A study of many-body phenomena in metal nanoclusters (Au, Cu) close to their transition to the nonmetallic state

The results of a study of many-body phenomena in gold and copper nanoclusters are presented. The measured conductivity as a function of nanocluster height h was found to have a minimum at h ≈ 0.6 nm. Conductivity was local in character at nanocluster sizes l ≤ l _c ≈ 2.5 nm. Changes in core hole screening and an anomalous increase in the Anderson singularity index α in gold and copper nanoclusters could be caused by changes in permittivity from metallic (? → ∞) to nonmetallic (? ∝ l ²). The many-body phenomenon characteristics observed in the X-ray photoelectron and tunnel spectra of gold and copper nanoclusters as the size of the nanoclusters changed led us to suggest changes in the band structure of the nanoclusters and, therefore, their possible transition from the metallic to nonmetallic state.     

Ab initio theory and calculations of X-ray spectra

There has been dramatic progress in recent years both in the calculation and interpretation of various x-ray spectroscopies. However, current theoretical calculations often use a number of simplified models to account for many-body effects, in lieu of first principles calculations. In an effort to overcome these limitations we describe in this article a number of recent advances in theory and in theoretical codes which offer the prospect of parameter free calculations that include the dominant many-body effects. These advances are based on ab initio calculations of the dielectric and vibrational response of a system. Calculations of the dielectric function over a broad spectrum yield system dependent self-energies and mean-free paths, as well as intrinsic losses due to multi-electron excitations. Calculations of the dynamical matrix yield vibrational damping in terms of multiple-scattering Debye–Waller factors. Our ab initio methods for determining these many-body effects have led to new, improved, and broadly applicable x-ray and electron spectroscopy codes. To cite this article: J.J. Rehr et al., C. R. Physique 10 (2009).     

Spatial-dispersion induced birefringence in cubic crystals: CuBr and CuI

A natural birefringence in single crystals of copper halides is observed and measured in the exciton part of the spectrum. This intrinsic birefringence is due to the spatial dispersion of the dielectric constant ?(ω, q). Its spectral dependence and strong enhancement near the energy gap can be explained only, if we take account of the strong excitonic contribution in these compounds. This effect is related to the valence band anisotropy (warning) and thus allows a direct determination of the Luttinger band parameters | γ₂ - γ₃ | for these compounds.     

A novel peroxy radical species formed in Na+/Y zeolites upon interaction with hydrogen peroxide: a CW-EPR study

A peroxy radical species is generated in the framework of Na⁺/Y zeolites, upon treatment with a hydrogen peroxide solution, drying and evacuation of the solid at 420 K. The amount of the species increases upon increasing the temperature of the treatment under vacuum up 570 K. The EPR spectrum of the species at 77 K is characterized by anisotropicg tensor (g ₁=2.059,g ₂=2.010,g ₃=2.007). Upon increasing the recording temperature the spectrum undergoes a dramatic evolution indicating the onset of motional phenomena. This dynamic behavior together with the values of theg tensor components and the high thermal stability of the species allow one to distinguish the observed species from the more common superoxide radical ion produced by oxygen adsorption on Na⁺/Y zeolites treated with metallic sodium.     

From random to self-avoiding walks

A brief review will be given of the current situation in the theory of self-avoiding walks (SAWs). The Domb-Joyce model first introduced in 1972 consists of a random walk on a lattice in which eachN step configuration has a weighting factor Π _i=0 ^N?2 Π_j=i+2/N(1?ωδ_ij). Herei andj are the lattice sites occupied by the ith and jth points of the walk. When ω=0 the model reduces to a standard random walk, and when ω=1 it is a self-avoiding walk. The universality hypothesis of critical phenomena will be used to conjecture the behavior of the model as a function ofω for largeN. The implications for the theory of dilute polymer solutions will be indicated.     

Nonlinear electron transport in Si δ-doped GaAs

In this paper we report abnormal non-ohmic behaviour observed in Si δ-doped GaAs. We have performed measurements in Hall bar and Van der Pauw geometries in which electron transport phenomena can be studiekd by looking into the dependence of the device resistance R_xx on the applied current I or input power per electron, P. Transport of electrons in single Si δ-doped layers in GaAs, grown by MOCVD, in the linear and non-linear response regimes was studied. Our experimental results show that: i) R_xx dramatically decreases with increasingI (P) when sample current (input power) is larger than a critical value I_c (P_c); ii) I_c increases with electron density (Si δ-doping concentration); and iii) the decrease in R_xx with increasing I in the non-linear response regime can be observed both at zero and high magnetic fields over a wide temperature range. When R_xx is plotted as a function of the power loss rate per electron (P) the values of the critical power (P_c) for different samples are roughly the same. We suggest that redistribution of the ionised donors in the sample occurring when I >I_c takes the major responsibility for the observed abnormal phenomena.     

