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We describe an approach that links the density-matrix theory for electron transport and relaxation with the density-functional theory for electronic structure. Our analysis of the electron dynamics at Si(100) reveals an unanticipated phonon bottleneck between bulklike and surface states. The fastest relaxation process observed in recent two-photon photoemission experiments is in good agreement with the calculated phonon-mediated intrasurface-band scattering

Linking density functional and density-matrix theory: Picosecond electron relaxation at the Si(100) surface