Experimental verification of the chemical sensitivity of two-site double core-hole states formed by an x-ray free-electron laser

We have performed x-ray two-photon photoelectron spectroscopy using the Linac Coherent Light Source x-ray free-electron laser in order to study double core-hole (DCH) states of CO2, N2O, and N2. The experiment verifies the theory behind the chemical sensitivity of two-site DCH states by comparing a set of small molecules with respect to the energy shift of the two-site DCH state and by extracting the relevant parameters from this shift.     

Double photoionization into double core-hole states in Xe

Double photoionization (DPI) leading to double core-hole states of Xe2+ 4d(-2) has been studied using a magnetic bottle time-of-flight spectrometer. The assignments of the Xe2+ 4d(-2) states are confirmed by the Auger lines extracted from fourfold coincidences including two photoelectrons and two Auger electrons. It is estimated that the core-core DPI into Xe2+ 4d(-2) at a photon energy of 301.6 eV has a favored cross section of about 0.3 MB. The intense core-core DPI is due to mixing of the 4d(-2) continuum with the 4p single photoionization, which is manifested in the relative intensities of the Xe2+ 4d(-2) components.     

Single impurity Anderson model versus density functional theory for describing Ce L3 x-ray absorption spectra of CeFe2: resolution of a recent controversy

We resolved a recent controversy on the structure of the Ce L(3) x-ray absorption spectra (XAS) of CeFe(2); i.e., which of the single impurity Anderson model (SIAM) and the first-principles band calculations based on the density-functional theory (DFT) describes more appropriately the Ce 4f states and their contribution to the Ce L(3) XAS? For this purpose, we examined the core-hole effect in Ce L(3) XAS as an application of our new method taking advantage of resonant x-ray emission spectroscopy. Our result clearly shows that the Ce L(3) XAS structure is caused by the mixed valence 4f character revealed by the core-hole potential effect as indicated by SIAM, but denies the possibility that the L(3) XAS structure is caused by the 5d band structure with a very small core-hole effect as predicted by band calculations based on DFT.     

Double core hole creation and subsequent Auger decay in NH3 and CH4 molecules

Energies of the hollow molecules CH(4)(2+) and NH(3)(2+) with double vacancies in the 1s shells have been measured using an efficient coincidence technique combined with synchrotron radiation. The energies of these states have been determined accurately by high level electronic structure calculations and can be well understood on the basis of a simple theoretical model. Their major decay pathway, successive Auger emissions, leads first to a new form of triply charged ion with a core hole and two valence vacancies; experimental evidence for such a state is presented with its theoretical interpretation. Preedge 2-hole-1-particle (2h-1p) states at energies below the double core-hole states are located in the same experiments and their decay pathways are also identified.     

Theory of core-level spectroscopy in f and d electron systems

A review is presented of many body effects in core-level spectroscopy (CLS) of f and d electron systems from a theoretical point of view. Historical developments and the most recent topics in this field are described. The impurity Anderson model (IAM) has been successfully applied to the analysis of X-ray photoemission spectra (XPS) and X-ray absorption spectra (XAS) in f and d electron systems, where the f and d electron states are treated as being on a single atomic site and they are hybridized with valence or conduction electron states. The effect of a core-hole potential in the final state of CLS plays an important role. Typical examples of calculated results for XPS in rare-earth compounds and transition metal compounds are given. Recent developments in the study of resonant X-ray emission spectra (RXES) are also introduced. A theoretical approach beyond the IAM is discussed mainly for the analysis of RXES of transition metal compounds.     

