Orbital dependent coherence temperature and optical anisotropy of V2O3 quasiparticles.

We report on an orbital and temperature dependent study of the onset of coherent quasiparticles in V2O3 single crystal. By using polarized infrared spectroscopy we demonstrate that the electronic coherence temperature is strongly orbital dependent, being about 400 K for [Formula: see text] orbitals and 500 K for the [Formula: see text]. This suggests that V2O3 low energy electrodynamics can be described in terms of two electron liquids differently renormalized by electronic correlations.

Ultrafast evolution and transient phases of a prototype out-of-equilibrium Mott-Hubbard material.

The study of photoexcited strongly correlated materials is attracting growing interest since their rich phase diagram often translates into an equally rich out-of-equilibrium behaviour. With femtosecond optical pulses, electronic and lattice degrees of freedom can be transiently decoupled, giving the opportunity of stabilizing new states inaccessible by quasi-adiabatic pathways. Here we show that the prototype Mott-Hubbard material V2O3 presents a transient non-thermal phase developing immediately after ultrafast photoexcitation and lasting few picoseconds. For both the insulating and the metallic phase, the formation of the transient configuration is triggered by the excitation of electrons into the bonding a1g orbital, and is then stabilized by a lattice distortion characterized by a hardening of the A1g coherent phonon, in stark contrast with the softening observed upon heating. Our results show the importance of selective electron-lattice interplay for the ultrafast control of material parameters, and are relevant for the optical manipulation of strongly correlated systems.

Surface Effects on the Mott-Hubbard Transition in Archetypal V{2}O{3}.

We present an experimental and theoretical study exploring surface effects on the evolution of the metal-insulator transition in the model Mott-Hubbard compound Cr-doped V{2}O{3}. We find a microscopic domain formation that is clearly affected by the surface crystallographic orientation. Using scanning photoelectron microscopy and x-ray diffraction, we find that surface defects act as nucleation centers for the formation of domains at the temperature-induced isostructural transition and favor the formation of microscopic metallic regions. A density-functional theory plus dynamical mean-field theory study of different surface terminations shows that the surface reconstruction with excess vanadyl cations leads to doped, and hence more metallic, surface states, which explains our experimental observations.

Reflectivity enhancement in titanium by ultrafast XUV irradiation.

The study of highly photo-excited matter at solid state density is an emerging field of research, which is benefitting the development of free-electron-laser (FEL) technology. We report an extreme ultraviolet (XUV) reflectivity experiment from a titanium (Ti) sample irradiated with ultrafast seeded FEL pulses at variable incident photon fluence and frequency. Using a Drude formalism we relate the observed increase in reflectivity as a function of the excitation fluence to an increase in the plasma frequency, which allows us to estimate the free electron density in the excited sample. The extreme simplicity of the experimental setup makes the present approach potentially a valuable complementary tool to determine the average ionization state of the excited sample, information of primary relevance for understanding the physics of matter under extreme conditions.

Tuning a Schottky barrier in a photoexcited topological insulator with transient Dirac cone electron-hole asymmetry.

The advent of Dirac materials has made it possible to realize two-dimensional gases of relativistic fermions with unprecedented transport properties in condensed matter. Their photoconductive control with ultrafast light pulses is opening new perspectives for the transmission of current and information. Here we show that the interplay of surface and bulk transient carrier dynamics in a photoexcited topological insulator can control an essential parameter for photoconductivity-the balance between excess electrons and holes in the Dirac cone. This can result in a strongly out of equilibrium gas of hot relativistic fermions, characterized by a surprisingly long lifetime of more than 50 ps, and a simultaneous transient shift of chemical potential by as much as 100 meV. The unique properties of this transient Dirac cone make it possible to tune with ultrafast light pulses a relativistic nanoscale Schottky barrier, in a way that is impossible with conventional optoelectronic materials.

Circular dichroism and superdiffusive transport at the surface of BiTeI.

We investigate the electronic states of BiTeI after the optical pumping with circularly polarized photons. Our data show that photoexcited electrons reach an internal thermalization within 300 fs of the arrival of the pump pulse. Instead, the dichroic contrast generated by the circularly polarized light relaxes on a time scale shorter than 80 fs. This result implies that orbital and spin polarization created by the circular pump pulse rapidly decays via manybody interaction. The persistent dichroism at longer delay times is due to the helicity dependence of superdiffussive transport. We ascribe it to the lack of inversion symmetry in an electronic system far from equilibrium conditions.

