ESR study of exchange coupled pairs in copper diethyldithiocarbamate—explanation of the low temperature hyperfine anomaly

A study of the hyperfine interaction in the ESR of Cu-Cu pairs in single crystals of copper diethyldithiocarbamate as a function of temperature has shown distinct differences in the hyperfine structure in the two fine structure transitions at 20 K, the spectrum not having the same hyperfine intensity pattern in the low field fine structure transition in contrast to that of the high field transition. The details of the structure of both the fine structure transitions in the 20 K spectrum have now been explained by recognizing the fact that the mixing of the nuclear spin states caused by the anisotropic hyperfine interaction affects the electron spin states | + 1 > and | −> differently. This has incidentally led to a determination of the sign ofD confirming the earlier model. The anomalous hyperfine structure is found to become symmetric at 77 K and 300 K. It is proposed that the reason for this lies in the dynamics of spin-lattice interaction which limits the lifetime of the spin states in each of the electronic levels | − 1 >, | 0 > and | + 1 > The estimate of spin-lattice relaxation time agrees with those indicated from other studies. The model proposed here for the hyperfine interaction of pairs in the electronic triplet state is of general validity.

Synthesis, characterization, thermal degradation, and comparative chain dynamics studies of weak-link polysulfide polymers

Synthesis, spectroscopic and thermal characterization of two new classes of polysulfide polymers: poly[1(phenoxymethyl) ethylene polysulfide] (PPMEP), and poly [1-(phenoxy) ethylene polysulfide] (PPEP) is presented. The direct pyrolysis mass spectrometry (DP-MS) technique, used to study the thermal degradation behavior of these polysulfide polymers, indicated that the polymers underwent degradation through the weak-links scission. The thermal stability of the polysulfide polymers decreased as the ``rank'' (number of sulfur atoms in the polysulfide linkage; n=1, 2, 4) increased. The main-chain flexibility of these polysulfide polymers in terms of their C-13 NMR spinlattice relaxation time (T-1) measurements on the backbone methine (-CH-) and methylene (-CH2-) carbons are reported here for the first time. A comparative study of the solution chain dynamics indicated that it increased as ``rank'' of the polysulfide linkages decreased as well as by introducing side chain spacers such as, ether (-O-) or methyleneoxy (-CH2O-) groups.

Simulation of laminar flow in a three-dimensional lid-driven cavity by lattice Boltzmann method

Purpose - The purpose of this paper is to apply lattice Boltzmann equation method (LBM) with multiple relaxation time (MRT) model, to investigate lid-driven flow in a three-dimensional (3D), rectangular cavity, and compare the results with flow in an equivalent two-dimensional (2D) cavity. Design/methodology/approach - The second-order MRT model is implemented in a 3D LBM code. The flow structure in cavities of different aspect ratios (0.25-4) and Reynolds numbers (0.01-1000) is investigated. The LBM simulation results are compared with those from numerical solution of Navier-Stokes (NS) equations and with available experimental data. Findings - The 3D simulations demonstrate that 2D models may predict the flow structure reasonably well at low Reynolds numbers, but significant differences with experimental data appear at high Reynolds numbers. Such discrepancy between 2D and 3D results are attributed to the effect of boundary layers near the side-walls in transverse direction (in 3D), due to which the vorticity in the core-region is weakened in general. Secondly, owing to the vortex stretching effect present in 3D flow, the vorticity in the transverse plane intensifies whereas that in the lateral plane decays, with increase in Reynolds number. However, on the symmetry-plane, the flow structure variation with respect to cavity aspect ratio is found to be qualitatively consistent with results of 2D simulations. Secondary flow vortices whose axis is in the direction of the lid-motion are observed; these are weak at low. Reynolds numbers, but become quite strong at high Reynolds numbers. Originality/value - The findings will be useful in the study of variety of enclosed fluid flows.

Multicarrier conduction and Boltzmann transport analysis of heavy hole mobility in HgCdTe near room temperature

Magnetotransport measurements in pulsed fields up to 15 T have been performed on mercury cadmium telluride (Hg1-xCdxTe, x similar to 0.2) bulk as well as liquid phase epitaxially grown samples to obtain the resistivity and conductivity tensors in the temperature range 220-300 K. Mobilities and densities of various carriers participating in conduction have been extracted using both conventional multicarrier fitting (MCF) and mobility spectrum analysis. The fits to experimental data, particularly at the highest magnetic fields, were substantially improved when MCF is applied to minimize errors simultaneously on both resistivity and conductivity tensors. The semiclassical Boltzmann transport equation has been solved without using adjustable parameters by incorporating the following scattering mechanisms to fit the mobility: ionized impurity, polar and nonpolar optical phonons, acoustic deformation potential, and alloy disorder. Compared to previous estimates based on the relaxation time approximation with outscattering only, polar optical scattering and ionized impurity scattering limited mobilities are shown to be larger due to the correct incorporation of the inscattering term taking into account the overlap integrals in the valence band.