Many-body effect in Auger-photoelectron coincidence spectroscopy spectra

When the shakeup/down excitations are not negligible in the core-level electron ionization, the photoelectron spectral peak measured in coincidence with a selected singles (noncoincidence) Auger-electron spectral peak does not necessarily coincide with the singles one. We discuss how the interference between the core-hole decay of a fully relaxed core-hole state and that of an incompletely relaxed one via the interaction between the final states created by the respective core-hole decays, affects the kinetic energy shift and asymmetrical lineshape change of the coincidence photoelectron spectrum compared to the singles one. When the final-state interaction is considerable, the interference reduces much the energy shift and the asymmetrical lineshape change. By the Auger-photoelectron coincidence spectroscopy (APECS) we can study the interference effect which does not manifest in the singles photoelectron spectrum. We discuss also the interference effect when the core-hole decay rates of both the fully relaxed core-hole state and the incompletely relaxed one depend critically on the changes in both the Auger-electron kinetic energy and the final-state potential. The effect is fairly independent of the changes.     

Core-hole screening effects in the initial state of Auger emission across the transition metal series

Supercell method is used to study the relaxation and screening effects on the initial state of the Auger transition in metals. Our consideration is based on the assumption that when a core-hole exists long enough before the Auger transition occurs, the occupied valence states relax to screen the core-hole which results in a redistribution of the valence electrons, in particular within the atom that contains the core-hole. In order to make the interaction between the core-holes sites at different atoms negligible, the real metal is simulated by supercells repeated periodically. In each supercell one atom is considered to have a core-hole and many others not to have one. The electronic states concerned by the Auger transition are calculated by the self-consistent full-potential linearized augmented plane wave (FLAPW) method. Different responses of the local valence band on the site of the core-hole have been shown depending on whether the d-bands are partially or completely filled. According to the final state rule, the screening to the two holes in the local valence band after the Auger transition has also been considered, as examples, for Ni and Cu metals. The result shows that, with the existence of two holes in them, the states of the local valence band of Cu relax to atomic-like impurity states, while the local valence band of Ni changes to a much narrow band at the bottom of the original band. As examples, L₃VV and M₁VV Auger spectral profiles of Cu have been calculated in reasonably good agreement with the experiment.     

Electron energy loss near edge structure (ELNES) spectra of AlN and AlGaN: a theoretical study using the Wien2k and Telnes programs

Several aspects of the modelling of the energy loss near edge structure (ELNES) using the Wien2k code and the Telnes program are discussed in this paper. A case study with ground state, partial and full core-hole calculations of wurtzite AlN was performed and the results were compared with experimental transmission electron microscopy data. The best agreement with the experimental observations was obtained for the full core-hole case. Changes in the ELNES spectra for various core-hole charges are explained by investigating the site and symmetry projected density of states. Directionally resolved N K-edge ELNES of AlN are discussed and the magic angle beta approximately 2.5mrad is identified which is in a good agreement with other theoretical predictions. Finally, preliminary results on a compositional study of Al(x)Ga(1-x)N are explored.     

Polarization entanglement generation at 1.5 μm based on walk-off effect due to fiber birefringence

In this Letter, a linear scheme to generate polarization entanglement at 1.5 μm based on commercial polarization maintained dispersion shifted fiber (PM-DSF) is proposed. The birefringent walk-off effect of the pulsed pump light in the PM-DSF provides an effective way to suppress the vector scattering processes of spontaneous four-wave mixing. A 90 deg offset of fiber polarization axes is introduced at the midpoint of the fiber to realize the quantum superposition of the two correlated photon states generated by the two scalar processes on different fiber polarization axes, leading to polarization entanglement generation. Experiments of the indistinguishable property on single-side and two-photon interference in two nonorthogonal polarization bases are demonstrated. A two-photon interference fringe visibility of 89±3% is achieved without subtracting the background counts, demonstrating its great potential in developing highly a efficient and stable fiber based polarization-entangled quantum light source at the optical communication band.     

Kaon absorption from kaonic atoms and formation spectra of kaonic nuclei

We considered the kaon absorption from atomic states into the nucleus. We found that the nuclear density probed by the atomic kaon significantly depends on the kaon orbit. Then, we re-examined the meanings of the observed strengths of one-body and two-body kaon absorption, and investigated the effects to the formation spectra of kaon bound states by in-flight (K ^-, p) reactions. As a natural consequence, if the atomic kaon probes a smaller nuclear density, the ratio of the two-body absorption at nuclear center is larger than the observed value in kaonic atoms, and the depth of the imaginary potential is deeper even at smaller kaon energies as in kaonic nuclear states because of the large phase space for the two-body processes. This deeper imaginary potential makes the signals of kaonic nucleus formation more unclear in the (K ^-, p) spectra.     

