Effects of plasmon energetics on light emission induced by scanning tunneling microscopy.

A theoretical model of plasmon and molecular luminescence induced by scanning tunneling microscopy using a molecule-covered tip on clean metal surfaces is developed. The effects of coupling between molecular exciton and interface plasmon on the luminescence spectra are investigated for variable energy of plasmon modes by means of the nonequilibrium Green's function method. It is found that spectral features arising from interference between the processes of energy absorption by the molecule and interface plasmons appear near the energy of the excitonic mode. For the energy of plasmon above (below) the energy of excitonic mode, an additional peak structure appears in the energy range slightly below (above) the energy of the excitonic mode. Prominent peak and dip structures observed in recent luminescence experiments are interpreted by the developed theory whereby its utility in the fields of plasmonics and nanophotonics is demonstrated.

Rationale for switching to nonlocal functionals in density functional theory.

Density functional theory (DFT) has been steadily improving over the past few decades, becoming the standard tool for electronic structure calculations. The early local functionals (LDA) were eventually replaced by more accurate semilocal functionals (GGA) which are in use today. A major persisting drawback is the lack of the nonlocal correlation which is at the core of dispersive (van der Waals) forces, so that a large and important class of systems remains outside the scope of DFT. The vdW-DF correlation functional of Langreth and Lundqvist, published in 2004, was the first nonlocal functional which could be easily implemented. Beyond expectations, the nonlocal functional has brought significant improvement to systems that were believed not to be sensitive to nonlocal correlations. In this paper, we use the example of graphene nanodomes growing on the Ir(111) surface, where with an increase of the size of the graphene islands the character of the bonding changes from strong chemisorption towards almost pure physisorption. We demonstrate how the seamless character of the vdW-DF functionals makes it possible to treat all regimes self-consistently, proving to be a systematic and consistent improvement of DFT regardless of the nature of bonding. We also discuss the typical surface science example of CO adsorption on (111) surfaces of metals, which shows that the nonlocal correlation may also be crucial for strongly chemisorbed systems. We briefly discuss open questions, in particular the choice of the most appropriate exchange part of the functional. As the vdW-DF begins to appear implemented self-consistently in a number of popular DFT codes, with numerical costs close to the GGA calculations, we draw the attention of the DFT community to the advantages and benefits of the adoption of this new class of functionals.

Extreme ultrafast dynamics of quasiparticles excited in surface electronic bands.

We develop a many-body description of the nonadiabatic dynamics of quasiparticles in surface bands valid on an extremely ultrashort time scale by combining the formalism for the calculation of quasiparticle survival probabilities with the self-consistent treatment of the electronic response of the system. Applying this approach to the benchmark Cu(111) surface, we assess the behavior and intervals of preasymptotic electron and hole dynamics in surface bands and locate the transition to the asymptotic regime of the exponential quasiparticle decay characterized by the corrected Fermi golden rule-type of transition rate. The general validity of these findings enables distinguishing the various regimes of ultrafast electron dynamics that may be revealed in time resolved experiments.

Entangled and disentangled decoherence of intermediate electron-hole pairs in two-photon photoemission from surface bands: beyond the adiabatic approximation.

We discuss the effects which combinations of entangled and disentangled decoherence and transient response induce on the early decay of coherent electron-hole pairs in the intermediate states of two-photon photoemission (2PPE) from image potential bands. We find that their interplay gives rise to deviations of the pair decay probabilities from simple exponential laws governed by independent quasiparticle lifetimes obtained in the self-energes based on the adiabatic hypothesis. Assessment of these effects for paradigmatic Cu(111) surface shows that they are most pronounced in the interval of pump-probe photon pulse delay times typical of current 2PPE experiments.

Linear versus nonlinear coupling effects in single- and multiphonon atom-surface scattering.

We present a comparative assessment of the features of inelastic atom-surface scattering spectra that are produced by different forms of linear and nonlinear phonon coupling to the projectile atom. Starting from a simple theoretical model of atom-surface scattering and employing recently developed exact numerical and approximate analytical methods we calculate and compare the scattering probabilities ensuing from each form of interaction. This enables us to demonstrate that in the regime of thermal energy atom scattering from surfaces the dominant contributions to the zero-, one-, and multiphonon excitation probabilities arise from linear coupling treated to all orders in the interaction.