Gelatin hydrogel electrolytes and their application to electrochemical supercapacitors

Gelatin hydrogel electrolytes (GHEs) with varying NaCl concentrations have been prepared by cross-linking an aqueous solution of gelatin with aqueous glutaraldehyde and characterized by scanning electron microscopy, differential scanning calorimetry, cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic chronopotentiometry. Glass transition temperatures for GHEs range between 339.6 and 376.9 K depending on the dopant concentration. Ionic conductivity behavior of GHEs was studied with varying concentrations of gelatin, glutaraldehyde, and NaCl, and found to vary between 10(-3) and 10(-1) S cm(-1). GHEs have a potential window of about 1 V. Undoped and 0.25 N NaCl-doped GHEs follow Arrhenius equations with activation energy values of 1.94 and 1.88 x 10(-4) eV, respectively. Electrochemical supercapacitors (ESs) employing these GHEs in conjunction with Black Pearl Carbon electrodes are assembled and studied. Optimal values for capacitance, phase angle, and relaxation time constant of 81 F g(-1), 75 degrees, and 0.03 s are obtained for 3 N NaCl-doped GHE, respectively. ES with pristine GHE exhibits a cycle life of 4.3 h vs 4.7 h for the ES with 3 N NaCl-doped GHE. (c) 2007 The Electrochemical Society.

1H NMR study of internal motions and quantum rotational tunneling in (CH3)4NGeCl3

(CH3)4NGeCl3 is prepared, characterized and studied using 1H NMR spin lattice relaxation time and second moment to understand the internal motions and quantum rotational tunneling. Proton second moment is measured at 7 MHz as function of temperature in the range 300-77 K and spin lattice relaxation time (T1) is measured at two Larmor frequencies, as a function of temperature in the range 270-17 K employing a homemade wide-line/pulsed NMR spectrometers. T1 data are analyzed in two temperature regions using relevant theoretical models. The relaxation in the higher temperatures (270-115 K) is attributed to the hindered reorientations of symmetric groups (CH3 and (CH3)4N). Broad asymmetric T1 minima observed below 115 K down to 17 K are attributed to quantum rotational tunneling of the inequivalent methyl groups.

Study of molecular reorientation and quantum rotational tunneling in tetramethylammonium selenate by H-1 NMR

H-1 NMR spin-lattice relaxation time measurements have been carried out in [(CH3)(4)N](2)SeO4 in the temperature range 389-6.6K to understand the possible phase transitions, internal motions and quantum rotational tunneling. A broad T, minimum observed around 280K is attributed to the simultaneous motions of CH3 and (CH3)(4)N groups. Magnetization recovery is found to be stretched exponential below 72 K with varying stretched exponent. Low-temperature T-1 behavior is interpreted in terms of methyl groups undergoing quantum rotational tunneling. (c) 2007 Elsevier Inc. All rights reserved.

Steady flow of a maxwell fluid in a porous cylindrical annulus with circular cross-section

When a fluid with memory is injected into any flow region some assumptions regarding the initial state of stress have to be made in order to determine the state of stress at any subsequent instant. For a Maxwell fluid, it is assumed that the fluid near the surface of injection is suddenly stressed and responds by starting flow in accordance with the mechanical model chosen. The flow of a Maxwell fluid with a single relaxation time has been determined under the above assumption in the following two cases: (i) annulus between two porous concentric circular cylinders, and (ii) space between two porous and infinitely extending parallel plates. The nature of flow in the present case is similar to that of the Reiner-Rivlin fluids obtained by Narasimhan2).

Energy landscape view of phase transitions and slow dynamics in thermotropic liquid crystals

Thermotropic liquid crystals are known to display rich phase behavior on temperature variation. Although the nematic phase is orientationally ordered but translationally disordered, a smectic phase is characterized by the appearance of a partial translational order in addition to a further increase in orientational order. In an attempt to understand the interplay between orientational and translational order in the mesophases that thermotropic liquid crystals typically exhibit upon cooling from the high-temperature isotropic phase, we investigate the potential energy landscapes of a family of model liquid crystalline systems. The configurations of the system corresponding to the local potential energy minima, known as the inherent structures, are determined from computer simulations across the mesophases. We find that the depth of the potential energy minima explored by the system along an isochor grows through the nematic phase as temperature drops in contrast to its insensitivity to temperature in the isotropic and smectic phases. The onset of the growth of the orientational order in the parent phase is found to induce a translational order, resulting in a smectic-like layer in the underlying inherent structures; the inherent structures, surprisingly, never seem to sustain orientational order alone if the parent nematic phase is sandwiched between the high-temperature isotropic phase and the low-temperature smectic phase. The Arrhenius temperature dependence of the orientational relaxation time breaks down near the isotropic-nematic transition. We find that this breakdown occurs at a temperature below which the system explores increasingly deeper potential energy minima.

