is the emergence of a power law dependence of the reaction yield on the laser fluence Y approximately F(n). We propose a model of multiple inelastic scattering by hot electrons which reproduces this power law and the observed exponents of several experiments. All parameters are calculated within density functional theory and the delta self-consistent field method. With a simplifying assumption, the power law becomes exact and we obtain a simple physical interpretation of the exponent n, which represents the number of adsorbate vibrational states participating in the reaction.