Magnetic Structure and Properties of the Rechargeable Battery Insertion Compound Na2FePO4F

The magnetic structure and properties of sodium iron fluorophosphate Na2FePO4F (space group Pbcn), a cathode material for rechargeable batteries, were studied using magnetometry and neutron powder diffraction. The material, which can be described as a quasi-layered structure with zigzag Fe-octahedral chains, develops a long-range antiferromagnetic order below similar to 3.4 K. The magnetic structure is rationalized as a super-exchange-driven ferromagnetic ordering of chains running along the a-axis, coupled antiferromagnetically by super-super-exchange via phosphate groups along the c-axis, with ordering along the b-axis likely due to the contribution of dipole dipole interactions.

Large-MIMO Receiver based on Linear Regression of MMSE Residual

Multiple input multiple output (MIMO) systems with large number of antennas have been gaining wide attention as they enable very high throughputs. A major impediment is the complexity at the receiver needed to detect the transmitted data. To this end we propose a new receiver, called LRR (Linear Regression of MMSE Residual), which improves the MMSE receiver by learning a linear regression model for the error of the MMSE receiver. The LRR receiver uses pilot data to estimate the channel, and then uses locally generated training data (not transmitted over the channel), to find the linear regression parameters. The proposed receiver is suitable for applications where the channel remains constant for a long period (slow-fading channels) and performs quite well: at a bit error rate (BER) of 10(-3), the SNR gain over MMSE receiver is about 7 dB for a 16 x 16 system; for a 64 x 64 system the gain is about 8.5 dB. For large coherence time, the complexity order of the LRR receiver is the same as that of the MMSE receiver, and in simulations we find that it needs about 4 times as many floating point operations. We also show that further gain of about 4 dB is obtained by local search around the estimate given by the LRR receiver.

BER Analysis of Space Shift Keying in Cooperative Multi-hop Multi-branch DF Relaying

Space shift keying (SSK) is an attractive modulation technique for multi-antenna communications. In SSK, only one among the available transmit antennas is activated during one channel use, and the index of the chosen transmit antenna conveys information. In this paper, we analyze the performance of SSK in multi-hop, multi-branch cooperative relaying systems. We consider the decode-and-forward relaying protocol, where a relay forwards the decoded symbol if it decodes the symbol correctly from the received signal. We derive closed-form expressions for the end-to-end bit error rate of SSK in this system. Analytical and simulation results match very well.

Evaluation of GODAS Using RAMA Mooring Observations from the Indian Ocean

We present a comparison of the Global Ocean Data Assimilation System (GODAS) five-day ocean analyses against in situ daily data from Research Moored Array for African-Asian-Australian Monsoon Analysis and Prediction (RAMA) moorings at locations 90 degrees E, 12 degrees N; 90 degrees E, 8 degrees N; 90 degrees E, 0 degrees N and 90 degrees E, 1.5 degrees S in the equatorial Indian Ocean and the Bay of Bengal during 2002-2008. We find that the GODAS temperature analysis does not adequately capture a prominent signal of Indian Ocean dipole mode of 2006 seen in the mooring data, particularly at 90 degrees E 0 degrees N and 90 degrees E 1.5 degrees S in the eastern India Ocean. The analysis, using simple statistics such as bias and root-mean-square deviation, indicates that standard GODAS temperature has definite biases and significant differences with observations on both subseasonal and seasonal scales. Subsurface salinity has serious deficiencies as well, but this may not be surprising considering the poorly constrained fresh water forcing, and possible model deficiencies in subsurface vertical mixing. GODAS reanalysis needs improvement to make it more useful for study of climate variability and for creating ocean initial conditions for prediction.

Metallic Nanoparticles Arranged in a Helical Geometry: Route Towards Strong and Broadband Chiro-optical Response

Recent advances in nanotechnology have paved ways to various techniques for designing and fabricating novel nanostructures incorporating noble metal nanoparticles, for a wide range of applications. The interaction of light with metal nanoparticles (NPs) can generate strongly localized electromagnetic fields (Localized Surface Plasmon Resonance, LSPR) at certain wavelengths of the incident beam. In assemblies or structures where the nanoparticles are placed in close proximity, the plasmons of individual metallic NPs can be strongly coupled to each other via Coulomb interactions. By arranging the metallic NPs in a chiral (e.g. helical) geometry, it is possible to induce collective excitations, which lead to differential optical response of the structures to right-and left circularly polarized light (e.g. Circular Dichroism - CD). Earlier reports in this field include novel techniques of synthesizing metallic nanoparticles on biological helical templates made from DNA, proteins etc. In the present work, we have developed new ways of fabricating chiral complexes made of metallic NPs, which demonstrate a very strong chiro-optical response in the visible region of the electromagnetic spectrum. Using DDA (Discrete Dipole Approximation) simulations, we theoretically studied the conditions responsible for large and broadband chiro-optical response. This system may be used for various applications, for example those related to polarization control of visible light, sensing of proteins and other chiral bio-molecules, and many more.

