Effect of pressure on the ionic conductivity of Li+ and Cl- ions in water

A molecular dynamics simulation study of aqueous solution of LiCl is reported as a function of pressure. Experimental measurements of conductivity of Li+ ion as a function of pressure shows an increase in conductivity with pressure. Our simulations are able to reproduce the observed trend in conductivity. A number of relevant properties have been computed in order to understand the reasons for the increase in conductivity with pressure. These include radial distribution function, void and neck distributions, hydration or coordination numbers, diffusivity, velocity autocorrelation functions, angles between ion-oxygen and dipole of water as well as OH vector, mean residence time for water in the hydration shell, etc. These show that the increase in pressure acts as a structure breaker. The decay of the self part of the intermediate scattering function at small wave number k shows a bi-exponential decay at 1 bar which changes to single exponential decay at higher pressures. The k dependence of the ratio of the self part of the full width at half maximum of the dynamic structure factor to 2Dk(2) exhibits trends which suggest that the void structure of water is playing a role. These support the view that the changes in void and neck distributions in water can account for changes in conductivity or diffusivity of Li+ with pressure. These results can be understood in terms of the levitation effect. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4756909]

Critical investigation on hydrogen bonding by Fourier transform infrared spectroscopy in hydrogenated amorphous silicon thin films

Fourier Transform Infrared (FTIR) spectroscopic analysis has been carried out on the hydrogenated amorphous silicon (a-Si:H) thin films deposited by DC, pulsed DC (PDC) and RF sputtering process to get insight regarding the total hydrogen concentration (C-H) in the films, configuration of hydrogen bonding, density of the films (decided by the vacancy and void incorporation) and the microstructure factor (R*) which varies with the type of sputtering carried out at the same processing conditions. The hydrogen incorporation is found to be more in RF sputter deposited films as compared to PDC and DC sputter deposited films. All the films were broadly divided into two regions namely vacancy dominated and void dominated regions. At low hydrogen dilutions the films are vacancy dominated and at high hydrogen dilutions they are void dominated. This demarcation is at C-H = 23 at.% H for RF, C-H = 18 at.% H for PDC and C-H = 14 at.% H for DC sputter deposited films. The microstructure structure factor R* is found to be as low as 0.029 for DC sputter deposited films at low C-H. For a given C-H, DC sputter deposited films have low R* as compared to PDC and RF sputter deposited films. Signature of dihydride incorporation is found to be more in DC sputter deposited films at low C-H.

Solid-liquid transition in polydisperse Lennard-Jones systems

We study melting of a face-centered crystalline solid consisting of polydisperse Lennard-Jones spheres with Gaussian polydispersity in size. The phase diagram reproduces the existence of a nearly temperature invariant terminal polydispersity (delta(t) similar or equal to 0.11), with no signature of reentrant melting. The absence of reentrant melting can be attributed to the influence of the attractive part of the potential upon melting. We find that at terminal polydispersity the fractional density change approaches zero, which seems to arise from vanishingly small compressibility of the disordered phase. At constant temperature and volume fraction the system undergoes a sharp transition from crystalline solid to the disordered amorphous or fluid state with increasing polydispersity. This has been quantified by second- and third-order rotational invariant bond orientational order, as well as by the average inherent structure energy. The translational order parameter also indicates a similar sharp structural change at delta similar or equal to 0.09 in case of T* = 1.0, phi = 0.58. The free energy calculation further supports the sharp nature of the transition. The third-order rotationally invariant bond order shows that with increasing polydispersity, the local cluster favors a more icosahedral arrangement and the system loses its local crystalline symmetry. Interestingly, the value of structure factor S(k) of the amorphous phase at delta similar or equal to 0.10 (just beyond the solid-liquid transition density at T* = 1) becomes 2.75, which is below the value of 2.85 required for freezing given by the empirical Hansen-Verlet rule of crystallization, well known in the theory of freezing.

