Magnetism, exchange and crystal field parameters in the orbitally unquenched Ising antiferromagnet FePS3

FePS3 is a layered antiferromagnet (T N=123 K) with a marked Ising anisotropy in magnetic properties. The anisotropy arises from the combined effect of the trigonal distortion from octahedral symmetry and spin-orbit coupling on the orbitally degenerate5 T 2g ground state of the Fe2+ ion. The anisotropic paramagnetic susceptibilities are interpreted in terms of the zero field Hamiltonian, ?=?i [?(L iz 2 ?2)+|?|L i .S i ]?? ij J ij S i .S j . The crystal field trigonal distortion parameter ?, the spin-orbit coupling ? and the isotropic Heisenberg exchange,J ij, were evaluated from an analysis of the high temperature paramagnetic susceptibility data using the Correlated Effective Field (CEF) theory for many-body magnetism developed by Lines. Good agreement with experiment were obtained for ?/k=215.5 K; ?/k=166.5 K;J nn k=27.7 K; andJ nnn k=?2.3 K. Using these values of the crystal field and exchange parameters the CEF predicts aT N=122 K for FePS3, which is remarkably close to the observed value of theT N. The accuracy of the CEF approximation was also ascertained by comparing the calculated susceptibilities in the CEF with the experimental susceptibility for the isotropic Heisenberg layered antiferromagnet MnPS3, for which the high temperature series expansion susceptibility is available.

The Reaction of a Nitro-Capped Cobalt(III) Cage Complex With Base: the Crystal Structure of a Contracted Cage Complex, and the Mechanism of Its Formation

The synthesis, properties and crystal structure of the cage complex (1-hydroxy-8-methyl-3,6,10,13,15,18-hexaazabicyclo[6.6.5]nonadecane)cobalt(III) chloride hydrate ([Co(Me,OH-absar)] C13.H2O) are reported. The mechanism of the formation of this contracted cavity cage from a nitro-capped hexaazabicycloicosane type cage has been investigated. Treatment of (1-methyl-8-nitro-3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane)cobalt(III) chloride ([Co(Me,NO2-sar)] 3+) with excess base in aqueous solution leads initially to rapid (t1/2 < 1 ms) and reversible deprotonation of one coordinated secondary amine. This species undergoes a retro-Mannich type reaction and imine hydrolysis (t1/2 almost-equal-to 90 s). Quenching the reaction with acid gives rise to a pair of isomeric intermediate species which have been isolated and characterized. They have a pendant arm macrocyclic structure, resulting from the loss of a methylene unit from one of the arms of the cap. Heating either isomer in aqueous solution gives the new cage compound with the contracted cap. It is postulated that this occurs through a Nef reaction, resulting in the formation of a ketone which then condenses with the coordinated primary amine. A comparison with the corresponding bicycloicosane analogue indicates a reduced chromophoric cavity size for the contracted cage. The reduction potential of the cobalt(III)/cobalt(II) couple is 170 mV more negative for the smaller cage, and, in the electronic spectrum of the cobalt(III) complex, the d-d transitions are both shifted to higher energy, corresponding to a stronger ligand field.

Trapped fermions in a synthetic non-Abelian gauge field

On increasing the coupling strength (lambda) of a non-Abelian gauge field that induces a generalized Rashba spin-orbit interaction, the topology of the Fermi surface of a homogeneous gas of noninteracting fermions of density rho similar to k(F)(3) undergoes a change at a critical value, lambda(T) approximate to k(F) [Phys. Rev. B 84, 014512 ( 2011)]. In this paper we analyze how this phenomenon affects the size and shape of a cloud of spin-1/2 fermions trapped in a harmonic potential such as those used in cold atom experiments. We develop an adiabatic formulation, including the concomitant Pancharatnam-Berry phase effects, for the one-particle states in the presence of a trapping potential and the gauge field, obtaining approximate analytical formulas for the energy levels for some high symmetry gauge field configurations of interest. An analysis based on the local density approximation reveals that, for a given number of particles, the cloud shrinks in a characteristic fashion with increasing.. We explain the physical origins of this effect by a study of the stress tensor of the system. For an isotropic harmonic trap, the local density approximation predicts a spherical cloud even for anisotropic gauge field configurations. We show, via a calculation of the cloud shape using exact eigenstates, that for certain gauge field configurations there is a systematic and observable anisotropy in the cloud shape that increases with increasing gauge coupling lambda. The reasons for this anisotropy are explained using the analytical energy levels obtained via the adiabatic approximation. These results should be useful in the design of cold atom experiments with fermions in non-Abelian gauge fields. An important spin-off of our adiabatic formulation is that it reveals exciting possibilities for the cold-atom realization of interesting condensed matter Hamiltonians by using a non-Abelian gauge field in conjunction with another potential. In particular, we show that the use of a spherical non-Abelian gauge field with a harmonic trapping potential produces a monopole field giving rise to a spherical geometry quantum Hall-like Hamiltonian in the momentum representation.

