Band structure effects in above threshold photoemission.

We have performed an angle-resolved two-photon and three-photon photoemission study of the Ag(111) surface employing ultrashort laser pulses as the excitation source. We show the presence of multi-photon resonances between electronic states at selected points of the Brillouin zone which appear in the high-order photoemission spectral region. We observe clear signatures of electronic band structure effects of the Ag crystal in above-threshold photoemission (ATP) processes, identifying two types of transitions, which either proceed via non-resonant multi-photon excitation from an occupied initial state, or involve a real intermediate state located above the vacuum level of the solid directly influencing the ATP process. For this latter class of phenomena, we suggest that electron populations created by incoherent processes give a contribution to the multi-photon transition, possibly allowing us to trace the transmission of photoexcited electrons through the crystal.

Coherent optical phonons of ZnO under near resonant photoexcitation.

Ultrafast electron-phonon coupling dynamics in ZnO are investigated by degenerate pump-probe reflectivity measurements using near resonant 400 nm light. Because of the below-gap excitation, photocarriers are excited primarily from deep levels of intrinsic point defects. At least six coherent phonon modes, including two E(2) modes and their combination, longitudinal optical (LO) mode and its overtone (2LO), are observed. Unlike the previous resonant Raman studies using 325 nm light, the intensity of the polar LO phonons is only moderately enhanced by the Fröhlich interaction. The non-polar E(2) phonons decay considerably faster than under visible excitation, indicative of strong deformation potential interaction with photocarriers. The overdamped oscillation centered at around 20 THz is tentatively attributed to the upper branch of the plasmon-phonon coupled mode. The pump-polarization dependence of the phonon amplitudes is consistent with the impulsive Raman generation.

Pi resonance of chemisorbed alkali atoms on noble metals.

We have performed a joint experimental and theoretical study of the unoccupied electronic structure of alkali adsorbates on the (111) surfaces of Cu and Ag. Combining angle- and time-resolved two-photon photoemission spectroscopy with wave packet propagation calculations we show that, along with the well known sigma resonance oriented along the surface normal, there exist long-lived alkali-localized resonances oriented parallel to the surface (pi symmetry). These new resonances are stabilized by the projected band gap of the substrate and emerge primarily from the mixing of the p and d Rydberg orbitals of the free alkali atom modified by the interaction with the surface.

Ultrafast optical spin injection into image-potential states of Cu(001).

We report the observation of a net spin polarization in the n=1 image-potential state at the Cu(001) surface. The spin polarization is achieved by spin-selective multiphoton excitation of electrons from the spin-orbit split Cu d bands to the image-potential state using circularly polarized ultrafast light pulses. We show that by tuning the exciting photon energy, we can adjust the resonant coupling of the image-potential state to d bands of different double-group symmetry. This allows us to tune the spin polarization injected into the image-potential state.

Mechanisms of high-order perturbative photoemission from Cu(001).

We observed high-order 2- to 4-photon photoemission and above threshold photoemission (ATP) processes with 3.07 eV light from the Cu(001) surface. The intensity of 3-photon photoemission via excitation through the n = 1 image potential state significantly exceeded that of the 2-photon process. The ATP occurs either via single photon transitions from the image potential resonances above the vacuum level or by multiphoton transitions from image potential states below the vacuum level. The experimental ratio of the m- to (m + 1)-photon process yields is sensitive to the electronic band structure of the solid.

Surface magnetism during oxygen-aided Fe homoepitaxy.

Magnetization-induced optical surface second harmonic generation (SHG) in the longitudinal geometry was used to study magnetism on the p(1 x 1)O/Fe(001) surface during a layer-by-layer Fe growth with surfactant oxygen. Considerable one-monolayer oscillations were observed. Minima of the magnetization-induced contributions to the second order dielectric susceptibility were detected at half-filled monolayers. These contributions were accessed either by measuring a purely magnetic SHG yield, or indirectly from the magnetization dependence of the overall SHG signal, both providing consistent results. The origin of the oscillatory surface magnetism is consistent with the expected oscillating oxygen induced relaxation due to the surface Fe islands.

Optical intersubband transitions and femtosecond dynamics in Ag/Fe(100) quantum wells.

The optical intersubband transitions and femtosecond dynamics of electrons in quantum well states in Ag/Fe(100) are investigated by interferometric time-resolved two-photon photoemission. The quantum well wave functions and transition probabilities are evaluated from the two-photon photoemission resonance energies and intensities using an extended phase accumulation model. Direct femtosecond pump-probe correlation measurements elucidate the importance of interfaces in confined structures.

Real-time observation of adsorbate atom motion above a metal surface

The dynamics of cesium atom motion above the copper(111) surface following electronic excitation with light was studied with femtosecond (10(-15) seconds) time resolution. Unusual changes in the surface electronic structure within 160 femtoseconds after excitation, observed by time-resolved two-photon photoemission spectroscopy, are attributed to atomic motion in a copper-cesium bond-breaking process. Describing the change in energy of the cesium antibonding state with a simple classical model provides information on the mechanical forces acting on cesium atoms that are "turned on" by photoexcitation. Within 160 femtoseconds, the copper-cesium bond extends by 0.35 angstrom from its equilibrium value.

Femtosecond Cr(4+):YAG laser with an L-fold cavity operating at a 1.2-GHz repetition rate.

Pulses of 55-fs width and 1.2-GHz repetition rate at 1.52 mum are generated from an L-fold cavity Cr(4+):YAG laser by optimization of the lasing-beam mode inside the gain medium. The pulse width is comparable with that obtained from a standard Z-fold cavity. The pulses are characterized by a second-harmonic-generation frequency-resolved optical gating method. The pulse shape deviates from a sech(2) function because of its broad shoulders. With further miniaturization it should be possible to extend the Cr(4+):YAG mode-locked operation to multigigahertz rates.

Understanding molecular dynamics quantum-state by quantum-state.

It is now possible to resolve completely the initial and final quantum states in chemical processes. Spectra of reactive intermediates, of highly vibrationally excited molecules, and even of molecules in the process of falling apart have been recorded. This information has led to greater understanding of the molecular structure and dynamics of small gas-phase molecules. Many of the concepts and spectroscopic techniques that have been developed will be valuable throughout chemistry.