ABSTRACT
The microscopic structures of two amorphous molecular solids with extremely nonlinear optical properties have been studied. They consist of organotetrel chalcogenide clusters with the chemical formula [(RSn)4S6]. The basic molecular building blocks are adamantane-like {Sn4S6} cores with organic ligands R attached to the Sn atoms. While the material equipped with R=naphthyl generates frequency doubling upon irradiation with a simple infrared laser diode, the material decorated with R=phenyl responds by emitting brilliant white light. The structural differences were investigated using x-ray scattering and extended x-ray absorption fine structure combined with molecular Reverse Monte Carlo. Transmission electron microscopy and scanning precession electron diffraction were used to examine structural differences from mesoscopic down to microscopic scales. Characteristic differences were found on all scales. While close core-to-core distances between {Sn4S6} cluster cores and molecular distortions are found in the white light emitting material, undistorted molecules and significantly larger core distances characterize the material showing frequency doubling. Here however, results of scanning precession electron diffraction reveal the formation of nanocrystalline structures in the amorphous matrix, which we identify as cause for the suppression of white light emission.
ABSTRACT
We have investigated the local atomic structures of several compositions of the amorphous phase of the system CuxGe50-xTe50(0⩽x⩽33.3), based on extended x-ray absorption fine-structure as well as anomalous x-ray scattering experiments, and discuss the unusual trend regarding their thermal stability as a function of the Cu content. At low concentrations (x⩽15), Cu atoms tend to agglomerate in flat nanoclusters reminiscent of the crystalline phase of metallic Cu, leading to a more and more Ge-deficient Ge-Te host network structure with growing Cu content and an increasing thermal stability. At higher Cu concentrations (x⩾25), Cu is incorporated into the network, leading to an overall weaker bonding situation which is associated with a decreasing thermal stability.
ABSTRACT
An inelastic x-ray scattering experiment has been performed on molten NaCl over wide wave vector and energy transfer ranges. Data of high statistical quality are analyzed using a memory function approach within a generalized Langevin equation. The approach with two relaxation times for the memory function provides a very good data description over the whole wave vector range beyond the hydrodynamic regime. A slow thermal and a fast structural relaxation process in the memory function completely define the density fluctuations in molten NaCl and evidences the thermal-viscoelastic model as the minimal description for collective particle dynamics in molten alkali halides. The obtained excitation frequencies demonstrate a large positive dispersion effect, which can be related to the viscoelastic reaction of the molten salt. A transition from the viscoelastic to a hydrodynamic response of the molten salt at small wave vectors is observed. In the hydrodynamic regime the resulting thermal diffusivity agrees well with values obtained through light scattering. The modeling indicates some deficiencies at small wave vectors and large energy transfers and the spectra of the current correlation function evidences additional intensity at high frequency. The frequency of these additional modes approach a non-zero value at zero wave vector and indicates a non-acoustic character of these excitations. The frequency center of this additional inelastic intensity coincides with optic-type modes in molten NaCl predicted by simulations.
ABSTRACT
We present a model equation of states for expanded metals, which contains a pressure term due to a screened-Coulomb potential with a screening parameter reflecting the Mott-Anderson metal-to-nonmetal transition. As anticipated almost 80 years ago by Zel'dovich and Landau, this term gives rise to a second coexistence line in the phase diagram, indicating a phase separation between a metallic and a nonmetallic liquid.
ABSTRACT
To date, the BRISP spectrometer represents the state-of-the-art for every instrument aiming to perform Brillouin neutron scattering. Exploiting accurate ray-tracing McStas simulations, we investigate an improved configuration of the BRISP primary spectrometer to provide a higher flux at the sample position, while preserving all the present capabilities of the instrument. This configuration is based on a neutron guide system and is designed to fit the instrument platform with no modifications of the secondary spectrometer. These evaluations show that this setup can achieve a flux gain factor ranging from 3 to 6, depending on the wavelength. This can expand the experimental possibilities of BRISP towards smaller samples, possibly using also complex sample environments.
ABSTRACT
The temperature dependence of the dynamic structure factor at next-neighbour distances has been investigated for liquid aluminium. This correlation function is a sensitive parameter for changes in the local environment and its Fourier transform was measured in a coherent inelastic neutron scattering experiment. The zero frequency amplitude decreases in a nonlinear way and indicates a change in dynamics around 1.4 â Tmelting. From that amplitude a generalized viscosity can be derived which is a measure of local stress correlations on next-neighbour distances. The derived generalized longitudinal viscosity shows a changing slope at the same temperature range. At this temperature the freezing out of degrees of freedom for structural relaxation upon cooling sets in which can be understood as a precursor towards the solid state. That crossover in dynamics of liquid aluminium shows the same signatures as previously observed in liquid rubidium and lead, indicating an universal character.
