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Image-potential states have been studied by two-photon photoemission for the surface of Al(100) where the whole series is energetically degenerate with free-electron-like bulk states. In contrast with expectations, the series of resonances is not smeared out to one broad structure as a result of a strong coupling to the bulk continuum. Instead, the first resonance (n = 1) is found to be suppressed, and the resonances with quantum numbers n = 2, 3, 4, 5 are resolved as individual peaks in the time-resolved spectra. Both effects are suggested to be a consequence of resonance trapping. [ABSTRACT FROM AUTHOR]

The geometrical and electronic properties of the monolayer (ML) of tetracene (Tc) molecules on Ag(111) are systematically investigated by means of DFT calculations with the use of a localized basis set. The bridge and hollow adsorption positions of the molecule in the commensurate γ-Tc/Ag(111) are revealed to be the most stable and equally favorable irrespective to the approximation chosen for the exchange-correlation functional. The binding energy is entirely determined by the long-range dispersive interaction. The former lowest unoccupied molecular orbital remains being unoccupied in the case of γ-Tc/Ag(111) as well as in the α phase with increased coverage. The unit cell of the α phase with point-on-line registry was adapted for calculations based on the available experimental data and computed structures of the γ phase. The calculated position of the Tc/Ag(111) interface state is found to be noticeably dependent on the lattice constant of the substrate, however its energy shift with respect to the Shockley surface state of the unperturbed clean side of the slab is sensitive only to the adsorption distance and in good agreement with the experimentally measured energy shift. [ABSTRACT FROM AUTHOR]

We present a theoretical study of lifetimes of interface states (IS) on metal-organic interfaces PTCDA/Ag(l 11), NTCDA/Ag(l 11), PFP/Ag(111), and PTCDA/Ag(100), describing and explaining the recent experimental data. By means of unfolding the band structure of one of the interfaces under study onto the Ag(l 11) Brillouin zone we demonstrate that the Brillouin zone folding upon organic monolayer deposition plays a minor role in the phase space for electron decay, and hence weakly affects the resulting lifetimes. The presence of the unoccupied molecular states below the IS gives a small contribution to the IS decay rate, which is mostly determined by the change of the phase space of bulk states upon the energy shift of the IS. The calculated lifetimes follow the experimentally observed trends. In particular, we explain the trend of the unusual increase of the IS lifetimes with rising temperature. [ABSTRACT FROM AUTHOR]

Time- and angle-resolved two-photon photoemission (2PPE) was used to study the electronic structure and ultrafast electron dynamics of the p-doped topological insulator Sb2Te3 and its derivative Sb2Te2S. Our 2PPE experiments directly reveal that the massless Dirac-cone like energy dispersion of topological surface states is realized above the Fermi energy in both materials. The observed bulk conduction bands of Sb2Te2S are found to be shifted to higher energies as compared to Sb2Te3. This shift has, however, surprisingly almost no influence on the electron dynamics in the topological surface state, which proceed on a picosecond time scale. [ABSTRACT FROM AUTHOR]

The unoccupied electronic states of epitaxially grown graphene on Ru(0001) have been explored by time- and angle-resolved two-photon photoemission. We identify a Ru derived resonance and a Ru/ graphene interface state at 0.91 and 2.58 eV above the Fermi level, as well as three image-potential derived states close to the vacuum level. The most strongly bound, short-lived, and least dispersing image-potential state is suggested to have some quantum-well character with a large amplitude below the graphene hills. The two other image-potential states are attributed to a series of slightly decoupled states. Their lifetimes and dispersions are indicative of electrons moving almost freely above the valley areas of the moire superstructure of graphene. [ABSTRACT FROM AUTHOR]

