Plasmon excitation in core-level photoemission

The surface and bulk plasmon satellites in photoemission from a core level are calculated, treating the photoelectron quantum mechanically and including plasmon dispersion. The long wavelength plasmon excitations are suppressed by interference between intrinsic and extrinsic processes, giving featureless satellites at low electron kinetic energy. Structure develops as the electron kinetic energy increases.     

Effects of configuration-dependent hybridization on core-level photoemission spectra

The Ni2p X-ray photoemission spectrum (XPS) for NiCl₂ is reanalyzed on the basis of a NiCl₆⁴⁻ cluster model. By taking into account the electron configuration dependence of the hybridization strengths between Ni3d and Cl3p orbitals, we show that the model can consistently reproduce the experimental 2p-XPS and the energy gap of the system.     

Revisiting the valence-band and core-level photoemission spectra of NiO

We have reexamined the valence-band (VB) and core-level electronic structure of NiO by means of hard and soft x-ray photoemission spectroscopies. The spectral weight of the lowest energy state was found to be enhanced in the bulk sensitive Ni 2p core-level spectrum. A configuration-interaction model including a bound state screening has shown agreement with the core-level spectrum and off- and on-resonance VB spectra. These results identify the lowest energy states in the core-level and VB spectra as the Zhang-Rice (ZR) doublet bound states, consistent with the spin-fermion model and recent ab initio calculations within dynamical mean-field theory. The results indicate that the ZR character first ionization (the lowest hole-addition) states are responsible for transport properties in NiO and doped NiO.     

Exploring 2D materials at surfaces through synchrotron-based core-level photoelectron spectroscopy

The interest in understanding and controlling the properties of two-dimensional materials (2DMs) has fostered in the last years a significant and multidisciplinary research effort involving condensed matter physics and materials science. Although 2DMs have been investigated with a wide set of different experimental and theoretical methodologies, experiments carried out with surface-science based techniques were essential to elucidate many aspects of the properties of this family of materials. In particular, synchrotron-based X-ray photoelectron spectroscopy (XPS) has been playing a central role in casting light on the properties of 2DMs, providing an in-depth and precise characterization of these materials and helping to elucidate many elusive and intricate aspects related to them. XPS was crucial, for example, in understanding the mechanism of growth of several 2DMs at surfaces and in identifying the parameters governing it. Moreover, the chemical sensitivity of this technique is crucial in obtaining knowledge about functionalized 2DMs and in testing their behavior in several model chemical reactions. The achievements accomplished so far in this field have reached a maturity point for which a recap of the milestones is desirable. In this review, we will showcase relevant examples of studies on 2DMs for which synchrotron-based XPS, in combination with other techniques and state-of-the-art theoretical modeling of the electronic structure and of the growth mechanisms, was essential to unravel many aspects connected to the synthesis and properties of 2DMs at surfaces. The results highlighted herein and the methodologies followed to achieve them will serve as a guidance to researchers in testing and comparing their research outcomes and in stimulating further investigations to expand the knowledge of the broad and versatile 2DMs family.     

Calculated oxygen 1s core-level photoemission spectra from cuprate superconductors

The observed O 1s X-ray photoemission spectra of the cuprate superconductors often exhibit a satellite at a higher binding energy to the main peak. The origin of this satellite is not fully understood. We have done model cluster calculations to investigate the origin of this satellite using the configuration interaction approach. The calculated spectra for the divalent and superconducting cuprates essentially exhibit a single peak. On distorting the cluster in-plane, the peak shifts to higher binding energies. This substantiates a deterioration of the surface leading to the observed satellite structure in the O 1s core-level photoemission spectra of the cuprate superconductors.     

