Low frequency surface resonance modes in electron energy loss spectroscopy

Electron energy loss spectroscopy has proved a powerful probe of vibrational modes of a wide variety of adsorbed species. Here the primary focus has been on modes with frequency well above the maximum phonon frequency of the substrate. Examples are internal vibration modes of adsorbed molecules, possibly shifted significantly in frequency from their gas phase analogues, and high frequency vibrations of an adsorbed molecule or atom against the substrate. Recent experiments explore features in the energy loss spectrum with frequency below the maximum phonon frequency of the substrate, for ordered overlayers of atoms adsorbed on low index metal surfaces. We shall summarize our theoretical studies of such spectra for several adsorbate/substrate combinations, with emphasis oh the physical origin of the features which appear in the calculations. We obtain a good account of the existing data, within the framework of a rather simple lattice dynamical model, and the calculations show that the features which appear are quite sensitive to the symmetry of the adsorption sits, and other details of the surface geometry. We shall illustrate this with several specific examples.     

Energy Transfer and Avalanche Upconversion of NdxY1-xVO4 Nanocrystals

We explore Nd3＋ concentration and excitation power dependences of the avalanche upconversion of NdxY1-xVO4 （x=0-1） nanocrystals with uniform size and shape. The avalanche threshold power caused by the near-resonant energy transfer between 4F5/2→4I13/2 and 4F5/2→2G9/2 significantly decreases as the Nd3＋ concentration increases. The off-resonant energy transfer between 4F5/2→4I13/2 and 4F5/2→4G11/2 in the strong excitation regime leads to apparent broadening on the blue-side of the upconversion spectrum of NdVO4 nanocrystals.     

Low frequency dielectric spectroscopy of the Peierls-Mott insulating state in the deuterated copper-DCNQI systems

We report a detailed characterization of an unique 3-fold commensurate insulating state in single crystals of the organic – inorganic d hybrid Cu(DMe-DCNQI)₂ systems with deuterated and partially deuterated DCNQI ring, by means of low-frequency dielectric spectroscopy. A broad relaxation mode of strength centred at kHz is observed in the hysteresis temperature region in which the insulating phase coexists with metallic islands. At lower temperatures, outside the nucleation range, the relaxation narrows, approaching a Debye-like form for an overdamped response of a system with a single degree of freedom. Both, the relaxation strength and the mean relaxation time () are much larger than that expected for single-particle excitations. These features suggest the origin of the dielectric relaxation as an intrinsic property of the N = 3 charge density wave state. Received 1 December 1999 and Received in final form 5 April 2000     

Ground state of the quasi-1D correlated electronic system BaVS3

In this paper we review the salient features of the different instabilities exhibited by the quasi-1D system BaVS₃ and show that there is a subtle interplay between the different phases stabilized. The analysis of the Peierls instability shows that the mobile dz² electrons are more localized than calculated because of their strong correlation with the localized e(t_2g) electrons. The complex AF magnetic structure of BaVS₃ incorporates the magnetization of the e(t_2g) electrons with the Peierls pairing of the dz² electrons into magnetic singlets. Finally, we propose that the zig-zag disorder remaining after an incomplete orthorhombic phase transition could change the sign of the magnetic coupling and thus help to stabilize the canted ferromagnetism observed in non stoichiometric BaVS_3−δ and Sr and Ba substituted compounds.     

Low frequency four-wave mixing spectroscopy of biopolymer hydration layers in aqueous solutions

Four-wave mixing (FWM) spectroscopy has been applied to detection of H₂O₂ molecules rotational resonances in both DNA and denatured DNA aqueous solutions in the range ±100 cm⁻¹. A considerable growth of rotational lines intensity of H₂O and H₂O₂ has been observed in comparison with distilled water. This fact was interpreted as an exhibition of specific property of a hydration layer formation at DNA/water and denatured DNA/water interfaces. The fitting of four-wave mixing spectra shows the increasing of the H₂O₂ rotational line’s amplitude by a factor of ∼3 in DNA solutions due to denaturizing. The shifting of FWM Brillouin resonances in opposite way in protein solution and SWNT (single wall carbon nanotube) suspension to comparison with water was observed and discussed.     