The dynamics of electrons in image-potential resonances on the Ag(111) surface, i.e., image-potential states that are resonant with bulk bands, have been studied by time-resolved two-photon photoemission in combination with quantum-beat spectroscopy. Energies and lifetimes of these resonances were determined up to a quantum number n = 7. Both quantities show a hydrogen-like scaling with quantum number n. The measured decay time of the first image-potential state (n = 1), which is still located in the projected band gap, is 31.5(1.5) fs. The decay time decreases to 23(2) fs for the resonance n = 2 and then increases up to 1 ps for n = 7. It is concluded that the elastic decay of the resonances due to elastic electron transfer into the bulk is nearly one order of magnitude faster than the inelastic electron-hole pair decay. Nevertheless, the elastic decay is found to be slower than theoretically predicted. The pure dephasing times of the resonances n = 3-7 are longer than the decay times. This suggests that electron-phonon scattering is weak despite a large bulk penetration of the resonance wave functions. [ABSTRACT FROM AUTHOR]

The properties of Shockley-type interface states between ir-conjugated organic molecular layers and metal surfaces are investigated by time-resolved two-photon photoemission experiments and density functional theory. For perylene- and naphthalene-tetracarboxylic acid dianhydride (PTCDA and NTCDA) adsorbed on Ag(111), a common mechanism of formation of the interface state from the partly occupied surface state of the bare Ag(111) is revealed. The energy position is found to be strongly dependent on the distance of the molecular carbon rings from the metal and their surface density. Bending of the carboxyl groups enhances the molecular overlap of the interface state. [ABSTRACT FROM AUTHOR]

Spatially resolved optical second-harmonic generation (SHG), that is, SHG microscopy, is shown to be a versatile tool for the investigation of femtosecond laser-induced surface processes such as adsorbate diffusion and desorption and their dependence on absorbed laser fluence. As an example, time-resolved measurements on the diffusion of O from the steps onto the terraces of a vicinal Pt(111) surface at low substrate temperature were performed. Using the sensitivity of SHG on step coverage and analyzing the signal change across the laser beam profile via SHG microscopy during laser-induced diffusion, the strong nonlinear fluence dependence of the diffusion rate could be determined. Using SHG microscopy in combination with a two-pulse correlation scheme, time-resolved information on the surface reaction was obtained as a function of absorbed laser fluence. [ABSTRACT FROM AUTHOR]

We present energy-momentum mapping of the surface Dirac photocurrent in the topological insulator Sb2Te3 by means of time- and angle-resolved two-photon photoemission spectroscopy combined with polarization-variable midinfrared pulsed laser excitation. It is demonstrated that a direct optical transition from the occupied to the unoccupied part of the surface Dirac cone permits the linear and circular photogalvanic effect, which thereby enables us to coherently control the electric surface photocurrent by laser polarization. Moreover, the photocurrent mapping directly visualizes ultrafast current dynamics in the Dirac cone as a function of time. We unravel the ultrafast intraband relaxation dynamics of the inelastic scattering and momentum scattering separately. Our observations pave the way for coherent optical control over surface Dirac electrons in topological insulators. [ABSTRACT FROM AUTHOR]

The theoretical modeling of metal-organic interfaces represents a formidable challenge, especially considering the delicate balance of various interaction mechanisms and the large size of the involved molecular species. In the present study, the energies of interface states, which are known to display a high sensitivity to the adsorption geometry and electronic structure of the deposited molecular species, have been used to test the suitability and reliability of current theoretical approaches. Two well-ordered overlayer structures (relaxed and compressed monolayers) of 1,4,5,8-naphthalene-tetracarboxylic acid dianhydride (NTCDA) on Ag(111) have been investigated using two-photon photoemission to derive precise interface-state energies for these closely related systems. The experimental values are reproduced by our density-functional theory (DFT) calculations with two approaches to treat dispersion interactions (semi-empirical correction DFT-D3 and parametrized functional optB88) and basis set approaches (localized numerical atomic orbitals, plane waves) with remarkable accuracy. Our results underline the trustworthiness and some of the limitations of current DFT-based methods regarding the description of geometric and electronic properties of metal-organic interfaces. [ABSTRACT FROM AUTHOR]

We combine tunable midinfrared (mid-IR) pump pulses with time- and angle-resolved two-photon photoemission to study ultrafast photoexcitation of the topological surface state (TSS) of Sb2Te3. It is revealed that mid-IR pulses permit a direct excitation from the occupied to the unoccupied part of the TSS across the Dirac point. The novel optical coupling induces asymmetric transient populations of the TSS at ±k∥, which reflects a macroscopic photoexcited electric surface current. By observing the decay of the asymmetric population, we directly investigate the dynamics of the long-lived photocurrent in the time domain. Our discovery promises important advantages of photoexcitation by mid-IR pulses for spintronic applications. [ABSTRACT FROM AUTHOR]

