A theory for the effect of a strong intra-atomic Coulomb repulsion U on the nonadiabatic transfer of charge between a metallic surface and a moving atomic species is presented. Using slave bosons and a nonequilibrium Green’s-function technique, we solve the equations appropriate for the U=∞ problem in the case when either the atom-surface hopping matrix element is small, or the number of degenerate atomic states is large. We generalize the earlier treatment of Langreth and Nordlander (LN) to include off-diagonal self-energies and present a general numerical scheme for the exact solution of the Dyson equations. We verify that our scheme gives the correct answer in several limiting cases where an exact solution is known, and give quantitative predictions of when deviations from these limits become important. These limits include (1) the simple master equation limit for low velocities and weak coupling, (2) the generalized master equation of LN for larger velocities and atom-surface coupling, (3) the approach to thermal equilibrium when the time dependence is removed, and (4) the maintenance of local thermal equilibrium when the energy parameters vary sufficiently slowly. From a calculation of the instantaneous (nonequilibrium) spectral function of the level on the scattering atom, we are able to study the rate of formation of the Kondo and mixed valent resonances near the Fermi level. We find a slow formation rate for such resonances relative to that of the broader parts of the spectral density centered near the bare atom level positions.

• Received 10 January 1994

DOI:https://doi.org/10.1103/PhysRevB.49.13929