Neutron scattering studies of molecular conformations in liquid crystal polymers

A comblike liquid crystal polymer (LPC) is a polymer on which mesogenic molecules have been grafted. It exhibits a succession of liquid crystal phases. Usually the equilibrium conformation of an ordinary polymeric chain corresponds to a maximum entropy, i.e., to an isotropic spherical coil. How does the backbone of a LCP behave in the nematic and smectic field? Small-angle neutron scattering may answer this question. Such measurements are presented here on four different polymers as a function of temperature. An anisotropy of the backbone conformation is found in all these studied compounds, much more pronounced in the smectic phase than in the nematic phase: the backbone spreads more or less perpendicularly to its hanging cores. A comparison with existing theories and a discussion of these results is outlined.     

Neutron brillouin scattering and liquid metal-molten salt mixtures

Summary The dispersion of collective density fluctuations (extended sound modes) has been measured in mixtures of liquid alkali metals and the corresponding molten alkali-halide salts. Mixtures with salt concentrations from 10 to 40% were investigated for momentum transfersQ between 4 and 14 nm⁻¹. ForQ-values larger than 11 nm⁻¹ the collective modes could even in the most favourable case no longer be separated from the quasi-elastic peak, the width of which increases roughly ∼Q ² in this region of momentum transfers. At a concentration of 10% RbCl in Rb we find a dispersion which would correspond to expanded liquid Rb at the temperature of the mixture (∼1000 K), demonstrating the dominant metallic character of the mixture (screening by nearly free electrons) at this salt concentration. At higher concentrations of salt, where influences from different partial dynamic structure factors interplay, the dispersions deviate from this simple structured dispersion curve, most likely due to the influence of an early onset of some ionic type of screening in the liquid. The proofs of this paper have been supervised by the Scientific Committee.     

Neutron scattering study of short-range correlations and ionic diffusion in copper selenide

The paper reports the results of a neutron scattering study of Cu_{2 - d}Se {\hbox{C}}{{\hbox{u}}_{{2 - \delta }}}{\hbox{Se}} superionic compounds. The crystallographic model fitted to the diffraction data shows the occupation of 8c and 32f sites by Cu atoms. Observed diffuse background is related to correlated thermal vibrations of Se and Cu atoms, with Se↔Cu (8c,32f) and Cu (8c)↔Cu (8c) correlations being most important. The quasi-elastic neutron experiments show the decrease of the self-diffusion coefficient with the deviation from the stoichiometry due to the longer residence time of Cu ions between diffusion hops. Combination of neutron diffraction, diffuse scattering and quasi-elastic scattering experimental data suggests that the Cu atoms diffuse between the nearest 8c sites through the 32f sites.     

Dynamics of a supercooled liquid

The theory of collective motion in liquids suggested by the authors has been found to explain successfully the recent experimental results of temperature dependent disorder in supercooled liquid gallium. Metastability limit is exhibited through a singularity of S(k, ω = 0) and corresponds to a critical value of correlation between different particles beyond which the supercooled liquid goes to the thermodynamically stable solid state.     

The primary-relaxation process in a supercooled liquid

Summary Dielectric and ultrasonic measurements have been performed in the temperature and in the frequency domain to investigate the α (or primary) relaxation in the supercooled state of a ?fragile? molecular liquid. This relaxation is strictly connected with the phenomenon of the glass transition and therefore an understanding of the former is a prerequisite for the explanation of the latter. The dynamic susceptibilities relative to these probes have been analysed with the Cole-Davidson function employing (where required) a Vogel-Fulcher-Tamman law to relate the main relaxation time to temperature. The results obtained are consistent with the dynamic behaviour of liquids of high fragility. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Dynamics of nanoparticles in a supercooled liquid

The dynamic properties of nanoparticles suspended in a supercooled glass forming liquid are studied by x-ray photon correlation spectroscopy. While at high temperatures the particles undergo Brownian motion the measurements closer to the glass transition indicate hyperdiffusive behavior. In this state the dynamics is independent of the local structural arrangement of nanoparticles, suggesting a cooperative behavior governed by the near-vitreous solvent.     

Neutron scattering from liquid helium three at elevated pressure

The inelastic neutron scattering from liquid³He at 0.7 K has been measured at the saturated vapour pressure, 10 bars, and 20 bars pressure, using the IN5 time of flight spectrometer at the Institut Laue-Langevin. Results were obtained for wavevector transfers,Q, in the region, 1.1<Q<2.4 Å^–1, and for energy transfers,, up to 27 K. There was no indication of a well defined zero sound mode even at an applied pressure of 20 bars. At low wavevector transfers, increasing the pressure increases the intensity at low energy transfers (<10 K), while at higher energy transfers, a decrease in intensity is observed with increasing pressure. At higher wavevector transfers, (Q1.9 Å^–1, the position of the roton minimum in superfluid⁴He), the scattering is a broad distribution, whose peak frequency decreases by more than a factor of 2, on increasing the pressure from S.V.P. to 20 bars. This is a considerably larger change in energy than is expected from previous estimates of the pressure dependence of the effective mass of³He.     

Local order of liquid and supercooled zirconium by ab initio molecular dynamics

It has been suggested that icosahedral short-range order (SRO) occurs in deeply undercooled melts of pure metallic elements. We report results of first-principles molecular dynamics simulations for stable and undercooled zirconium liquids. Our results emphasize the occurrence of a local order more complex than the icosahedral one. For stable liquid, the local order is interpreted on the basis of a competition between a polytetrahedral SRO and a bcc-type SRO. We also demonstrate that a bcc-type SRO increases with the degree of undercooling.     