Momentum-structure of remnant Mott-gap in prototype hole doped cuprates

Momentum dependent charge excitation of 2D cuprate class La_2−xSr_xCuO₄ with different hole-doping levels (x) is measured using high resolution resonant inelastic X-ray scattering. Although a low-energy continuum is built up with doping, a remnant excitation gap behavior continues to exist even in highly doped metallic phase which we have studied in some detail. The excitation of the Mott gap becomes less dispersive with the increase of doping level and suggests a many-body coupling between charge fluctuation and magnetic character of the lattice. The results can be described within the framework of t-t′-t″-U model.     

Ellipsometry study of interband transitions in TlGaS2xSe2(1−x) mixed crystals (0≤x≤1)

In this paper, the spectroscopic ellipsometry measurements on TlGaS_2xSe_2(1?x) mixed crystals (0≤x≤1) were carried out on the layer-plane (001) surfaces with light polarization E⊥c^? in the 1.2–6.2 eV spectral range at room temperature. The real and imaginary parts of the dielectric function, refractive index and extinction coefficient were calculated from ellipsometric data using the ambient-substrate optical model. The critical point energies in the above-band gap energy range have been obtained from the second derivative spectra of the dielectric function. Particularly for TlGaSe₂ crystals, the determined critical point energies were assigned tentatively to interband transitions using the available electronic energy band structure. The effect of the isomorphic anion substitution (sulfur for selenium) on critical point energies in TlGaS_2xSe_2(1?x) mixed crystals was established.     

Probing spin physics in the quantum Hall regime by heat capacity and magnetotransport measurements

We review recent heat capacity and magnetotransport experiments on GaAs/AlGaAs heterostructures containing multilayer two-dimensional electron systems (2DESs) in the quantum Hall regime. Emphasis in this article is on the study of the heat capacity near Landau level filling factor ν=1. We also present a detailed survey of the development of the quantum Hall effect in tilted-magnetic fields for ν≲2. Among the novel phenomena we address is the strong coupling between the nuclear spins and the electrons associated with the spin phase transitions of the 2DES at ν=4/3 and near ν=1. To cite this article: S. Melinte et al., C. R. Physique 3 (2002) 667–676.     

Ionic displacement caused by electronic excitations

Electronic excitations are often accompanied by displacement of the ions from their ground-state equilibrium positions. This leads to line broadening of optical spectra, Stokes shifts, conformational changes, and photoinduced reactions. Here we discuss approaches to these features within ab-initio methods, in particular within many-body perturbation theory. A number of various systems, including molecules, point defects, polymers, and surfaces, are discussed to illustrate issues like localization and self-trapping that are relevant for a detailed understanding of the interrelation between excited states and geometrical structure. To cite this article: M. Rohlfing, C. R. Physique 10 (2009).     

Spin susceptibility divergence in high-temperature superconductors

Neutron scattering experiments at low frequency reveal susceptibility peaks in La_2−xSr_xCuO₄ which diverge as the temperature is lowered toward the superconducting transition. This divergence at a nesting momentum stands out from the conventional Pauli susceptibility of this cuprate at long wavelengths. We explain the peak singularity by calculating many-body Coulomb correlations which originate from Fermi surface nesting and dominant vertex corrections. We sum the leading singularities using the parquet method and find that the susceptibility diverges as T^−α, where α depends on the Coulomb interaction. Our theory also explains a similar susceptibility surge in the metallic V₂O₃.     

