Ultra-fast dynamics of electron thermalization, cooling and transport effects in Ru(001)

Abstract

Time-resolved two-photon photoelectron spectroscopy is used to study the dynamics of non-equilibrium electron and hole distributions at bare and D2O-covered Ru(001) following optical excitation (55-fs, 800-nm pulses) with variable fluence (0.04–0.6 mJ cm-2). Within the first 0.5 ps we observe an ultra-fast transient of the excited-carrier population and energy density at the surface which is accompanied by pronounced deviations of the electron-energy distribution from a (thermalized) Fermi–Dirac distribution. Comparison of the transient energy density of the photoexcited electrons at the surface with predictions of the two-temperature model provides fair agreement up to 400 fs, but exhibits a systematically lower energy density at later times, where electrons and phonons are equilibrated. We propose that this reduced energy density at the surface originates from ultra-fast energy transport of non-thermal electrons into the bulk in competition to electron–phonon coupling at the surface. This is corroborated by extending the two-temperature model to account for non-thermal, photoexcited electrons, whereby quantitative agreement with experiment can only be achieved if ballistic transport and reduced electron–phonon coupling is incorporated for non-thermal electrons. Implications for surface femtochemistry are discussed.