Splitting of core-level lines in photoemission spectra of transition metal compounds

The multiplet structure of core-electron binding energies in Cr 3s, Cr 3p and Cr 2p levels of CrCl₃ and CrBr₃ compounds has been investigated by X-ray photoelectron spectroscopy. The Cr 3s levels show a doublet splitting (about 4.3?eV) for the main emission in both halides. Satellites features are observed in Cr 3s, 3p and 2p levels at higher binding energies. In the Cr 3s spectrum, the main emission is assigned to unscreened intra-atomic multiplet splittings with correlation-induced satellites. The Cr 3p and 2p spectra can be better explained by the multiplet splitting arising from the interaction between valence band 3d electrons and core p holes in the crystal field. Final state screening (charge-transfer) effects do not play a major role in Cr 3s main emission nor do they affect the satellite structures in a relevant way. This explains why the Cr 3s exchange splitting in chromium halides is proportional to the local magnetic moment.     

Theory of angle-resolved photoemission from localised orbitals at solid surfaces

The theory of angle resolved photoemission from localised orbitals is reviewed and is cast in a form requiring the calculation of the purely outgoing wave emanating from an emitting atom, that describes the final state of the photoelectron, rather than using the more usual approach based on time reversed scattering states. An explicit expression is written down for the superposition of partial waves that results from emission from an atomic orbital, and it is pointed out that emission from more complex initial states such as localised bonds or Bloch and surface states, can be described by coherently combining such sets of partial waves. The effect of the crystal surface environment in damping and scattering the waves is described briefly. Model calculations are performed to investigate the major influences on the angular distribution of the photoelectrons. The profound effect of varying the polarisation direction of the incident light relative to the surface is discussed, with examples from the literature, showing how it can be used to determine the type of initial orbital. Emission from directed orbitals is studied and it is shown that scattering by the emitter potential can be an important effect, so that the radial wave function of the outgoing electron, which determines the amplitudes and phases of the outgoing waves, must be calculated with care. Different choices of these quantities lead in the model calculations to very different angular profiles, that sometimes bear little relation to the shape of the initial orbital. The consideration of emission from localised bonds shows that provided that bonds are not too strongly polarised, interference between waves from different centres is always significant at higher energies, and can also be important at energies of a few eV relative to the vacuum. Scattering by the ion cores of the surface region can strongly distort the angular distribution, or may have little effect. But it is generally difficult to decide a priori which influences are dominant for a particular case, so that the interpretation of angular profiles must be based on careful calculations including all these effects. The optimum energy range for the interpretation of experimental data is that from about 30 to 100 eV.     

Plasmon response of a quantum-confined electron gas probed by core-level photoemission

We demonstrate the existence of quantized "bulk" plasmons in ultrathin magnesium films on Si(111) by analyzing plasmon-loss satellites in core-level photoemission spectra, recorded as a function of the film thickness d. Remarkably, the plasmon energy is shown to vary as 1/d2 all the way down to three atomic layers. The loss spectra are dominated by the n=1 and n=2 normal modes, consistent with the excitation of plasmons involving quantized electronic subbands. With decreasing film thickness, spectral weight is gradually transferred from the plasmon modes to the low-energy single-particle excitations. These results represent striking manifestations of the role of quantum confinement on plasmon resonances in precisely controlled nanostructures.     

Valence band and core-level photoemission spectra of black phosphorus single crystals

Valence band structures of black phosphorus have been measured by synchrotron-radiation photoemission spectroscopy. The excitation photon-energy dependence of the spectra has provided information about the 3s-3p hybridization. As for inner core-levels, binding energies of 2p and 2s core-levels, $\text{2p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{?2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ splitting, and the bulk plasmon energy are estimated from X-ray photoemission spectroscopy.     

Remnant fermi surfaces in photoemission

Recent experiments have introduced a new concept for analyzing the photoemission spectra of correlated electrons-the remnant Fermi surface (rFs), which can be measured even in systems which lack a conventional Fermi surface. Here, we analyze the rFs in a number of interacting electron models, and find that the results fall into two classes. For systems with particle-particle (pairing) instabilities, the rFs is an accurate replica of the true Fermi surface. In the presence of particle-hole (nesting) instabilities, the rFs is a map of the resulting superlattice Brillouin zone. The results suggest that the gap in Ca2CuO2Cl2 is of particle-hole origin.