Anomalous behavior of the surface tension at the interface of the metallic and insulating phases in the vicinity of the metal-insulator phase transition in a magnetic field

Mean-field equations describing the metal-insulator (MI) transition are formulated. They involve two coupled order parameters characterizing this transition: (i) a scalar order parameter describing the density change accompanying the transition from the insulating state to the metallic one and (ii) an order parameter (a two-component vector) describing the electron density in the metallic or semimetallic phase affected by the applied magnetic field. Two components of this vector correspond to different possible spin states of electrons in the applied magnetic field. The transition in the density of metallic and insulating phases being a first order phase transition is treated in terms of the Cahn-Hilliard-type gradient expansion. The transition in the electron density is a second order phase described by the Ginzburg-Landau-type functional. The coupling of these two parameters is described by the term linearly dependent on the electron density n in the metal with the proportionality factor being a function of the density of the metallic phase. The derived equations are solved in the case of the MI interface in the presence of both parallel and perpendicular uniform magnetic fields. The calculated surface tension Σ_mi between the metallic and insulating phases has a singular behavior. In the limit of zero electron density n ? 0, Σ_mi ～ n ^3/2. Near the MI transition point T _c(h) in the applied magnetic field, Σ_mi ～ [T - T _c(h)]^3/2. The singular behavior of the surface tension at the MI interface results in the clearly pronounced hysteresis accompanying the transition from the insulating to metallic state and vice versa.     

Surface plasmon THz waves on gratings

Because of their long propagation length at a metal surface in the far infrared, surface plasmons make potentially feasible the design and realization of 2D integrated terahertz systems over a metallic substrate. The coupling of a terahertz beam to the surface plasmon wave is very efficiently achieved by diffraction gratings engraved at the metal surface. In this article, we present a review of some recent works we performed in view of characterizing this coupling phenomenon. The analysis of the experimental data supplied by terahertz time-domain spectroscopy allows us to point out the main parameters that govern this diffraction process and the propagation of a surface plasmon over a flat or corrugated metal surface. To cite this article: M. Nazarov et al., C. R. Physique 9 (2008).     

Electro-absorption sampling at terahertz frequencies in III-V semiconductors

We review recent advances in the development of a new sampling technique for ultra high-speed electrical signals. It is based on the electro-absorption phenomena in semiconductors (Franz–Keldysh effect). We demonstrate that it is usable up to the terahertz range. The theory is exposed and we show two practical set-ups. The first uses the semiconductor substrate (internal sampling). The second uses a small semiconductor probe bonded on the circuit (external sampling). In this last case, the theoretical temporal resolution is about 200 fs. In practice, we measure a risetime of about 500 fs with 60 dB of dynamic range. To cite this article: J.-F. Lampin et al., C. R. Physique 9 (2008).     

Ab-initio optical properties and dielectric response of open-shell spinel zinc ferrite

In the present work, we predict the optical properties and the dielectric response spectrum of the spinel zinc ferrite Zn₂Fe₄O₈, and show in particular the impact of many-body effects on the absorption spectrum, using advanced many-body perturbation approach. The excitonic effects remarkably redistribute the spectral weights causing a red-shift of 1.6 eV of the maximum of the independent particle G ₀ W ₀?(IP-G ₀ W ₀) towards the electron-hole affected spectrum. The excitation spectrum of the zinc ferrite exhibits a low lying doubly degenerated bound dark exciton at 1.84 eV with a fully symmetric excited-state density, and a narrow optical gap setting on at 1.93 eV. We further analyse the electronic transitions and exciton density distributions giving insights to the nature of excitations. The dielectric response of Zn₂Fe₄O₈ shows a particular sensitivity to the excitations higher than the electronic band gap, however it abruptly becomes passive to the incoming electro-magnetic wave and propagates to the negative regions at high energy regimes.     

Dynamical Aspects of Mean Field Plane Rotators and the Kuramoto Model

The Kuramoto model has been introduced in order to describe synchronization phenomena observed in groups of cells, individuals, circuits, etc. We look at the Kuramoto model with white noise forces: in mathematical terms it is a set of N oscillators, each driven by an independent Brownian motion with a constant drift, that is each oscillator has its own frequency, which, in general, changes from one oscillator to another (these frequencies are usually taken to be random and they may be viewed as a quenched disorder). The interactions between oscillators are of long range type (mean field). We review some results on the Kuramoto model from a statistical mechanics standpoint: we give in particular necessary and sufficient conditions for reversibility and we point out a formal analogy, in the N→∞ limit, with local mean field models with conservative dynamics (an analogy that is exploited to identify in particular a Lyapunov functional in the reversible set-up). We then focus on the reversible Kuramoto model with sinusoidal interactions in the N→∞ limit and analyze the stability of the non-trivial stationary profiles arising when the interaction parameter K is larger than its critical value K _c . We provide an analysis of the linear operator describing the time evolution in a neighborhood of the synchronized profile: we exhibit a Hilbert space in which this operator has a self-adjoint extension and we establish, as our main result, a spectral gap inequality for every K>K _c .     