Synthesis and characterization of self-assembled nanofiber-bundles of V(2)O(5): their electrochemical and field emission properties

High-quality self-assembled V(2)O(5) nanofiber-bundles (NBs) are synthesized by a simple and direct hydrothermal method using a vanadium(V) hydroxylamido complex as a vanadium source in the presence of HNO(3). The possible reaction pathway for the formation of V(2)O(5) NBs is discussed and demonstrated that HNO(3) functions both as an oxidizing and as an acidification agent. V(2)O(5) NBs are single-crystals of an orthorhombic phase that have grown along the [010] direction. A bundle is made of indefinite numbers of homogeneous V(2)O(5) nanofibers where nanofibers have lengths up to several micrometres and widths ranging between 20 and 50 nm. As-prepared V(2)O(5) NBs display a high electrochemical performance in a non-aqueous electrolyte as a cathode material for lithium ion batteries. Field emission properties are also investigated which shows that a low turn-on field of similar to 1.84 V mu m(-1) is required to draw the emission current density of 10 mu Lambda cm(-2).

General classical theory of spinning particles in a meson field

An exact classical theory of the motion of a point dipole in a meson field is given which takes into account the effects of the reaction of the emitted meson field. The meson field is characterized by a constant $\chi =\mu /\hslash $ of the dimensions of a reciprocal length, $\mu $ being the meson mass, and as $\chi \rightarrow $ 0 the theory of this paper goes over continuously into the theory of the preceding paper for the motion of a spinning particle in a Maxwell field. The mass of the particle and the spin angular momentum are arbitrary mechanical constants. The field contributes a small finite addition to the mass, and a negative moment of inertia about an axis perpendicular to the spin axis. A cross-section (formula (88 a)) is given for the scattering of transversely polarized neutral mesons by the rotation of the spin of the neutron or proton which should be valid up to energies of 10$^{9}$ eV. For low energies E it agrees completely with the old quantum cross-section, having a dependence on energy proportional to p$^{4}$/E$^{2}$ (p being the meson momentum). At higher energies it deviates completely from the quantum cross-section, which it supersedes by taking into account the effects of radiation reaction on the rotation of the spin. The cross-section is a maximum at E $\sim $ 3$\cdot $5$\mu $, its value at this point being 3 $\times $ 10$^{-26}$ cm.$^{2}$, after which it decreases rapidly, becoming proportional to E$^{-2}$ at high energies. Thus the quantum theory of the interaction of neutrons with mesons goes wrong for E $\gtrsim $ 3$\mu $. The scattering of longitudinally polarized mesons is due to the translational but not the rotational motion of the dipole and is at least twenty thousand times smaller. With the assumption previously made by the present author that the heavy partilesc may exist in states of any integral charge, and in particular that protons of charge 2e and - e may occur in nature, the above results can be applied to charged mesons. Thus transversely polarised mesons should undergo a very big scattering and consequent absorption at energies near 3$\cdot $5$\mu $. Hence the energy spectrum of transversely polarized mesons should fall off rapidly for energies below about 3$\mu $. Scattering plays a relatively unimportant part in the absorption of longitudinally polarized mesons, and they are therefore much more penetrating. The theory does not lead to Heisenberg explosions and multiple processes.

Structural characterisation of reaction zone for friction stir welded aluminium-stainless steel joint

In the present investigation, commercially pure Al has been joined with 304 stainless steel (SS) by friction stir welding. The assembly finds widespread application in the field of cryogenics, nuclear, structural industries and domestic appliances. Microstructural characterisation was carried out using scanning and transmission electron microscopes. It has been found that diffusion of Fe, Cr and Ni is substantial within Al; however, diffusion of Al within 304SS is limited. Owing to interdiffusion of chemical species across the bondline, discrete islands of Fe3Al intermetallic form within the reaction zone. The rubbing action of tool over the butting edge of 304SS removed fine particles from 304SS, which were embedded in the stirring zone of Al matrix. Subsequently, austenite underwent phase transformation to ferrite due to large strain within this grain. Fracture path mainly moves through stirring zone of Al alloy under tensile loading; however, in some places, presence of Fe3Al compound has been also found.