Effect of Substrate Temperature on the Microstructure Variation in Sputter-deposited Hydrogenated Amorphous Silicon Thinfilms

Vacancy, void incorporation and Si-H-x configuration in hydrogenated amorphous silicon (a-Si:H) thin films was studied. Films were grown by Direct Current (DC), pulsed DC and Radio Frequency (RF) magnetron sputtering. Fourier Transform Infrared (FTIR) spectroscopic analysis has been carried out on the films and found that, the a-Si: H films grown by DC magnetron sputtering are of good quality compared to pulsed DC and RF deposited films. The effect of Substrate temperature (T-S) on the total hydrogen concentration (C-H), configuration of hydrogen bonding, density (decided by the vacancy and void incorporation) and the microstructure factor (R*) was studied. T-S is found to be an active parameter in affecting the above said properties of the films. The films contain both vacancies and voids. At low hydrogen dilutions the films are vacancy dominated and at high hydrogen dilutions they are void dominated. It is found that T-S favors monohydride (Si-H) bonding at the cost of dihydride (Si-H-2) bonding. This dividing line is at C-H=14 at.% H for DC sputter deposited films. The microstructure structure factor R* is found to be zero for as deposited DC films at T-S=773K. The threshold C-H for void dominated region is found to be C-H=23 at.% H for RF, C-H=18 at.% H for PDC and C-H similar to 14 at.%H for DC sputter deposited films.

Anomalous power law decay in solvation dynamics of DNA: a mode coupling theory analysis of ion contribution

Several time dependent fluorescence Stokes shift (TDFSS) experiments have reported a slow power law decay in the hydration dynamics of a DNA molecule. Such a power law has neither been observed in computer simulations nor in some other TDFSS experiments. Here we observe that a slow decay may originate from collective ion contribution because in experiments DNA is immersed in a buffer solution, and also from groove bound water and lastly from DNA dynamics itself. In this work we first express the solvation time correlation function in terms of dynamic structure factors of the solution. We use mode coupling theory to calculate analytically the time dependence of collective ionic contribution. A power law decay in seen to originate from an interplay between long-range probe-ion direct correlation function and ion-ion dynamic structure factor. Although the power law decay is reminiscent of Debye-Falkenhagen effect, yet solvation dynamics is dominated by ion atmosphere relaxation times at longer length scales (small wave number) than in electrolyte friction. We further discuss why this power law may not originate from water motions which have been computed by molecular dynamics simulations. Finally, we propose several experiments to check the prediction of the present theoretical work.

Studies on a frustrated Heisenberg spin chain with alternating ferromagnetic and antiferromagnetic exchanges

We study Heisenberg spin-1/2 and spin-1 chains with alternating ferromagnetic (J(1)(F)) and antiferromagnetic (J(1)(A)) nearest-neighbor interactions and a ferromagnetic next-nearest-neighbor interaction (J(2)(F)). In this model frustration is present due to the non-zero J(2)(F). The model with site spin s behaves like a Haldane spin chain, with site spin 2s in the limit of vanishing J(2)(F) and large J(1)(F)/J(1)(A). We show that the exact ground state of the model can be found along a line in the parameter space. For fixed J(1)(F), the phase diagram in the space of J(1)(A)-J(2)(F) is determined using numerical techniques complemented by analytical calculations. A number of quantities, including the structure factor, energy gap, entanglement entropy and zero temperature magnetization, are studied to understand the complete phase diagram. An interesting and potentially important feature of this model is that it can exhibit a macroscopic magnetization jump in the presence of a magnetic field; we study this using an effective Hamiltonian.

Structural Basis for Feed-Forward Transcriptional Regulation of Membrane Lipid Homeostasis in Staphylococcus aureus

11 p.