Coherent phonon coupling to individual Bloch states in photoexcited bismuth.

We investigate the temporal evolution of the electronic states at the bismuth (111) surface by means of time- and angle-resolved photoelectron spectroscopy. The binding energy of bulklike bands oscillates with the frequency of the A(1g) phonon mode, whereas surface states are insensitive to the coherent displacement of the lattice. A strong dependence of the oscillation amplitude on the electronic wave vector is correctly reproduced by ab initio calculations of electron-phonon coupling. Besides these oscillations, all the electronic states also display a photoinduced shift towards higher binding energy whose dynamics follows the evolution of the electronic temperature.

Ultrafast surface carrier dynamics in the topological insulator Bi2Te3.

We discuss the ultrafast evolution of the surface electronic structure of the topological insulator Bi(2)Te(3) following a femtosecond laser excitation. Using time and angle-resolved photoelectron spectroscopy, we provide a direct real-time visualization of the transient carrier population of both the surface states and the bulk conduction band. We find that the thermalization of the surface states is initially determined by interband scattering from the bulk conduction band, lasting for about 0.5 ps; subsequently, few picoseconds are necessary for the Dirac cone nonequilibrium electrons to recover a Fermi-Dirac distribution, while their relaxation extends over more than 10 ps. The surface sensitivity of our measurements makes it possible to estimate the range of the bulk-surface interband scattering channel, indicating that the process is effective over a distance of 5 nm or less. This establishes a correlation between the nanoscale thickness of the bulk charge reservoir and the evolution of the ultrafast carrier dynamics in the surface Dirac cone.

Full characterization and optimization of a femtosecond ultraviolet laser source for time and angle-resolved photoemission on solid surfaces.

A novel experimental apparatus for time and angle-resolved photoemission on solid surfaces is presented. A 6.28 eV laser source operating at 250 kHz repetition rate is obtained by frequency mixing in nonlinear beta barium borate crystals. This UV light source has a high photon flux of 10(13) photons/s with relatively low number of photons/pulse so that Fermi surface mapping over a wide region of the Brillouin zone is possible while mitigating space charge effects. The UV source has been fully characterized spatially, spectrally, and temporally. Its potential for time and angle-resolved photoemission is demonstrated through Fermi surface mapping and photoexcited electron dynamics in Bismuth. True femtosecond time resolution <65 fs is obtained while the energy resolution of 70 meV appears to be mainly limited by the laser bandwidth.

Giant anisotropy of spin-orbit splitting at the bismuth surface.

We investigate the bismuth (111) surface by means of time and angle resolved photoelectron spectroscopy. The parallel detection of the surface states below and above the Fermi level reveals a giant anisotropy of the spin-orbit spitting. These strong deviations from the Rashba-like coupling cannot be treated in k·p perturbation theory. Instead, first principles calculations could accurately reproduce the experimental dispersion of the electronic states. Our analysis shows that the giant anisotropy of the spin-orbit splitting is due to a large out-of plane buckling of the spin and orbital texture.

High prevalence of hearing impairment in HIV-infected Peruvian children.

OBJECTIVES: To measure the prevalence and to identify risk factors of hearing impairment in human immunodeficiency virus-infected children living in Peru. STUDY DESIGN: Cross-sectional observational study. SETTING: Two public hospitals and 1 nonprofit center in Lima, Peru, between August 2009 and April 2010. SUBJECTS: A total of 139 HIV-infected children, ages 4 to 19 years. METHODS: Hearing impairment and otologic health were assessed with pure tone audiometry, tympanometry, and otoscopy. The primary outcome was hearing loss, defined as average threshold >25dB for 0.5, 1, 2, and 4 kHz, in one or both ears. Historical and socioeconomic information was obtained through parental survey and medical chart review. Statistical analysis included univariate analysis and multivariate logistic regression. RESULTS: Fifty-four (38.8%) of 139 children had hearing impairment. On multivariate analysis, risk factors included: tympanic membrane perforation (odds ratio [OR] 7.08; 95% confidence interval [CI], 1.65-30.5; P = .01), abnormal tympanometry (OR 2.71; 95% CI, 1.09-6.75; P = .03), cerebral infection (OR 11.6; 95% CI, 1.06-126; P = .05), seizures (OR 5.20; 95% CI, 1.21-22.4; P = .03), and CD4 cell count <500 cells/mm(3) (OR 3.53; 95% CI, 1.18-10.5; P = .02). CONCLUSIONS: The prevalence of hearing impairment in HIV-infected children in Lima, Peru was 38.8%. Middle ear disease, prior cerebral infection, and low CD4 cell count were significantly associated with hearing impairment. The high prevalence of hearing impairment emphasizes the need for periodic hearing assessment in the routine clinical care of HIV-infected children.