Stress induced phase transition in monomolecular perfluroalkylsilane film self assembled on aluminium surface

We control the stiffnesses of two dual double cantelevers placed in series to control penetration into a perflurooctyltrichlorosilane monolayer self assembled on aluminium and silicon substrates. The top cantilever which carries the probe is displaced with respect to the bottom cantilever which carries the substrate, the difference in displacement recorded using capacitors gives penetration. We further modulate the input displacement sinusoidally to deconvolute the viscoelastic properties of the monolayer. When the intervention is limited to the terminal end of the molecule there is a strong viscous response in consonance with the ability of the molecule to dissipate energy by the generation of gauche defects freely. When the intervention reaches the backbone, at a contact mean pressure of 0.2GPa the damping disappears abruptly and the molecule registers a steep rise in elastic modulus and relaxation time constant, with increasing contact pressure. We offer a physical explanation of the process and describe this change as due to a phase transition from a liquid like to a solid like state.

Determination of distances of sugar protons from Mn2+ in concanavalin A

1H NMR spin-lattice relaxation time (T1) measurements have been carried out with various sugars, viz. methyl alpha-D-glucopyranoside (alpha-MeGluP), methyl beta-D-lucopyranoside (beta-MeGluP), methyl alpha--annopyranoside (alpha-MeManP), maltose (4-O-alpha-D-glucopyranosyl--glucose), nigerose (3-O-alpha-D-glucopyranosyl-D-glucose), p-nitrophenyl alpha-maltoside (PNP-alpha-maltoside) and p-nitrophenyl beta-maltoside (PNP-beta-maltoside) to determine the distances of sugar protons from Mn2+ in concanavalin A (Con A). With a rotational correlation time of 1.58 x 10(-10) s determined, distances were calculated using Solomon-Bloembergen equation. The data obtained indicated differences in disposition of different groups in the binding site of Con A. An average value of about 10 A was obtained for the distances of sugar protons from Mn2+ in Con A. In the case of mono and disaccharides, the non-reducing end sugar unit was found to be closer to Mn2+ than the reducing end one.

Microstructure related influence on the electrical properties of pulsed laser ablated (Ba, Sr)TiO3 thin films

The microstructural dependence of electrical properties of (Ba, Sr)TiO3(BST) thin films were studied from the viewpoint of dc and ac electrical properties. The films were grown using a pulsed laser deposition technique in a temperature range of 300 to 600 degrees C, inducing changes in grain size, structure, and morphology. Consequently, two different types of films were realized, of which type I, was polycrystalline, multigrained, while type II was [100] oriented possessing a densely packed fibrous microstructure. Leakage current measurements were done at elevated temperatures to provide evidence of the conduction mechanism present in these films. The results revealed a contribution from both electronic and ionic conduction. In the case of type I films, two trapping levels were identified with energies around 0.5 and 2.73 eV, which possibly originate from oxygen vacancies V-O and Ti3+ centers, respectively. These levels act as shallow and deep traps and are reflected in the current-voltage characteristics of the BST thin films. The activation energy associated with oxygen vacancy motion in this case was obtained as 1.28 eV. On the contrary, type II films showed no evidence of deep trap energy levels, while the identified activation energy associated with shallow traps was obtained as 0.38 eV. The activation energy obtained for oxygen vacancy motion in type II films was around 1.02 eV. The dc measurement results were further elucidated through ac impedance analysis, which revealed a grain boundary dominated response in type I in comparison to type II films where grain response is highlighted. A comparison of the mean relaxation time of the two films revealed three orders of magnitude higher relaxation time in the case of type I films. Due to smaller grain size in type I films the grains were considered to be completely depleted giving rise to only grain boundary response for the bulk of the film. The activation energy obtained from conductivity plots agree very well with that of dc measurements giving values 1.3 and 1.07 eV for type I and type II films, respectively. Since oxygen vacancy transport have been identified as the origin of resistance degradation in BST thin films, type I films with their higher value of activation energy for oxygen ion mobility explains the improvement in breakdown characteristics under constant high dc field stress. The role of microstructure in controlling the rate of degradation is found useful in this instance to enhance the film properties under high electric field stresses. (C) 2000 American Institute of Physics. [S0021-8979(00)00418-7].