Horizontal Bloch line motion in magnetic bubble materials

The purpose of this work is to extend experimental and theoretical understanding of horizontal Bloch line (HBL) motion in magnetic bubble materials. The present theory of HBL motion is reviewed, and then extended to include transient effects in which the internal domain wall structure changes with time. This is accomplished by numerically solving the equations of motion for the internal azimuthal angle ɸ and the wall position q as functions of z, the coordinate perpendicular to the thin-film material, and time. The effects of HBL's on domain wall motion are investigated by comparing results from wall oscillation experiments with those from the theory. In these experiments, a bias field pulse is used to make a step change in equilibrium position of either bubble or stripe domain walls, and the wall response is measured by using transient photography. During the initial response, the dynamic wall structure closely resembles the initial static structure. The wall accelerates to a relatively high velocity (≈20 m/sec), resulting in a short (≈22 nsec ) section of initial rapid motion. An HBL gradually forms near one of the film surfaces as a result of local dynamic properties, and moves along the wall surface toward the film center. The presence of this structure produces low-frequency, triangular-shaped oscillations in which the experimental wall velocity is nearly constant, v_s≈ 5-8 m/sec. If the HBL reaches the opposite surface, i.e., if the average internal angle reaches an integer multiple of π, the momentum stored in the HBL is lost, and the wall chirality is reversed. This results in abrupt transitions to overdamped motion and changes in wall chirality, which are observed as a function of bias pulse amplitude. The pulse amplitude at which the n^th punch- through occurs just as the wall reaches equilibrium is given within 0.2 0e by H_n = (2v_sH'/γ)^1/2 • (nπ)^1/2 + H_sv), where H' is the effective field gradient from the surrounding domains, and H_sv is a small (less than 0.03 0e), effective drag field. Observations of wall oscillation in the presence of in-plane fields parallel to the wall show that HBL formation is suppressed by fields greater than about 40 0e (≈2πM_s), resulting in the high-frequency, sinusoidal oscillations associated with a simple internal wall structure.

STUDY OF MICROSTRUCTURE AND DEFECTS IN HYDROGENATED MICROCRYSTALLINE SILICON FILMS

Microcrystalline silicon films were deposited by very high frequency (VHF) plasma-enhanced chemical vapor deposition (PECVD) with different hydrogen dilution. The microstructure of these films was investigated using Raman spectroscopy and infrared absorption (IR) spectra. The crystalline, amorphous, and grain boundary volume fractions X-c, X-a and X-gb were estimated from Raman measurements. An interface structure factor (R-if) is proposed to characterize the grain boundary volume fractions in IR spectroscopy. The density of states (DOS) of the microcrystalline crystalline silicon films were studied by phase-shift analysis of modulated photocurrent (MPC) and photoconductivity spectroscopy. It was observed that DOS increases with increasing grain boundary volume fractions, while the values of electron mobility-lifetime product mu T-e(e) disease.

GIUSAXS and AFM Studies on Surface Reconstruction of Latex Thin Films during Thermal Treatment

The structural evolution of a single-layer latex film during annealing was studied via grazing incidence ultrasmall-angle X-ray scattering (GIUSAXS) and atomic force microscopy (AFM). The latex particles were composed of a low-T-g (-54 degrees C) core (n-butylacrylate, 30 wt %) and a high-T-g (41 degrees C) shell (t-butylacrylate, 70 wt %) and had an overall diameter of about 500 nm. GIUSAXS data indicate that the q(y) scan at q(z) = 0.27 nm(-1) (out-of-plane scan) contains information about both the structure factor and the form factor. The GIUSAXS data on latex films annealed at various temperatures ranging from room temperature to 140 degrees C indicate that the structure of the latex thin film beneath the surface changed significantly. The evolution of the out-of-plane scan plot reveals the surface reconstruction of the film. Furthermore, we also followed the time-dependent behavior of structural evolution when the latex film was annealed at a relatively low temperature (60 degrees C) where restructuring within the film can be followed that cannot be detected by AFM, which detects only surface morphology.

Uniaxial deformation of overstretched polyethylene: In-situ synchrotron small angle X-ray scattering study

Synchrotron small angle X-ray scattering was used to study the deformation mechanism of high-density polyethylene that was stretched beyond the natural draw ratio. New insight into the cooperative deformational behavior being mediated via slippage of micro-fibrils was gained. The scattering data confirm on the one hand the model proposed by Peterlin on the static structure of oriented polyethylene being composed of oriented fibrils, which are built by bundles of micro-fibrils. On the other hand it was found that deformation is mediated by the slippage of the micro-fibrils and not the slippage of the fibrils. In the micro-fibrils, the polymer chains are highly oriented both in the crystalline and in the amorphous regions. When stretching beyond the natural draw ratio mainly slippage of micro-fibrils past each other takes place. The thickness of the interlamellar amorphous layers increases only slightly. The coupling force between micro-fibrils increases during stretching due to inter-microfibrillar polymer segments being stretched taut thus increasingly impeding further sliding of the micro-fibrils leading finally to slippage of the fibrils.