A microscopic view on the Mott transition in chromium-doped V(2)O(3).

V(2)O(3) is the prototype system for the Mott transition, one of the most fundamental phenomena of electronic correlation. Temperature, doping or pressure induce a metal-to-insulator transition (MIT) between a paramagnetic metal (PM) and a paramagnetic insulator. This or related MITs have a high technological potential, among others, for intelligent windows and field effect transistors. However the spatial scale on which such transitions develop is not known in spite of their importance for research and applications. Here we unveil for the first time the MIT in Cr-doped V(2)O(3) with submicron lateral resolution: with decreasing temperature, microscopic domains become metallic and coexist with an insulating background. This explains why the associated PM phase is actually a poor metal. The phase separation can be associated with a thermodynamic instability near the transition. This instability is reduced by pressure, that promotes a genuine Mott transition to an eventually homogeneous metallic state.

Significant reduction of electronic correlations upon isovalent Ru substitution of BaFe2As2.

We investigate Ba(Fe0.65Ru0.35)2As2, a compound in which superconductivity appears at the expense of magnetism, by transport measurements and angle resolved photoemission spectroscopy. By resolving the different Fermi surface pockets and deducing from their volumes the number of hole and electron carriers, we show that Ru induces neither hole nor electron doping. However, the Fermi surface pockets are about twice larger than in BaFe2As2. A change of sign of the Hall coefficient with decreasing temperature evidences the contribution of both carriers to the transport. Fermi velocities increase significantly with respect to BaFe2As2, suggesting a reduction of correlation effects.

Inequivalent routes across the Mott transition in V2O3 explored by X-ray absorption.

The changes in the electronic structure of V2O3 across the metal-insulator transition induced by temperature, doping, and pressure are identified using high resolution x-ray absorption spectroscopy at the V pre-K edge. Contrary to what has been taken for granted so far, the metallic phase reached under pressure is shown to differ from the one obtained by changing doping or temperature. Using a novel computational scheme, we relate this effect to the role and occupancy of the a{1g} orbitals. This finding unveils the inequivalence of different routes across the Mott transition in V2O3.

Quasiparticles at the Mott transition in V2O3: wave vector dependence and surface attenuation.

We present an angle resolved photoemission study of V2O3, a prototype system for the observation of Mott transitions in correlated materials. We show that the spectral features corresponding to the quasiparticle peak in the metallic phase present a marked wave vector dependence, with a stronger intensity along the GammaZ direction. The analysis of their intensity for different probing depths shows the existence of a characteristic length scale for the attenuation of coherent electronic excitations at the surface. This length scale, which is larger than the thickness of the surface region as normally defined for noncorrelated electronic states, is found to increase when approaching the Mott transition. These results are in agreement with the behavior of quasiparticles at surfaces as predicted by Borghi et al.

Potentiometric-spectroscopic evaluation of metal-ion complexes by humic fractions extracted from corn tissue.

Humic fraction (HF) functional group-type and content are expected to depend on molecular size, which in turn, is expected to influence formation of heavy-metal complexes. In this study, corn (Zea mays L.) stalks and leaves were decomposed for an 8-month period to produce water-soluble humic substances. These substances were separated into three water-soluble fractions, HF1, HF2 and HF3, from highest to lowest relative molecular size. Functional group determination showed that carboxylic, and phenolic OH acidity increased as relative molecular size of humic fractions decreased. We also observed decreasing C/O ratios from larger to smaller corn tissue-derived humic fractions, whereas N/C and H/C ratios remained relatively unaffected. Furthermore, using potentiometric titration and FTIR spectroscopy we studied formation of Ca2+-, Cd2+-, and Cu2+-humic fraction complexes and how they were affected by pH and molecular size. We determined that metal-humic complexes exhibited at least two types of functional group-sites with respect to Ca2+, Cd2+, and Cu2+ complexation. Strength of metal-ion humic complexes followed the order Cu2+ > Cd2+ > Ca2+ and was affected by pH, especially for low affinity sites. Carboxylic groups were most likely the dominant group-sites involved in complex formation. Magnitude of the metal-humic formation constants in the logarithmic form at the lowest equilibrium metal-ion concentration, under the various pH values tested, varied from 5.39 to 5.90 for Ca2+, 5.36 to 6.01 for Cd2+, and 6.93 to 7.71 for Cu2+. Furthermore, the formation constants appeared to be positively influenced by decreasing molecular size of water-soluble humic fraction, and increasing pH. However, our molecular spectra showed that the pKa of corn humic fractions increased with decreasing relative molecular size and that Cu2+ was more covalently bonded by humic fractions than were Ca2+ and Cd2+, and the nature of the covalent bond character was independent of pH.