Determination of electric field at and near the focus of a cylindrical lens for applications in fluorescence microscopy

We present an explicit computable integral solution of the electric field generated at the focal region of a cylindrical lens. This representation is based on vectorial diffraction theory and further enables the computation of the system point spread function of a cylindrical lens. It is assumed that there is no back-scattering and the contribution from the evanescent field is negligible. Stationary phase approximation along with the Fresnel transmission coefficients are employed for evaluating the polarization dependent electric field components. Studies were carried out to determine the polarization effects and to calculate the system resolution. The effect of s -, p - and randomly polarized light is studied on the fixed sample (electric dipole is fixed in space). Proposed approach allows better understanding of electric field effects at the focus of a cylindrical aplanatic system. This opens up future developments in the field of fluorescence microscopy and optical imaging. (C) 2013 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

Dynamics of the reaction between the free end of a tethered self-avoiding polymer and a flat penetrable surface: A renormalization group study

The average time tau(r) for one end of a long, self-avoiding polymer to interact for the first time with a flat penetrable surface to which it is attached at the other end is shown here to scale essentially as the square of the chain's contour length N. This result is obtained within the framework of the Wilemski-Fixman approximation to diffusion-limited reactions, in which the reaction time is expressed as a time correlation function of a ``sink'' term. In the present work, this sink-sink correlation function is calculated using perturbation expansions in the excluded volume and the polymer-surface interactions, with renormalization group methods being used to resum the expansion into a power law form. The quadratic dependence of tau(r) on N mirrors the behavior of the average time tau(c) of a free random walk to cyclize, but contrasts with the cyclization time of a free self-avoiding walk (SAW), for which tau(r) similar to N-2.2. A simulation study by Cheng and Makarov J. Phys. Chem. B 114, 3321 (2010)] of the chain-end reaction time of an SAW on a flat impenetrable surface leads to the same N-2.2 behavior, which is surprising given the reduced conformational space a tethered polymer has to explore in order to react. (C) 2014 AIP Publishing LLC.

Improved quasiparticle wave functions and mean field for G(0)W(0) calculations: Initialization with the COHSEX operator

The GW approximation to the electron self-energy has become a standard method for ab initio calculation of excited-state properties of condensed-matter systems. In many calculations, the G W self-energy operator, E, is taken to be diagonal in the density functional theory (DFT) Kohn-Sham basis within the G0 W0 scheme. However, there are known situations in which this diagonal Go Wo approximation starting from DFT is inadequate. We present two schemes to resolve such problems. The first, which we called sc-COHSEX-PG W, involves construction of an improved mean field using the static limit of GW, known as COHSEX (Coulomb hole and screened exchange), which is significantly simpler to treat than GW W. In this scheme, frequency-dependent self energy E(N), is constructed and taken to be diagonal in the COHSEX orbitals after the system is solved self-consistently within this formalism. The second method is called off diagonal-COHSEX G W (od-COHSEX-PG W). In this method, one does not self-consistently change the mean-field starting point but diagonalizes the COHSEX Hamiltonian within the Kohn-Sham basis to obtain quasiparticle wave functions and uses the resulting orbitals to construct the G W E in the diagonal form. We apply both methods to a molecular system, silane, and to two bulk systems, Si and Ge under pressure. For silane, both methods give good quasiparticle wave functions and energies. Both methods give good band gaps for bulk silicon and maintain good agreement with experiment. Further, the sc-COHSEX-PGW method solves the qualitatively incorrect DFT mean-field starting point (having a band overlap) in bulk Ge under pressure.

On the control of rapidly rotating convection by an axially varying magnetic field

The magnetic field in rapidly rotating dynamos is spatially inhomogeneous. The axial variation of the magnetic field is of particular importance because tall columnar vortices aligned with the rotation axis form at the onset of convection. The classical picture of magnetoconvection with constant or axially varying magnetic fields is that the Rayleigh number and wavenumber at onset decrease appreciably from their non-magnetic values. Nonlinear dynamo simulations show that the axial lengthscale of the self-generated azimuthal magnetic field becomes progressively smaller as we move towards a rapidly rotating regime. With a small-scale field, however, the magnetic control of convection is different from that in previous studies with a uniform or large-scale field. This study looks at the competing viscous and magnetic mode instabilities when the Ekman number E (ratio of viscous to Coriolis forces) is small. As the applied magnetic field strength (measured by the Elsasser number Lambda) increases, the critical Rayleigh number for onset of convection initially increases in a viscous branch, reaches an apex where both viscous and magnetic instabilities co-exist, and then falls in the magnetic branch. The magnetic mode of onset is notable for its dramatic suppression of convection in the bulk of the fluid layer where the field is weak. The viscous-magnetic mode transition occurs at Lambda similar to 1, which implies that small-scale convection can exist at field strengths higher than previously thought. In spherical shell dynamos with basal heating, convection near the tangent cylinder is likely to be in the magnetic mode. The wavenumber of convection is only slightly reduced by the self-generated magnetic field at Lambda similar to 1, in agreement with previous planetary dynamo models. The back reaction of the magnetic field on the flow is, however, visible in the difference in kinetic helicity between cyclonic and anticyclonic vortices.