Low frequency dielectric spectroscopy of two room temperature chiral liquid crystal mixtures

Dielectric spectroscopy of two room temperature chiral liquid crystal mixtures (W-96 and W-97) have been carried out in the frequency range of 100?mHz–10?MHz. Low frequency dielectric relaxation modes corresponding to collective behavior of molecules (Goldstone- and soft-modes) in the SmC* phase have been found to be masked by the ionic conductance. Two slow modes of dielectric relaxation due to the ionic conductance have been detected (below 15?Hz) in planar-aligned samples. It has been observed that the effect of ionic conductance decreases with the number of thermal annealing cycles on the materials. With large number of thermal annealing cycles it has been possible to wipe out the effects of ionic conductance and then to detect other weak modes of dielectric relaxation which are otherwise masked.     

Low barrier methyl rotation in 3-pentyn-1-ol as observed by microwave spectroscopy

ABSTRACT

The rotational spectrum of 3-pentyn-1-ol, CH₃?C≡C?CH₂CH₂OH, was measured using a molecular beam Fourier transform microwave spectrometer operating in the frequency range from 2 to 26.5 GHz. A two-dimensional potential energy surface was calculated at the MP2/6-311++G(d,p) level of theory for a conformational analysis, yielding five conformers. The most stable conformer exhibits C₁ symmetry and was assigned in the spectrum by comparison with the results from quantum chemical calculations. The barrier to internal rotation of the propynyl methyl group CH₃?C≡C? was found to be only 9.4552(94) cm^?1. Molecular parameters and internal rotation parameters could be accurately determined using the program xiam and belgi-C₁. The internal rotation barrier was compared with those of other molecules containing a propynyl methyl group.     

Fano resonance in 3D system of metallic nanoparticles

Computations for the Fano resonance in a 3D system of identical prolate metallic nanospheroids located at the vertices of a regular tetrahedron are presented. The long axis of one of the spheroids is oriented along the symmetry axis of the third order of the tetrahedron (Z-axis), and the long axes of the remaining three spheroids lie in the orthogonal plane forming angles 2π/3 with each other. The polarization vector of the incident light wave oscillates along the Z-axis and directly excites plasmon oscillations in only one spheroid. The results of computations are given, which show the strong nonuniformity of energy distribution between spheroids for various orientations of spheroids perpendicular to the Z-axis.     

Three-dimensional correlated accordion NMR spectroscopy of proteins

A major step toward the protein structure determination by nuclear magnetic resonance (NMR) spectroscopy is the assignment of multidimensional NMR signals that provide through-bond and through-space inter-atomic correlations. Ambiguities often occur during the assignment process due to resonance degeneracy, which challenges high resolution and larger size protein structure determination. Here, we present a method that will significantly improve the efficiency and accuracy of the NMR signal assignment. The method is based on a correlated accordion principle that, when incorporated into conventional three-dimensional (3D) heteronuclear NMR experiments, allows the retrieval of additional frequency correlation information at high resolution. We show that 3D spectra derived from this method are as effective as the impractical high resolution four-dimensional (4D) spectra with substantially reduced signal ambiguity as compared to their conventional counterparts. The approach promises increased accuracy and size of protein structures determined by NMR.     

Submillimeter spectroscopy of materials with correlated electrons

We describe the techniques which permit one to measure the electrodynamic response of conductive materials in the millimeter and submillimeter wavelength ranges. Results of studying dielectric spectra of a number of materials whose properties are determined by electron correlations, e.g., superconductors, one-dimensional conductors, and compounds with heavy fermions, are presented.     

Low frequency electroluminescence in ferroelectric BaTiO3 single crystals

Electroluminescence has been studied in ferroelectric BaTiO₃ single crystals. The variation of EL with potential temperature and d.c. biasing suggests the existence of complex surface charge layer on the surface of these crystals. The mode of growth of EL pulses reveals the nature of these layers.     

Cavity ring-down spectroscopy of metallic gold nanoparticles

The optical properties of supported gold nanoparticles with sizes of 1.3 nm, 1.6 nm, 2.5 nm, and 2.9 nm have been studies by using cavity ring-down spectroscopy in the photon energy range between 1.8 eV and 3.0 eV. The obtained results show the possibility to obtain optical information of nanoassembled materials with high sensitivity. The experimental findings are compared to calculations using Mie-Drude theory. Whereas the broadening of the surface plasmon resonance with decreasing size is well described by this model, the observed blue-shift of the surface plasmon resonance contradicts the predictions of the Mie-Drude theory. The latter effect can be explained by the presence of a skin region with decreased polarizability typical for coinage metal particles. Furthermore, it is found that the supported gold nanoparticles are robust under ambient conditions, an important issue when using these materials for optical applications.     