The temperature dependence of the dynamics of electrons in the n=1 image potential state on the Ag(111) surface has been investigated by means of time-resolved two-photon photoemission spectroscopy and many-body calculations. We show that the decay rate of electrons in this state grows linearly with temperature. The thermal shortening of the lifetime is caused by the increase of the electron-electron scattering rate, due to deeper penetration of the image state wave function into the bulk metal at higher temperature. The electron-phonon scattering in this state is found to be small. [ABSTRACT FROM AUTHOR]

The dependence of the inelastic lifetime of electrons in the first n = 1 image-potential state of clean and rare-gas covered Ag(111), Cu(111), and Cu(100) surfaces on their momentum parallel to the surface has been studied experimentally by means of time- and angle-resolved two-photon photoemission spectroscopy (2PPE) and theoretically by calculations based on the many-body theory within the self-energy formalism. Similar to the previously studied clean Cu(100) surface, the theoretical results are in excellent agreement with the experiment findings for Cu(111). For Ag(111), the theory overestimates the decay rate and its momentum dependence, which is attributed to the neglect of surface plasmon excitations. With increasing parallel momentum, the n = 1 state shifts out of the projected bulk band gap on both surfaces and turns into an image-potential resonance. This opens an additional decay channel by resonant electron transfer into the bulk, which is theoretically treated by the application of the wave packet propagation approach. The expected stronger increase of the decay rate upon crossing the edge of the band gap, however, is not observed in the experiment. The decoupling of the image-potential states from the metal surface upon adsorption of rare-gas layers results in a decrease of the decay rate as well as of its momentum dependence by a similar factor, which can be successfully explained by the change of interband and intraband contributions to the total decay rate. [ABSTRACT FROM AUTHOR]

Electrons in image-potential states on the surface of bulk helium represent a unique model system of a two-dimensional electron gas. Here, we investigate their properties in the extreme case of reduced film thickness: a monolayer of helium physisorbed on a single-crystalline (111)-oriented Cu surface. For this purpose we have utilized a customized setup for time-resolved two-photon photoemission at very low temperatures under ultrahigh vacuum conditions. We demonstrate that the highly polarizable metal substrate increases the binding energy of the first (n=1) image-potential state by more than 2 orders of magnitude as compared to the surface of liquid helium. An electron in this state is still strongly decoupled from the metal surface due to the large negative electron affinity of helium and we find that even 1 monolayer of helium increases its lifetime by 1 order of magnitude compared to the bare Cu(111) surface.

We combine tunable midinfrared (mid-IR) pump pulses with time- and angle-resolved two-photon photoemission to study ultrafast photoexcitation of the topological surface state (TSS) of Sb_{2}Te_{3}. It is revealed that mid-IR pulses permit a direct excitation from the occupied to the unoccupied part of the TSS across the Dirac point. The novel optical coupling induces asymmetric transient populations of the TSS at ±k_{∥}, which reflects a macroscopic photoexcited electric surface current. By observing the decay of the asymmetric population, we directly investigate the dynamics of the long-lived photocurrent in the time domain. Our discovery promises important advantages of photoexcitation by mid-IR pulses for spintronic applications.

We investigate macroscopic interference effects in high-order harmonic generation using a Ti:sapphire laser operating at a 100 kHz repetition rate. The structure and behavior of spectral and spatial interference fringes are explained and analytically described by transient phase matching of the long electron trajectory contribution. Time-frequency mapping due to the temporal chirp of the harmonic emission allows us to observe Maker fringes directly in the spectral domain.

The lifetimes of electrons at the interface between 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) and Ag(111) have been studied by means of time- and angle-resolved two-photon photoemission. We observe a dispersing unoccupied state 0.6 eV above the Fermi level with an effective electron mass of 0.39m{e} at the Gamma[over ] point. The short lifetime of 54 fs is indicative of a large penetration of the wave function into the metal. Supported by model calculations this interface state is interpreted as predominantly arising from an upshift of the occupied Shockley surface state of the clean metal due to the interaction with the PTCDA overlayer.

