| AVS 59th Annual International Symposium and Exhibition | |
| Surface Science | Monday Sessions |
| Session SS-MoM |
| Session: | Nonequillibrium and Nonlinear Processes |
| Presenter: | D.J. Auerbach, University of California, Santa Barbara |
| Authors: | D.J. Auerbach, University of California, Santa Barbara K. Golibrzuch, University of Göttingen, Germany A. Kandratsenka, Max Planck Institute for Biophysical Chemistry, Germany R. Cooper, University of Göttingen, Germany C. Bartels, University of Göttingen, Germany I. Rahinov, The Open University of Israel A.M. Wodtke, University of Göttingen, Germany |
| Correspondent: | Click to Email |
Interactions of molecules at metal surfaces can result in nonadiabatic electronic energy exchange with the metal. This complicates theoretical strategies designed to simulate surface reactivity, most of which today are based on the assumption that the electronic motion can be treated adiabatically, i.e. within the Born-Oppenheimer approximation. One widely applied electronically nonadiabatic theory that makes the leap beyond the Born-Oppenheimer approximation is “electronic friction”. In this method coupling of adsorbate motion to metal electrons is treated as a weak perturbation involving frictional forces modifying the molecular dynamics in a systematic and simple way.
Recent experiments on multiquantum vibrational excitation at metal surfaces suggest that at least for certain systems, multi quantum transitions involve energy transfer between the molecule and a single electron hole pair of the solid. These processes might better be described as an electron transfer reaction than as friction. These results suggest that theoretical approaches that go beyond electron weak coupling and electronic friction will be needed to properly treat electronically nonadiabatic effects in surface chemistry.