Evolution of multivariant microstructures with anisotropic misfit: A phase field study

We study, in two dimensions, the effect of misfit anisotropy on microstructural evolution during precipitation of an ordered beta phase from a disordered alpha matrix; these phases have, respectively, 2- and 6-fold rotation symmetries. Thus, precipitation produces three orientational variants of beta phase particles, and they have an anisotropic (and crystallographically equivalent) misfit strain with the matrix. The anisotropy in misfit is characterized using a parameter t = epsilon(yy)/epsilon(xx), where epsilon(xx) and epsilon(yy) are the principal components of the misfit strain tensor. Our phase field, simulations show that the morphology of beta phase particles is significantly influenced by 1, the level of misfit anisotropy. Particles are circular in systems with dilatational misfit (t = 1), elongated along the direction of lower principal misfit when 0 < t < 1 and elongated along the invariant direction when - 1 <= t <= 0. In the special case of a pure shear misfit strain (t = - 1), the microstructure exhibits star, wedge and checkerboard patterns; these microstructural features are in agreement with those in Ti-Al-Nb alloys.

A New Tetrahydrofurannulation Via Tandem Radical Cyclization Reaction-Reductive Deoxygenation Sequence

Treatment of bromoketals 2, derived from allyl alcohols 1, with tributyltin chloride, sodium cyanoborohydride and AIBN furnishes the tetrahydrofurannulated products 3 via a 5-exo-trig radical cyclisation reaction followed by reductive cleavage of ketal 4.

Unsteady-Flow Of A Viscous-Fluid Between 2 Parallel Disks With A Time-Varying Gap Width And A Magnetic-Field

The unsteady incompressible viscous fluid flow between two parallel infinite disks which are located at a distance h(t*) at time t* has been studied. The upper disk moves towards the lower disk with velocity h'(t*). The lower disk is porous and rotates with angular velocity Omega(t*). A magnetic field B(t*) is applied perpendicular to the two disks. It has been found that the governing Navier-Stokes equations reduce to a set of ordinary differential equations if h(t*), a(t*) and B(t*) vary with time t* in a particular manner, i.e. h(t*) = H(1 - alpha t*)(1/2), Omega(t*) = Omega(0)(1 - alpha t*)(-1), B(t*) = B-0(1 - alpha t*)(-1/2). These ordinary differential equations have been solved numerically using a shooting method. For small Reynolds numbers, analytical solutions have been obtained using a regular perturbation technique. The effects of squeeze Reynolds numbers, Hartmann number and rotation of the disk on the flow pattern, normal force or load and torque have been studied in detail

A High-Resolution Transmission of the Precipitation Process in a Electron Microscopy Study Dilute Ti-N Alloy

The precipitation processes in dilute nitrogen alloys of titanium have been examined in detail by conventional transmission electron microscopy (CTEM) and high-resolution electron microscopy (HREM). The alloy Ti-2 at. pct N on quenching from its high-temperature beta phase field has been found to undergo early stages of decomposition. The supersaturated solid solution (alpha''-hcp) on decomposition gives rise to an intimately mixed, irresolvable product microstructure. The associated strong tweed contrast presents difficulties in understanding the characteristic features of the process. Therefore, HREM has been carried out with a view to getting a clear picture of the decomposition process. Studies on the quenched samples of the alloy suggest the formation of solute-rich zones of a few atom layers thick, randomly distributed throughout the matrix. On aging, these zones grow to a size beyond which the precipitate/matrix interfaces appear to become incoherent and the alpha' (tetragonal) product phase is seen distinctly. The structural details, the crystallography of the precipitation process, and the sequence of precipitation reaction in the system are illustrated.

Vanadium Catalysis in Bromoperoxidation Reaction

Peroxidative bromination of phenol red to its tetrabromo derivative, bromophenol blue, required vanadate in addition to H2O2 when carried out in the pH range of 5-7. Excess H2O2, with ratio of H2O2:vanadate of 2:1 and above, prevented the reaction. Diperoxovanadate, known to be formed in such reaction mixtures, was ineffective by itself and needed uncomplexed vanadate (V-v) or vanadyl (V-iv) to support bromination. Bromide-assisted reduction of the excess vanadate to vanadyl appeared to be an essential secondary reaction. In the absence of phenol red oxygen was released, and concomitantly bromide was oxidized to a form competent to brominate phenol red added after termination of oxygen release. These findings indicated participation of reactions leading to an intermediate derived from vanadyl and diperoxovanadate, previously described from this laboratory (Arch. Biochem. Biophys. 316, 319-326, 1995). Continuous bromination of phenol red occurred when glucose oxidase-glucose system was used as a source of continuous flow of H2O2. A scheme of reactions involving peroxovanadates (mono-, di-, mu-, and bromo-) is proposed for the formation and utilization of an active brominating species and for the recycling of the product, mono-peroxovanadate, by H2O2, which explains the catalytic role of vanadium in the bromoperoxidation reaction.