Polarization Caging in Diffusion-Controlled Electron Transfer Reactions in Solution

In some bimolecular diffusion-controlled electron transfer (ET) reactions such as ion recombination (IR), both solvent polarization relaxation and the mutual diffusion of the reacting ion pair may determine the rate and even the yield of the reaction. However, a full treatment with these two reaction coordinates is a challenging task and has been left mostly unsolved. In this work, we address this problem by developing a dynamic theory by combining the ideas from ET reaction literature and barrierless chemical reactions. Two-dimensional coupled Smoluchowski equations are employed to compute the time evolution of joint probability distribution for the reactant (P-(1)(X,R,t)) and the product (p((2))(X,R,t)), where X, as is usual in ET reactions, describes the solvent polarization coordinate and R is the distance between the reacting ion pair. The reaction is described by a reaction line (sink) which is a function of X and R obtained by imposing a condition of equal energy on the initial and final states of a reacting ion pair. The resulting two-dimensional coupled equations of motion have been solved numerically using an alternate direction implicit (ADI) scheme (Peaceman and Rachford, J. Soc. Ind. Appl. Math. 1955, 3, 28). The results reveal interesting interplay between polarization relaxation and translational dynamics. The following new results have been obtained. (i) For solvents with slow longitudinal polarization relaxation, the escape probability decreases drastically as the polarization relaxation time increases. We attribute this to caging by polarization of the surrounding solvent, As expected, for the solvents having fast polarization relaxation, the escape probability is independent of the polarization relaxation time. (ii) In the slow relaxation limit, there is a significant dependence of escape probability and average rate on the initial solvent polarization, again displaying the effects of polarization caging. Escape probability increases, and the average rate decreases on increasing the initial polarization. Again, in the fast polarization relaxation limit, there is no effect of initial polarization on the escape probability and the average rate of IR. (iii) For normal and barrierless regions the dependence of escape probability and the rate of IR on initial polarization is stronger than in the inverted region. (iv) Because of the involvement of dynamics along R coordinate, the asymmetrical parabolic (that is, non-Marcus) energy gap dependence of the rate is observed.

Reactivity studies of highly electrophilic ruthenium complexes

The 16-electron, coordinatively unsaturated, dicationic ruthenium complex Ru(P(OH)(2)(OMe))(dppe)(2)]OTf](2) (1a) brings about the heterolysis of the C-H bond in phenylacetylene to afford the phenylacetylide complex trans-Ru(C CPh)(P(OH)(2)(OMe))(dppe)(2)]OTf] (2). The phenylacetylide complex undergoes hydrogenation to give a ruthenium hydride complex trans-Ru(H)(P(OH)(2)(OMe))(dppe)(2)]OTf] (3) and phenylacetylene via the addition of H-2 across the Ru-C bond. The 16-electron complex also reacts with HSiCl3 quite vigorously to yield a chloride complex trans-Ru(Cl)(P(OH)(2)(OMe))(dppe)(2)]OTf] (4). On the other hand, the other coordinatively unsaturated ruthenium complex Ru(P(OH)(3))(dppe)(2)]OTf](2) (1b) reacts with a base N-benzylideneaniline to afford a phosphonate complex Ru(P(O)(OH)(2))(dppe)(2)]OTf] (5) via the abstraction of one of the protons of the P(OH)(3) ligand by the base. The phenylacetylide, chloride, and the phosphonate complexes have been structurally characterized. The phosphonate complex reacts with H-2 to afford the corresponding dihydrogen complex trans-Ru(eta(2)-H-2)(P(O)(OH)(2))(dppe)(2)]OTf] (5-H2). The intact nature of the H-H bond in this species was established using variable temperature H-1 spin-lattice relaxation time measurements and the observation of a significant J(H,D) coupling in the HD isotopomer trans-Ru(eta(2)-HD)(P(O)(OH)(2))(dppe)(2)]OTf] (5-HD). (C) 2010 Elsevier B. V. All rights reserved.

Communication: Unusual dynamics of hybrid nanoparticles and their binary mixtures

We present the results on the evolution of microscopic dynamics of hybrid nanoparticles and their binary mixtures as a function of temperature and wave vector. We find unexpectedly a nonmonotonic dependence of the structural relaxation time of the nanoparticles as a function of the morphology. In binary mixtures of two of the largest nanoparticles studied, we observe re-entrant vitrification as a function of the volume fraction of the smaller nanoparticle, which is unusual for such high diameter ratio. Possible explanation for the observed behavior is provided. (C) 2010 American Institute of Physics. doi:10.1063/1.3495480]