Berlin 2018 – scientific programme

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CPP: Fachverband Chemische Physik und Polymerphysik

CPP 27: Focus Session: Frontiers of Electronic-Structure Theory: Correlated Electron Materials III (joint session O/MM/DS/TT/CPP)

CPP 27.4: Talk

Tuesday, March 13, 2018, 12:00–12:30, HL 001

A first-principles approach to hot-electron-induced ultrafast dynamics at metal surfaces — •Reinhard J. Maurer — Department of Chemistry, University of Warwick, Gibbet Hill Road, CV4 7AL Coventry, UK

Low-lying electronic excitations in metals, so-called hot electrons, couple efficiently to molecular adsorbate motion. In doing so, they give rise to a number of curious experimental observations. This includes pico-second-scale energy loss of molecular adsorbate vibration, highly inelastic atomic and molecular scattering from metal surfaces, and light-assisted molecular desorption and chemical transformations, recently coined "hot-electron chemistry". In this talk, I will present a first-principles treatment of hot-electron-induced molecular dynamics based on Density Functional Theory that correctly captures the magnitude and mode-specificity of hot-electron mediated adsorbate-substrate energy transfer [1]. Utilizing our efficient all-electron local-orbital implementation of hot-electron-induced frictional forces based on Time-Dependent Perturbation Theory, [2] I will show how we correctly capture vibrational relaxation in large-scale metal-mounted molecular catalysts as well as the energy loss and coupled electron-nuclear dynamics of small molecular adsorbates in both thermal and laser-heated conditions. [3] We scrutinize our approach in comparison to recent Sum-Frequency Generation (SFG) spectroscopy and molecular beam scattering experiments. [1] Phys. Rev. Lett. 116, 217601 (2016) ; [2] Phys. Rev. B 94, 115432 (2017); [3] Phys. Rev. Lett. 118, 256001 (2017);