Fluctuating micro-heterogeneity in water-tert-butyl alcohol mixtures and lambda-type divergence of the mean cluster size with phase transition-like multiple anomalies

Water-tert-butyl alcohol (TBA) binary mixture exhibits a large number of thermodynamic and dynamic anomalies. These anomalies are observed at surprisingly low TBA mole fraction, with x(TBA) approximate to 0.03-0.07. We demonstrate here that the origin of the anomalies lies in the local structural changes that occur due to self-aggregation of TBA molecules. We observe a percolation transition of the TBA molecules at x(TBA) approximate to 0.05. We note that ``islands'' of TBA clusters form even below this mole fraction, while a large spanning cluster emerges above that mole fraction. At this percolation threshold, we observe a lambda-type divergence in the fluctuation of the size of the largest TBA cluster, reminiscent of a critical point. Alongside, the structure of water is also perturbed, albeit weakly, by the aggregation of TBA molecules. There is a monotonic decrease in the tetrahedral order parameter of water, while the dipole moment correlation shows a weak nonlinearity. Interestingly, water molecules themselves exhibit a reverse percolation transition at higher TBA concentration, x(TBA) approximate to 0.45, where large spanning water clusters now break-up into small clusters. This is accompanied by significant divergence of the fluctuations in the size of largest water cluster. This second transition gives rise to another set of anomalies around. Both the percolation transitions can be regarded as manifestations of Janus effect at small molecular level. (C) 2014 AIP Publishing LLC.

Linewidths and line shapes in the vicinity of graphene

It is well known that graphene, by virtue of its pi-cloud delocalization, has a continuum of electronic energy states and thus behaves nearly like a metal. Instances involving quenching of electronic energy excitation in fluorophores placed in the proximity of graphene sheets are well documented. In this paper, we perform theoretical investigations on the broadening of vibrational and electronic transitions in the vicinity of graphene. We find that for CO vibrations in the vicinity of undoped graphene, the broadening at a distance of 5 angstrom is similar to 0.008 cm(-1)((kappa) over tilde = 2, (kappa) over tilde being the effective dielectric constant). In comparison, for electronic transitions, the linewidth is much larger, being of the order of several cm(-1). Also, if the transition dipole were parallel to the graphene sheet, the linewidth would be reduced to half the value for the case where it is perpendicular, an observation which should be easy to check experimentally for electronic transitions. This should be observable for the f - f transitions (which are rather narrow) of Lanthanide complexes placed within a distance of a few nanometers from a graphene sheet. Further the linewidth would have a (distance)(-4) dependence as one varies the distance from graphene. (C) 2014 AIP Publishing LLC.

On Precoding for Constant K-User MIMO Gaussian Interference Channel With Finite Constellation Inputs

This paper considers linear precoding for the constant channel-coefficient K-user MIMO Gaussian interference channel (MIMO GIC) where each transmitter-i (Tx-i) requires the sending of d(i) independent complex symbols per channel use that take values from fixed finite constellations with uniform distribution to receiver-i (Rx-i) for i = 1, 2, ..., K. We define the maximum rate achieved by Tx-i using any linear precoder as the signal-to-noise ratio (SNR) tends to infinity when the interference channel coefficients are zero to be the constellation constrained saturation capacity (CCSC) for Tx-i. We derive a high-SNR approximation for the rate achieved by Tx-i when interference is treated as noise and this rate is given by the mutual information between Tx-i and Rx-i, denoted as I(X) under bar (i); (Y) under bar (i)]. A set of necessary and sufficient conditions on the precoders under which I(X) under bar (i); (Y) under bar (i)] tends to CCSC for Tx-i is derived. Interestingly, the precoders designed for interference alignment (IA) satisfy these necessary and sufficient conditions. Furthermore, we propose gradient-ascentbased algorithms to optimize the sum rate achieved by precoding with finite constellation inputs and treating interference as noise. A simulation study using the proposed algorithms for a three-user MIMO GIC with two antennas at each node with d(i) = 1 for all i and with BPSK and QPSK inputs shows more than 0.1-b/s/Hz gain in the ergodic sum rate over that yielded by precoders obtained from some known IA algorithms at moderate SNRs.

