Vibrational Relaxation at a Metal Surface: Electronic Friction Versus Classical Master Equations

Abstract

Within a 2-D scattering model, we investigate the vibrational relaxation of an idealized molecule colliding with a metal surface. Two perturbative nonadiabatic dynamics schemes are compared: $(i)$ electronic friction (EF) and $(ii)$ classical master equations (CME). In addition, we also study a third approach, $(iii)$ a broadened classical master equation (BCME) that interpolates between approaches $(i)$ and $(ii)$. Two conclusions emerge. First, even though we do not have exact data to compare against, we find there is strong evidence suggesting that EF results may be spurious for scattering problems with more than one nuclear dimension. Second, we find that there is an optimal molecule-metal coupling that maximizes vibrational relaxation rates by inducing large nonadiabatic interactions.

References in corpus (2)

• Ab-initio tensorial electronic friction for molecules on metal surfaces: nonadiabatic vibrational relaxation
• Electron-hole pair creation by atoms incident on a metal surface

Cited by in corpus (1)

• Configuration interaction approaches for solving quantum impurity models