Bremsstrahlung-induced Auger peaks

For highly-polar nitro-substituted aromatic compounds, characterization of the nitro-N 1s core-hole states from the standpoint of intramolecular charge-transfer (CT) interaction is obtained through analysis of the energy difference between the satellite and the main peak, and the relative intensity of the satellite compared to the main peak.Two-dimensional configuration interaction (CI) is considered between the no-bond (covalent) and the CT (ionic) structures in both the initial and the final states. The off-diagonal element between these two structures is given in terms of the core resonance integral between the ring carbon and the nitro nitrogen, and can therefore be reduced by steric hindrance, and is also closely related to the π-electron density at the adjacent carbon in the donor orbital. The absolute magnitude of the off-diagonal element and the ionization potential of the donor are important factors determining the relative intensity of the CT satellite.It was found that in the case of some nitro-N 1s core-hole ions the CT structure is located below the no-bond structure, and that two-dimensional CI calculations are valid as far as the ground and the CT states are concerned.     

Effect of relaxation and decay of a charge transfer shakeup satellite on Auger-electron spectroscopy spectra and Auger-photoelectron coincidence spectroscopy spectra of adsorbates

An electron excited to an unoccupied part of adsorbate–substrate hybrid states in a chemisorbed molecule by a resonant core electron excitation or charge transfer (CT) shakeup may delocalize on time scale of core-hole decay so that the excited core-hole state relaxes partly or completely to a fully relaxed one. The Auger decay of the fully relaxed core-hole state via the relaxation of the excited one introduces an additional feature in the resonant Auger-electron spectroscopy (RAES) spectrum and the AES spectrum. However, the additional feature in the RAES spectrum is a normal AES spectrum by decay of the fully relaxed core-hole state, whereas the one in the AES spectrum is the AES spectrum by decay of the fully relaxed core-hole state broadened by the photoelectron spectroscopy (PES) CT shakeup satellite weighted by the branching ratio of the relaxation width. The discrepancies between the AES spectrum measured at high above the ionization threshold and the additional feature in the RAES spectrum consist of the symmetric-like part by the decay of the fully relaxed core-hole state via the relaxation of the CT shakeup state and the asymmetric part by the direct decay of the shakeup states. The asymmetric part increases with a decrease in the hybridization strength. This explains the variation with the hybridization strength in the discrepancies between the RAES spectra and the AES spectra of chemisorbed molecules such as CO/Ni, CO/Cu and CO/Ag. A comparison of the singles PES spectrum with the one measured in coincidence with the AES main line of a selected kinetic energy (KE) provides the delocalization rate of the excited electron in the CT shakeup state as a function of photoelectron KE. The coincidence measurement to obtain the partial singles PES spectrum is discussed.     

Complete two-electron spectra in double photoionization: the rare gases Ar,Kr, and Xe

A new spectroscopic technique, giving complete two-dimensional e(-)-e(-) coincidence spectra in single photon double photoionization, is presented. The technique resolves the states of doubly charged ions and provides spectra of the individual electrons emitted in formation of each final dication state. Complete spectra for double photoionization of Xe, Kr, and Ar at photon energies up to 51 eV have been recorded. Overall and surprisingly, the np(4) 3P, 1D, and 1S states are populated according to their statistical weights. When the evident autoionization is excluded, the supposedly favored 3P states are in fact disfavored. Detailed information on the autoionization processes is also made available.     

Polaron Effect of a Two Electron Parabolic Quantum Dot

Polaron induced double electron in a quantum dot is investigated using the exact diagonalization techniques and the compact density-matrix approach. The dependence of nonlinear optical processes on the incident photon energies and the polaronic effect are brought out. The linear, third order non-linear optical absorption coefficients and the refractive index changes of singlet and triplet states as a function of photon energy are obtained with and without the inclusion of polaronic effect. It is found that the geometrical confinement and the effect of polaron have great influence on the optical properties of dots.     