Channel Hardening-Exploiting Message Passing (CHEMP) Receiver in Large-Scale MIMO Systems

In this paper, we propose a multiple-input multiple-output (MIMO) receiver algorithm that exploits channel hardening that occurs in large MIMO channels. Channel hardening refers to the phenomenon where the off-diagonal terms of the matrix become increasingly weaker compared to the diagonal terms as the size of the channel gain matrix increases. Specifically, we propose a message passing detection (MPD) algorithm which works with the real-valued matched filtered received vector (whose signal term becomes, where is the transmitted vector), and uses a Gaussian approximation on the off-diagonal terms of the matrix. We also propose a simple estimation scheme which directly obtains an estimate of (instead of an estimate of), which is used as an effective channel estimate in the MPD algorithm. We refer to this receiver as the channel hardening-exploiting message passing (CHEMP) receiver. The proposed CHEMP receiver achieves very good performance in large-scaleMIMO systems (e.g., in systems with 16 to 128 uplink users and 128 base station antennas). For the considered large MIMO settings, the complexity of the proposed MPD algorithm is almost the same as or less than that of the minimum mean square error (MMSE) detection. This is because the MPD algorithm does not need a matrix inversion. It also achieves a significantly better performance compared to MMSE and other message passing detection algorithms using MMSE estimate of. Further, we design optimized irregular low density parity check (LDPC) codes specific to the considered large MIMO channel and the CHEMP receiver through EXIT chart matching. The LDPC codes thus obtained achieve improved coded bit error rate performance compared to off-the-shelf irregular LDPC codes.

The role of buoyancy in polarity reversals of the geodynamo

We investigate polarity reversals in the geodynamo using a rotating, convection-driven dynamo model. As the flow in rapidly rotating convection is dominated by columns aligned with the axis of rotation, the focus is on the dynamics of columnar vortices. By studying the growth of a seed magnetic field to a stable axial dipole field, we show that the magnetic field acts in ways that significantly enhance the relative helicity between cyclonic and anticyclonic vortices. This flow asymmetry is the hallmark of a dipolar dynamo. Strong buoyancy, on the other hand, offsets the effect of the magnetic field, establishing parity between positive and negative vortices. As the dipole field is deprived of the helicity required to support itself, the dynamo is pushed into a reversing state. This is a likely regime for polarity reversals in the Earth's core. The integral lengthscale at which buoyancy injects energy is not significantly different from the convective flow lengthscale, which implies that buoyancy does not feed vortices at the small scales where non-linear inertia is present. The lengthscale at which the Lorentz force acts in the reversing dynamo is small, which may allow the passive presence of non-linear inertia in the small scales.

Charge density distribution and electrostatic interactions of ethionamide: an inhibitor of the enoyl acyl carrier protein reductase (inhA) enzyme of Mycobacterium tuberculosis

An experimental charge density analysis of an anti-TB drug ethionamide was carried out from high resolution X-ray diffraction at 100 K to understand its charge density distribution and electrostatic properties. The experimental results were validated from periodic theoretical charge density calculations performed using CRYSTAL09 at the B3LYP/6-31G** level of theory. The electron density rho(bcp)(r) and the Laplacian of electron density del(2)(rho bcp)(r) of the molecule calculated from both the methods display the charge density distribution of the ethionamide molecule in the crystal field. The electrostatic potential map shows a large electropositive region around the pyridine ring and a large electronegative region at the vicinity of the thiol atom. The calculated experimental dipole moment is 10.6D, which is higher than the value calculated from theory (8.2D). The topological properties of C-H center dot center dot center dot S, N-H center dot center dot center dot N and N-H center dot center dot center dot S hydrogen bonds were calculated, revealing their strength. The charge density analysis of the ethionamide molecule determined from both the experiment and theory gives the topological and electrostatic properties of the molecule, which allows to precisely understand the nature of intra and intermolecular interactions.

Photoluminescence, photocatalysis and Judd-Ofelt analysis of Eu3+-activated layered BiOCl phosphors

Eu3+-activated layered BiOCl phosphors were synthesized by the conventional solid-state method at relatively low temperature and shorter duration (400 degrees C for 1 h). All the samples were crystallized in the tetragonal structure with the space group P4/nmm (no. 129). Field emission scanning electron microscopy (FE-SEM) studies confirmed the plate-like morphology. Photoluminescence spectra exhibit characteristic luminescent D-5(0) -> F-7(J) (J = 0-4) intra-4f shell Eu3+ ion transitions. The electric dipole transition located at 620 nm (D-5(0) -> F-7(2)) was stronger than the magnetic dipole transition located at 594 nm (D-5(0) -> F-7(1)). The evaluated Commission International de l'Eclairage (CIE) color coordinates of Eu3+-activated BiOCl phosphors were close to the commercial Y2O3:Eu3+ and Y2O2S:Eu3+ red phosphors. Intensity parameters (Omega(2), Omega(4)) and various radiative properties such as transition probability (A(tot)), radiative lifetime (tau(rad)), stimulated emission cross-section (sigma(e)), gain bandwidth (sigma(e) x Delta lambda(eff)) and optical gain (sigma(e) x tau(rad)) were calculated using the Judd-Ofelt theory. The experimental decay curves of the D-5(0) level in Eu3+-activated BiOCl have a single exponential profile. In comparison with other Eu3+ doped materials, Eu3+-activated BiOCl phosphors have a long lifetime (tau(exp)), low non-radiative relaxation rate (W-NR), high quantum efficiency (eta) and better optical gain (sigma(e) x tau(rad)). The determined radiative properties revealed the usefulness of Eu3+-activated BiOCl in developing red lasers as well as optical display devices. Further, these samples showed efficient photocatalytic activity for the degradation of rhodamine B (RhB) dye under visible light irradiation. These photocatalysts are useful for the removal of toxic and non-biodegradable organic pollutants in water.