Stability of Ca2+-, Cd2+-, and Cu2+-illite complexes.

In this study, using ion selective electrode techniques, we investigated the influence of pH on metal-ion, Ca2+, Cd2+, and Cu2+, adsorption by Fithian illite. The results showed that Fithian illite exhibited at least two types of metal-ion adsorption sites, high and low strength with the strength of metal-ion-illite surface complexes following the order of Cu2+ > Cd2+ > Ca2+ (strongest to weakest acids) at any of the pH values tested. The ability of metal-ions to form complexes with illite surfaces was affected by type of metal-ions and pH, especially for low metal-ion affinity sites. These sites formed stronger metal-ion complexes at high pH than at low pH, which implicated clay edge sites and indicated that H+ competed with metal-ions for available complexation sites. The data also showed that illite functional groups forming the strongest metal-ion complex did not appear to be pH-sensitive, which implicated wedge siloxane cavities or extremely low pKa clay-edge OH functional groups, but the total number of such sites were very small. The magnitude of the metal-ion-illite stability constants, as metal-ion solution concentration approached zero, on a log-scale, varied from 3.52 to 4.21 for Ca2+, 4.38 to 5.18 for Cd2+, and from 5.23 to 5.83 for Cu2+. These constants were approximately an order of magnitude smaller than those representing illite with sorbed humic fractions. The above results along with the results from our previous studies imply that metal-ion mobility and bioavailability would be affected by soil mineral surface properties, which would be significantly influenced by sorption of humic substances.

Spectroscopic Techniques using Synchrotron Radiation and Free-Electron and Conventional Lasers.

Considerable progress in the investigation of the electronic and vibrational properties of atoms, molecules, materials, surfaces and interfaces has been achieved by combining different photon sources of complementary characteristics. In this paper some experimental results obtained recently at LURE by using two synchronized sources, such as the IR free-electron laser (FEL) CLIO, the VUV storage ring FEL, synchrotron radiation and table lasers, are presented. Using CLIO synchronized with a YAG laser allows the investigation of the vibrational properties of adsorbed species by the non-linear optical technique of visible-IR sum (difference) frequency generation, as shown for the adsorption of hydrogen on platinum in the electrochemical environment. The second result reported here relates to the study of the intersubband stimulated emission in GaAs/GaAlAs quantum wells by pump-probe experiments using the two-colour configuration of CLIO. The combination of a mode-locked Ar(+) laser and synchrotron radiation has been used for investigations in a pump-probe arrangement of the ionization of Xe atoms via the resonant state Xe* 5p(5)5d [3/2](1). The final example is a time-resolved core-level spectroscopy study of photoexcited Si(111) 2 x 1 surfaces by using a combination of the naturally synchronized UV storage ring laser and synchrotron radiation.

A novel approach to the control of experimental environments: the ESCA microscopy data-acquisition system at ELETTRA.

An efficient control system is today one of the key points for the successful operation of a beamline at third-generation synchrotron radiation sources. The high cost of these ultra-bright light sources and the limited beam time requires effective instrument handling in order to reduce any waste of measurement time. The basic requirements for such control software are reliability, user-friendliness, modularity, upgradability, as well as the capability of integrating a horde of different instruments, commercial tools and independent pre-existing systems in a possibly distributed environment. A novel approach has been adopted to implement the data-acquisition system of the ESCA microscopy beamline at ELETTRA. The system is based on YASB, a software bus, i.e. an underlying control model to coordinate information exchanges and networking software to implement that model. This 'middleware' allows the developer to model applications as a set of interacting agents, i.e. independent software machines. Agents can be implemented using different programming languages and be executed on heterogeneous operating environments, which promotes an effective collaboration between software engineers and experimental physicists.