Inelastic neutron scattering on sodium aluminosilicate melts: sodium diffusion and intermediate range order

Kargl, Florian; Meyer, A., (2004) 'Inelastic neutron scattering on sodium aluminosilicate melts: sodium diffusion and intermediate range order', Chemical Geology 213(1-3) pp.165-172 RAE2008

Channel formation and intermediate range order in sodium silicate melts and glasses

Kargl, Florian; Meyer, A.; Horbach, J.; Kob, W., (2004) 'Channel formation and intermediate range order in sodium silicate melts and glasses', Physical Review Letters 93(2) pp.027801 RAE2008

A new instrument for measuring anticoagulation-related quality of life: development and preliminary validation.

BACKGROUND: Anticoagulation can reduce quality of life, and different models of anticoagulation management might have different impacts on satisfaction with this component of medical care. Yet, to our knowledge, there are no scales measuring quality of life and satisfaction with anticoagulation that can be generalized across different models of anticoagulation management. We describe the development and preliminary validation of such an instrument - the Duke Anticoagulation Satisfaction Scale (DASS). METHODS: The DASS is a 25-item scale addressing the (a) negative impacts of anticoagulation (limitations, hassles and burdens); and (b) positive impacts of anticoagulation (confidence, reassurance, satisfaction). Each item has 7 possible responses. The DASS was administered to 262 patients currently receiving oral anticoagulation. Scales measuring generic quality of life, satisfaction with medical care, and tendency to provide socially desirable responses were also administered. Statistical analysis included assessment of item variability, internal consistency (Cronbach's alpha), scale structure (factor analysis), and correlations between the DASS and demographic variables, clinical characteristics, and scores on the above scales. A follow-up study of 105 additional patients assessed test-retest reliability. RESULTS: 220 subjects answered all items. Ceiling and floor effects were modest, and 25 of the 27 proposed items grouped into 2 factors (positive impacts, negative impacts, this latter factor being potentially subdivided into limitations versus hassles and burdens). Each factor had a high degree of internal consistency (Cronbach's alpha 0.78-0.91). The limitations and hassles factors consistently correlated with the SF-36 scales measuring generic quality of life, while the positive psychological impact scale correlated with age and time on anticoagulation. The intra-class correlation coefficient for test-retest reliability was 0.80. CONCLUSIONS: The DASS has demonstrated reasonable psychometric properties to date. Further validation is ongoing. To the degree that dissatisfaction with anticoagulation leads to decreased adherence, poorer INR control, and poor clinical outcomes, the DASS has the potential to help identify reasons for dissatisfaction (and positive satisfaction), and thus help to develop interventions to break this cycle. As an instrument designed to be applicable across multiple models of anticoagulation management, the DASS could be crucial in the scientific comparison between those models of care.

Neutron quasi-elastic scattering in disordered solids: a Monte Carlo study of metal-hydrogen systems

The dynamic structure factor of neutron quasi-elastic scattering has been calculated by Monte Carlo methods for atoms diffusing on a disordered lattice. The disorder includes not only variation in the distances between neighbouring atomic sites but also variation in the hopping rate associated with each site. The presence of the disorder, particularly the hopping rate disorder, causes changes in the time-dependent intermediate scattering function which translate into a significant increase in the intensity in the wings of the quasi-elastic spectrum as compared with the Lorentzian form. The effect is particularly marked at high values of the momentum transfer and at site occupancies of the order of unity. The MC calculations demonstrate how the degree of disorder may be derived from experimental measurements of the quasi-elastic scattering. The model structure factors are compared with the experimental quasi-elastic spectrum of an amorphous metal-hydrogen alloy.