Diffusion of atomic oxygen on a vicinal Pt111 surface induced by femtosecond laser pulses has been studied using optical second-harmonic generation as a sensitive in situ probe of the step coverage. Time-resolved studies of the hopping rate for step-terrace diffusion with a two-pulse correlation scheme reveal a time constant of 1.5 ps for the energy transfer from the electronic excitation of the substrate to the frustrated translations of the adsorbate.

We demonstrate the existence of buried image-potential states at the interface between thick Ar films and a Cu(100) substrate. The electron dynamics of these solid-solid interface states, energetically located above the vacuum level in the band gaps of both materials, could be investigated with time-resolved two-photon photoemission for an Ar layer thickness up to 200 A. Relaxation on time scales between 40 and 200 fs occurs via two distinct channels, resonant tunneling through the insulating layer into the vacuum and electron-hole pair decay in the metal.

The optically induced electron dynamics at a Si(001) surface is studied using a five-wave-mixing setup which measures the diffracted second-harmonic intensity induced by three ultrashort (13 fs) laser pulses. Depending on the time ordering of the pulses, this technique is capable of monitoring the temporal evolution of photoexcited one- or two-photon coherences, or populations. For a particular pulse sequence, the experiments show a delayed rise and a decay of the diffracted signal intensity on time scales of 50 and 250 fs, respectively. This response can be described by optical Bloch equations by including rapid scattering of the photoexcited carriers in the D(down) band of Si(001).

The effect of an atomically thin Ar layer on the image-potential states on Cu(100) surfaces is studied in a joint experimental-theoretical study, allowing a detailed analysis of the interaction between a surface electron and a thin insulator layer. A microscopic theoretical description of the Ar layer is developed based on mutually polarizing Ar atoms. Account of the 3D Ar layer structure allows one to predict energies and lifetimes of the image states in excellent agreement with the observations. The Ar layer, even as thin as one monolayer, is efficiently insulating the state from the metal.

The angular dependence of the dissociative adsorption of molecular hydrogen at terrace and step sites of vicinal single-domain Si(001) surfaces was investigated by means of molecular beam techniques and optical second-harmonic generation. A strongly anisotropic behavior was observed for terrace adsorption with polar distributions of cos3theta and cos12theta parallel and perpendicular to the dimer, respectively. The D(B)-steps show enhanced reactivity under glancing incidence in the upwards direction. The results are traced back to the directionality of the covalent surface bonds.

The dependence of the inelastic lifetime of electrons in the image-potential states of Cu(100) on their momentum parallel to the surface has been studied experimentally by means of time- and angle-resolved two-photon photoemission and theoretically by evaluating the electron self-energy within the GW approximation. The pronounced decrease of the n = 1 lifetime from 40 fs at normal emission (k(parallel) = 0) to 20 fs for k(parallel) = 0.33 A(-1) cannot be accounted for by interband decay processes to bulk states. We show that intraband transitions within the image-state band give a contribution to this decrease comparable in magnitude with the interband channel.

Dissociative adsorption of molecular hydrogen on clean Si(001) surfaces has been investigated by means of scanning tunneling microscopy. The dissociated hydrogen atoms are found to occupy Si atoms of adjacent dimers. In addition to this interdimer configuration associated with the adsorption of isolated hydrogen molecules, pairs of adjacent doubly occupied dimers are readily formed. They arise from the enhanced reactivity of partially occupied dimers following the initial H2 adsorption step. The results are considered in light of recent adsorption and desorption measurements.

The ability of the Si(001) surface to adsorb H2 molecules dissociatively increases by orders of magnitude when appropriate surface dangling bonds are terminated by H atoms. Through molecular beam techniques the energy dependent sticking probability at different adsorption sites on H-precovered and stepped surfaces is measured to obtain information about the barriers to adsorption, which decrease systematically with an increase in coadsorbed H atoms. With the help of density functional calculations for interdimer adsorption pathways, this effect is traced back to the electronic structure of the different adsorption sites and its interplay with local lattice distortions.