Brillouin scattering from supercooled adsorbates

Brillouin scattering is used as a sensitive probe of structural properties of gases adsorbed on porous glass. Evidence is seen for extensive supercooling behavior in both oxygen and nitrogen.     

Solidification of a supercooled liquid in a narrow channel

We simulate solidification in a narrow channel through the use of a phase-field model with an adaptive grid. In different regimes, we find that the solid can grow in fingerlike steady-state shapes, or become unstable, exhibiting unsteady growth. At low melt undercoolings, we find good agreement between our results, theoretical predictions, and experiment. For high undercoolings, we report evidence for a new stable steady-state finger shape which exists in experimentally accessible ranges for typical materials.     

Elastic modulus of supercooled liquid and hot solid silicon measured by inelastic X-ray scattering

The dynamical structure factors of supercooled-liquid and hot-solid silicon are measured by inelastic X-ray scattering at the same temperature, 1620 K. Two significant changes in the averaged longitudinal sound velocities and in the longitudinal modulus are observed. First, we observe a different longitudinal modulus in the polycrystalline hot-solid silicon compared to the extrapolated value obtained from the single-crystal measurement. This reduction of the modulus may be a precursor of the semiconductor-to-metal transition. Second, the increase in the longitudinal modulus in the liquid upon supercooling is consistent with an increase in the degree of the directional bonding.     

Neutron scattering in intermetallics

Inelastic and elastic neutron scattering as a probe of long range and disordered magnetism is discussed for example cases in rare earth intermetallic crystalline compounds and amorphous analogues. The determination of the sublattice site magnetizations is illustrated for RFe₂ and Y₆(Mn_xFe_1−x)₂₃ compounds. The latter are shown to exhibit strong exchange disorder effects for intermediate compositions, as manifested by the development of short range antiferromagnetic clusters. The effect of randomization of the crystal field interaction in destroying long range order is illustrated in amorphous rare earth compounds and in rare earth compound hydrides. Results of inelastic scattering measurements on Laves phase Fe, Co, and Al compounds are summarized which yield exchange and crystal field parameters.     

Light scattering by longitudinal acoustic modes in molecular supercooled liquids I: phenomenological approach

We derive expressions for the intensity of the Brillouin polarized spectrum of a molecular liquid formed of axially symmetric molecules. These expressions take into account both the molecular dielectric anisotropy and the modulation of the local polarisability by density fluctuations. They also incorporate all the retardation effects which occur in such liquids. We show that the spectrum splits into a q-independent rotational contribution and q-dependent term, which reflects the propagation of longitudinal acoustic modes. In the latter, the two light scattering mechanisms enter on an equal footing and generate three scattering channels. We study the influence of the two new channels and show that they may substantially modify the Brillouin line-shape when the relaxation time of the supercooled liquid and the period of the acoustic excitation are of the same order of magnitude. Received 14 August 2002 Published online 4 February 2003 RID="a" ID="a"e-mail: franosch@hmi.de     

Anomalous scattering in supercooled ST2 water

ABSTRACT

Large-scale molecular dynamics (MD) simulations of systems containing up to 256,000 molecules were performed to investigate the scattering behaviour of the ST2 water model at deeply supercooled conditions. The simulations reveal that ST2 exhibits anomalous scattering, reminiscent of that observed in experiment, which is characterised by an increase in the static structure factor at low wavenumbers. This unusual behaviour in ST2 is linked with coupled fluctuations in density and local tetrahedral order in the liquid. The Ornstein–Zernike correlation length estimated from the anomalous scattering component exhibits power-law growth upon cooling, consistent with the existence of a liquid–liquid critical point (LLCP) in the ST2 model at ca. 245 K. Further, spontaneous liquid–liquid phase separation is observed upon thermally quenching a large system with 256,000 water molecules below the predicted critical temperature into the two-phase region. The large-scale MD simulations therefore confirm the existence of a metastable liquid–liquid phase transition in ST2 and support findings from previous computational studies performed using smaller systems containing only a few hundred molecules. We anticipate that our analysis may prove useful in interpreting recent scattering experiments that have been performed to search for an LLCP in deeply supercooled water.     

Compressed-exponential relaxations in supercooled liquid trehalose

We investigated the α-relaxations in supercooled liquid trehalose by using photon correlation spectroscopy (PCS) and found an interesting compressed-exponential relaxation at temperatures above 140 °C. The q^?1 dependence of its relaxation time corresponds to an ultraslow ballistic motion due to the local structure rearrangements. In the same temperature range, we found the glycosidic bond structure changes in trehalose molecule from the Raman scattering and the X-ray direction measurements. We concluded that the compressed-exponential relaxation in supercooled liquid trehalose might originate from the intra-molecular (glycosidic bond) structure change.     

Correlation of primary and secondary relaxations in a supercooled liquid

The widespread assumption that primary and secondary relaxations in glass-forming materials are independent processes is scrutinized using spin-lattice relaxation weighted stimulated-echo spectroscopy. This nuclear magnetic resonance (NMR) technique is simultaneously sensitive to the dynamics on well-separated time scales. For the deeply supercooled liquid sorbitol, which exhibits a strong secondary relaxation, the primary relaxation (that is observable using NMR) can be modified by suppressing the contributions of those subensembles which are characterized by relatively slow secondary relaxations. This is clear evidence for a correlation between primary and secondary relaxation times. In the disordered crystal orthocarborane high-frequency processes are absent and consequently no such modifications could be achieved.