Sonochemical effect on two new Ruthenium(II) complexes with ligand (E)-N-((6-bromopyridin-2-yl)methylene)-4-(methylthio)aniline precursors for synthesis of RuO2 nanoparticles

Two novel Ru(II) complexes [(η⁶-p-cymene)RuCl(L2)]PF₆ (R2) and [(η⁶-C₆H₆)RuCl(L2)]PF₆ (R4), with ligand (E)-N-((6-bromopyridin-2-yl)methylene)-4-(methylthio)aniline (L2), were synthesized and characterized by elemental analysis, ¹H NMR, ¹³C NMR and IR spectroscopy. Based on X-ray crystallography studies, complexes R2 and R4 have coordination environments with formulated (η⁶-p-cymene)Ru(N₂Cl) and (η⁶-C₆H₆)Ru(N₂Cl), respectively. The thermal stabilities of compounds R2 and R4 were studied by thermal gravimetric (TG) and differential scanning calorimetry (DSC). Thermal decomposition of these complexes was at 280 °C and 260 °C under air atmosphere respectively. The interaction of these complexes with calf thymus DNA (CT-DNA) was explored through electronic absorption spectra, fluorescence and redox behavior studies. The results showed that the complexes bind to CT-DNA with electrostatic interactions. Nanoparticles of RuO₂ were prepared by calcination of R2 and R4. Also the role of the ultrasound waves on the characteristics of the RuO₂ nanoparticles was studied. The nanoparticles were characterized by IR spectroscopy and X-ray diffraction (XRD). Also size and morphology of nanoparticles were studied by scanning electron microscopy (SEM).     

Longitudinal relaxation spectra of the transverse Ising model close to Tc

The correlative effects of the nature of the interaction and of the method of calculation on the shape of the longitudinal relaxation function (LRF) for the transverse Ising model are analysed. The LRF is calculated in two ways: (i) its continued fraction representation within the three pole approximation (TPA); and (ii) the resolution of kinetic equations derived for the correlation functions beyond the random phase approximation (RPA). The effects of the nature of the interaction on the LRF spectral characteristics are investigated using an interaction made of three variable contributions: uniaxial dipolar, isotropic infinite range and anisotropic nearest-neighbour interactions. Contrary to the TPA, the kinetic-equation-method (KEM) leads to LRF's exhibiting a three peak structure for every q-value except q = 0 (q = 0_⊥ if the interaction is of dipolar nature) whatever the interaction. The approximations underlying both methods are specified and discussed. Comments on recent neutron scattering experiments on Li Tb_pY_1-pF₄ by Youngblood et al. are made.     

Measurement of Δ1J(199Hg, 31P) in [HgPCy3(OAc)2]2 and relativistic ZORA DFT investigations of mercury–phosphorus coupling tensors

Using ³¹P solid-state NMR spectroscopy, anisotropy in the indirect ¹⁹⁹Hg-³¹P spin–spin coupling tensor (ΔJ) for powdered [HgPCy₃(OAc)₂]₂ (1) has been measured as 4700±300 Hz. Zeroth-order regular approximation (ZORA) density functional theory (DFT) calculations, including scalar and spin-orbit relativistic effects, performed on 1 and a series of other related compounds show that ΔJ(¹⁹⁹Hg, ³¹P) arises entirely from the ZORA Fermi-contact–spin-dipolar cross term. The calculations validate assumptions made in the spectral analysis of 1 and in previous determinations of ΔJ in powder samples, namely that J is axially symmetric and shares its principal axis system with the direct dipolar coupling tensor (D). Agreement between experiment and theory for various ¹⁹⁹Hg, ³¹P spin–spin coupling anisotropies is reasonable; however, experimental values of ¹J(¹⁹⁹Hg, ³¹P)_iso are significantly underestimated by the calculations. The most important improvements in the agreement were obtained as a result of including more of the crystal lattice in the model used for the calculations, e.g., a change of 43% was noted for ¹J(¹⁹⁹Hg, ³¹P)_iso in [HgPPh₃(NO₃)₂]₂ depending on whether the two or three nearest nitrate ions are included in the model. Finally, we have written a computer program to simulate the effects of non-axial symmetry in J and of non-coincidence of the J and D on powder NMR spectra. Simulations clearly show that both of these effects have a pronounced impact on the ³¹P NMR spectrum of ¹⁹⁹Hg–³¹P spin pairs, suggesting that the effects should be observable experimentally if a suitable compound can be identified.