Ionization and population transfer in lithium Rydberg states with ultrashort chirped laser pulses

We present a theoretical study of dynamics of Rydberg states of lithium using ultra short chirped laser pulse having a Gaussian envelope. The population transfer probabilities are calculated of different Rydberg states on chirped laser factors. The calculations are performed by direct numerical integration of Schr?dinger equation using fourth order Runge-Kutta method. The behavior of dynamics of Rydberg states for these factors is of great significance. These results are of potential interest in coherent quantum control, quantum computation and in many physical and chemical processes.     

Lineshape studies of the X-ray photoemission of small metal clusters

It is shown that the lineshape asymmetry of the X-ray photoelectron spectra of the Pt(4f) and Pd(3d) core-levels in small metal clusters decreases with the size of the cluster. Such changes are related to the changes of the density of states of the valence electrons and the effective core-hole potential at the Fermi level. The decrease of the asymmetry leads to a shift of the line position toward a higher binding energy (about half of the observed shift) as governed by the first moment rule.     

Ab initio theory of dynamical core-hole screening in graphite from x-ray absorption spectra

We have implemented the effect of dynamical core-hole screening, as given by Mahan, Nozières, and De Dominicis, in a first-principles based method and applied the theory to the x-ray absorption (XA) spectrum of graphite. It turns out that two of the conspicuous peaks of graphite are well described, both regarding the position, shape, and relative intensity, whereas one peak is absent in the theory. Only by incorporation of both excitonic and delocalized processes can a full account of the experimental spectrum be obtained theoretically, and we interpret the XA spectrum in graphite to be the result of a well screened and a poor screened process, much in the same way as is done for core level x-ray photoelectron spectroscopy.     

Optical absorption in asymmetric double quantum wells driven by two intense terahertz fields

Optical absorption is investigated for asymmetric double quantum wells driven by a resonant terahertz field and a varied terahertz field both polarized along the growth direction. Rich nonlinear dynamics of the replica peak and the Autler-Townes splitting of various dressed states are systematically studied in undoped asymmetric double quantum wells by taking account of multiple factors, such as the frequency of the varied terahertz field and the strength of the resonant terahertz field. Each electron subband splits into two dressed states when the resonant terahertz field is applied in the absence of the varied terahertz field, the optical absorption spectrum shows the first order Autler-Townes splitting of the electron subbands. When a varied terahertz field is added into the resonant system, the replica peak and the second order Autler-Townes splitting of the dressed states near the band edge respectively emerge when the varied terahertz field is non-resonant and resonant with these dressed states. When the strength of the resonant terahertz field is increased, the first order Autler-Townes double peaks and the replica peak in the optical absorption spectrum shift with the shifts of the dressed states. The presented results have potential applications in electro-optical devices.     

12C induced transfer reactions on 56Fe

Transfer reactions ⁵⁶Fe(¹²C, xN) have been investigated. Angular distributions of particles following elastic scattering, one neutron and one proton transfer reaction channels leading to low lying states in respective residual nuclei have been measured. These are analysed using the coupled reaction channel (CRC) formalism. Starting with a double folded real potential, the elastic scattering angular distribution is calculated using the computer code FRESCO. Inclusion of couplings to first excited states in both the target and the projectile already tends to describe the experimental elastic scattering distribution. Additional coupling of one neutron transfer reaction to first five excited states in ⁵⁵Fe and one proton transfer reaction to first three low lying states in ⁵⁷Co improves fit to the elastic scattering angular distribution. Further refinement in fit is brought about by addition of a weak imaginary potential to the complex potential calculated by ERESCO to simulate the absorption effects due to those channels whose coupling is not included explicitly. Such a potential describes the experimental angular distributions for elastic, one neutron and one proton transfer channels correctly in shape and magnitude without any arbitrary normalisation.