ABSTRACT
Inelastic neutron scattering was applied to measure the acoustic-type excitations in the molten alkali halide rubidium bromide. For molten RbBr neutron scattering is mainly sensitive to the number density fluctuation spectrum and is not influenced by charge fluctuations. Utilizing a dedicated Brillouin scattering spectrometer, we focused on the small-wave-vector range. From inelastic excitations in the spectra a dispersion relation was obtained, which shows a large positive dispersion effect. This frequency enhancement is related to a viscoelastic response of the liquid at high frequencies. Towards small wave vectors we identify the transition to hydrodynamic behavior. This observation is supported by a transition of the sound velocity from a viscoelastic enhanced value to the adiabatic speed of sound for the acoustic-type excitations. Furthermore, the spectrum transforms into a line shape compatible with a prediction from hydrodynamics.
ABSTRACT
Transverse acoustic (TA) excitation modes were observed in inelastic x-ray scattering (IXS) spectra of liquid Sn. The excitation energies and widths of the TA modes are in good agreement with results of an ab initio molecular dynamics simulation. By comparing current correlation spectra between the experimental and theoretical results quantitatively, we have concluded that the TA modes can be detected experimentally through the quasi-TA branches in the longitudinal current correlation spectra. The lifetime and propagation length of the TA modes were determined to be ~0.7 ps and 0.8-1.0 nm, respectively, corresponding to the size of cages formed instantaneously in liquid Sn.
ABSTRACT
The transverse acoustic excitation modes were detected by inelastic x-ray scattering in liquid Ga in the Q range above 9 nm(-1) although liquid Ga is mostly described by a hard-sphere liquid. An ab initio molecular dynamics simulation clearly supports this finding. From the detailed analysis for the S(Q,omega) spectra with a good statistic quality, the lifetime of 0.5 ps and the propagating length of 0.4-0.5 nm can be estimated for the transverse acoustic phonon modes, which may correspond to the lifetime and size of cages formed instantaneously in liquid Ga.
ABSTRACT
Owing to their large relatively thermal conductivity, peculiar, nonhydrodynamic features are expected to characterize the acousticlike excitations observed in liquid metals. We report here an experimental study of collective modes in molten nickel, a case of exceptional geophysical interest for its relevance in earth interior science. Our result shed light on previously reported contrasting evidences: In the explored energy-momentum region, no deviation from the generalized hydrodynamic picture describing nonconductive fluids is observed. Implications for high frequency transport properties in metallic fluids are discussed.
ABSTRACT
The dynamic structure factor S(Q,ω) of liquid Ga was measured at 100 °C using a high resolution inelastic x-ray scattering (IXS) spectrometer at 3-ID-C/APS. The spectra obtained clearly demonstrate the existence of longitudinal propagating modes at small Q values, like a previous IXS result at 42 °C obtained by Scopigno et al and an inelastic neutron scattering (INS) one at 47 °C obtained by Bove et al, but unlike an INS study at 57 °C by Bermejo et al. The dispersion relation of the excitations deviates positively from the hydrodynamic prediction by about 13%. There are two new findings from this experiment. Firstly, an additional lower energy excitation is necessary to reproduce S(Q,ω) spectra in the Q range beyond 10 nm(-1), in agreement with the result of a first-principles molecular dynamic simulation, which may indicate a transverse acoustic mode in this peculiar liquid metal. Secondly, the quasielastic line comprises a Gaussian contribution at Q values near the first maximum in S(Q), which may indicate the existence of short-lived covalent correlation in liquid Ga with a lifetime of 0.39 ps.
ABSTRACT
This paper gives a survey of the particle dynamics in the liquid alkali metals observed with inelastic x-ray and neutron scattering experiments. Liquid rubidium and sodium are chosen as model fluids to represent the behaviour of this group of fluids. In the dense metallic monatomic melt the microscopic dynamics is characterized by collective excitations similar to those in the corresponding solids. The collective particle behaviour is appropriately described using a memory function formalism with two relaxation channels for the density correlation. A similar behaviour is found for the single particle motion where again two relaxation mechanisms are needed to accurately reproduce the experimental findings. Special emphasis is given to the density dependence of the particle dynamics. An interesting issue in liquid metals is the metal to non-metal transition, which is observed if the fluid is sufficiently expanded with increasing temperature and pressure. This causes distinct variations in the interparticle interactions, which feed back onto the motional behaviour. The associated variations in structure and dynamics are reflected in the shape of the scattering laws. The experimentally observed features are discussed and compared with simple models and with the results from computer simulations.