Sensitivity of polarization fluctuations to the nature of protein-water interactions: Study of biological water in four different protein-water systems

Since the time of Kirkwood, observed deviations in magnitude of the dielectric constant of aqueous protein solution from that of neat water (similar to 80) and slower decay of polarization have been subjects of enormous interest, controversy, and debate. Most of the common proteins have large permanent dipole moments (often more than 100 D) that can influence structure and dynamics of even distant water molecules, thereby affecting collective polarization fluctuation of the solution, which in turn can significantly alter solution's dielectric constant. Therefore, distance dependence of polarization fluctuation can provide important insight into the nature of biological water. We explore these aspects by studying aqueous solutions of four different proteins of different characteristics and varying sizes, chicken villin headpiece subdomain (HP-36), immunoglobulin binding domain protein G (GB1), hen-egg white lysozyme (LYS), and Myoglobin (MYO). We simulate fairly large systems consisting of single protein molecule and 20000-30000 water molecules (varied according to the protein size), providing a concentration in the range of similar to 2-3 mM. We find that the calculated dielectric constant of the system shows a noticeable increment in all the cases compared to that of neat water. Total dipole moment auto time correlation function of water < dM(W) (0)delta M-W (t) > is found to be sensitive to the nature of the protein. Surprisingly, dipole moment of the protein and total dipole moment of the water molecules are found to be only weakly coupled. Shellwise decomposition of water molecules around protein reveals higher density of first layer compared to the succeeding ones. We also calculate heuristic effective dielectric constant of successive layers and find that the layer adjacent to protein has much lower value (similar to 50). However, progressive layers exhibit successive increment of dielectric constant, finally reaching a value close to that of bulk 4-5 layers away. We also calculate shellwise orientational correlation function and tetrahedral order parameter to understand the local dynamics and structural re-arrangement of water. Theoretical analysis providing simple method for calculation of shellwise local dielectric constant and implication of these findings are elaborately discussed in the present work. (C) 2014 AIP Publishing LLC.

Ionic Bonding between Artificial Atoms

Conventional solids are prepared from building blocks that are conceptually no larger than a hundred atoms. While van der Waals and dipole-dipole interactions also influence the formation of these materials, stronger interactions, referred to as chemical bonds, play a more decisive role in determining the structures of most solids. Chemical bonds that hold such materials together are said to be ionic, covalent, metallic, dative, or otherwise a combination of these. Solids that utilize semiconductor nanocrystal quantum dots as building units have been demonstrated to exist; however, the interparticle forces in such materials are decidedly not chemical. Here we demonstrate the formation of charge transfer states in a binary quantum dot mixture. Charge is observed to reside in quantum confined states of one of the participating quantum dots. These interactions lead to materials that may be regarded as the nanoscale analog of an ionic solid. The process by which these materials form has interesting parallels to chemical reactions in conventional chemistry.

Performance Analysis of Space-Shift Keying in Decode-and-Forward Multihop MIMO Networks

In this paper, space-shift keying (SSK) is considered for multihop multiple-input-multiple-output (MIMO) networks. In SSK, only one among n(s) = 2(m) available transmit antennas, chosen on the basis of m information bits, is activated during transmission. We consider two different systems of multihop co-operation, where each node has multiple antennas and employs SSK. In system I, a multihop diversity relaying scheme is considered. In system II, a multihop multibranch relaying scheme is considered. In both systems, we adopt decode-and-forward (DF) relaying, where each relay forwards the signal only when it correctly decodes. We analyze the end-to-end bit error rate (BER) and diversity order of both the systems with SSK. For binary SSK (n(s) = 2), our analytical BER expression is exact, and our numerical results show that the BERs evaluated through the analytical expression overlap with those obtained through Monte Carlo simulations. For nonbinary SSK (n(s) > 2), we derive an approximate BER expression, where the analytically evaluated BER results closely follow the simulated BER results. We show the comparison of the BERs of SSK and conventional phase-shift keying (PSK) and also show the instances where SSK outperforms PSK. We also present the diversity analyses for SSK in systems I and II, which predict the achievable diversity orders as a function of system parameters.