Chapter 10 Electron Transfer and Nonadiabaticity

Journal article, 2008

Electron processes at solid surfaces are numerous and important. Nonadiabaticity (NA) is a concept that is well documented but that seems to face some resistance towards general acceptance in surface dynamics. There is a great multitude of surface processes, and in many subfields NA is just taken for granted, while in other areas some reluctance can be spotted. Even recently, gas-surface interactions could be reviewed cautiously by saying that there is "growing evidence" that "there exist cases where understanding means need to go beyond BOA" (the Born-Oppenheimer approximation), that is to apply NA. No doubt, surface dynamics does seldom provide spectacular manifestations of NA, but still there are numerous NA effects, as listed in this chapter. Electron transfer (ET) is part of such processes. The multitude of ET phenomena at surfaces is reviewed, with a focus on key concepts connected with electron-structure features in the surface region. Documentation for ET and NA in thermal surface processes is also provided. Finally, some attempts are made to find factors for surface-dynamical processes that can be described in adiabatic terms.