W-band 1/3 frequency dividers

In this article the theoretical and experimental performances of a Gunn harmonically synchronized frequency divider are presented. The results show that such a divider has a 96-32GHz division, with 15-mW output power over the operating band greater than 1400MHz at 10-mW input power level.     

High resolution Auger electron spectroscopy of metallic copper

Part of the LMM Auger spectrum from metallic copper has been studied in a high resolution X-ray photoelectron spectrometer. Fine structure not earlier reported has been observed. The main L₃M_4,5M_4,5 peak is very narrow, 1.0 eV, although the valence band is involved in the transition. The agreement between experimental and calculated Auger electron energies is very good. Since fine structure is found to be an intrinsic property in Auger spectra the interpretation of “satellite” peaks as due to electron—plasmon interactions should be used with care. The L₃M_4,5M_4,5 peak is very sensitive to the copper surface conditions. Surface oxygen affects the peak in a characteristic way.     

Ultrafast IR and THz spectroscopy of photo-induced insulator to metal transition in highly correlated organic system

Photo-induced insulator to metal transitions (PIMT) in quarter filled layered organic conductors ET [bis(ethylenedithio)tetrathiafulvalene]-based salts α-(ET)₂I₃, θ-(ET)₂RbZn(SCN)₄, and κ-(d-ET)₂Cu[N(CN)₂Br] were investigated using ultrafast spectroscopy in the near, mid-infrared and terahertz (THz) regions. In charge ordered salts α-(ET)₂I₃ and θ-(ET)₂RbZn(SCN)₄, an immediate (<30 fs) generation of a microscopic metallic state is driven by the electronic process. Subsequently, condensation of the microscopic metallic domain to the macroscopic scale is accompanied by a small molecular rearrangement in α-(ET)₂I₃. However, in θ-(ET)₂RbZn(SCN)₄, a large structural difference between the insulator and metallic phases prevents stabilization of the macroscopic metallic state. In a dimer Mott insulator κ-(d-ET)₂Cu[N(CN)₂Br], photo-generation of the metallic state shows a finite rise time of ca. 1 ps, which is attributable to the photo-induced change of on-site Coulomb energy on each dimer (U_dim) through dimeric molecular rearrangement. Thus, the ultrafast dynamics of PIMT depend strongly on the molecular arrangement in the layer of ET salts.     

Low frequency fluctuations of laser beam intensity run through the system of cavitation water clusters

Experiments on water cavitation in ultrasonic field have been carried out. Low frequency fluctuations of the intensity of laser beam run through the cavitation area have been studied. Experiments have proved presence of low-frequency random fluctuations with frequency dependence of power spectra, S ∼ 1/f ^α where the exponent α ranged within 0.8 ≤ α ≤ 1.2. From experimental realizations, large-scale low frequency pulsations characterized by scale invariance, which duration is distributed according to the power law, have been distinguished. The results are explained on the basis of mathematical model for the rise of scale invariant fluctuations with 1/f ^α power spectrum in the system of two nonlinear stochastic differential equations describing interaction of heterogeneous phase transitions. Distribution of extreme low frequency emissions obtained from numerical solutions to stochastic equations takes the power series form. Correlations of dynamic scaling between critical indicators determining frequency dependence of pulsations power spectra α and distribution functions of extreme low frequency pulsation amplitudes β have been determined. It is shown that both in the experiments on acoustic cavitation of water and in the theoretical model of interacting phase transitions critical indicators are bound with the correlation α + β = 2. Spectra of fluctuation power are determined in the experiments simpler and more accurately than the function of extreme amplitudes distribution. In case when only one frequency dependence of fluctuation capacity spectra is known correlations between indicators serve to obtain information on the distribution of large scale emissions and to estimate critical amplitudes.     

Enhancement of passive Q-switching performance with mixed Nd:LuxGd1-xVO4 laser crystals

Passive Q-switching operation has been demonstrated with a class of mixed Nd:Lu(x)Gd(1-x)VO(4) laser crystals. With respect to that obtained with Nd:GdVO(4), the passive Q-switching performance, including threshold, pulse energy, and peak power, was found to be greatly enhanced with the mixed vanadate crystals. The shortest pulse width of 6.2 ns, largest pulse energy of 192.5 microJ, and highest peak power of 31.1 kW were obtained at the incident pump power of 13.75 W with the mixed crystal for x=0.5.