Complete 'melting' of charge order in hydrothermally grown Pr0.57Ca0.41Ba0.02MnO3 nanowires

Nanowires of Pr0.57Ca0.41Ba0.02MnO3 (PCBM) (diameter similar to 80-90 nm and length similar to 3.5 mu m) were synthesized by a low reaction temperature hydrothermal method. Single-phase nature of the sample was confirmed by XRD experiments. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the morphology and microstructures of the nanowires. While the bulk PCBM is known to exhibit charge order (CO) below 230 K along with a ferromagnetic transition at 110 K, SQUID measurements on the nanowires of PCBM show that the charge order is completely absent and a ferromagnetic transition occurs at 115 K. However, the magnetization in the nanowires is observed to be less compared to that in the bulk. This observation of the complete 'melting' of the charge order in the PCBM nanowires is particularly significant in view of the observation of only a weakening of the CO in the nanowires of Pr0.5Ca0.5MnO3. Electron paramagnetic resonance experiments were also carried out on the PCBM nanowires using an X-band EPR spectrometer. Characteristic differences were observed in the line width of nanowires when compared with that of the bulk.

Crystal packing and melting temperatures of small oxalate esters: the role of C-H center dot center dot center dot O hydrogen bonding

The simple dialkyl oxalates are generally liquids at room temperature except for dimethyl and di-tert-butyl oxalate which melt at 327 and 343 K. The crystal structures of diethyl, di-iso-propyl, di-n-butyl, di-tert-butyl and methyl ethyl oxalates were determined. The liquid esters were crystallized using the cryocrystallization technique. A comparison of the intermolecular interactions and packing features in these crystal structures was carried out. The crystal structure of dimethyl oxalate was redetermined at various temperatures. The other compounds were also studied at several temperatures in order to assess the attractive nature of the hydrogen bonds therein. A number of moderate to well defined C-H center dot center dot center dot O interactions account for the higher melting points of the two solid esters. Additionally, a diminished entropic contribution Delta S(m) in di-tert-butyl oxalate possibly increases the melting point of this compound further.

Microstructure, shape, stability and melting inembeddednanoparticles

The present article reviews some of the current work on a new class of materials which are nanoscale granular materials. We shall discuss in this paper two phase granular materials where one of the phases having nanometric dimension is embedded in a matrix of larger dimension. Known as nanoembedded materials, nanocomposites or ultrafine granular materials, this class of materials has attracted attention because of the opportunity of basic studies on the effect of size and embedding matrix on transformation behaviors as well as some novel properties, which include structural, magnetic and transport properties. These are in addition to the tremendous interests in what is known as quantum structures(embedded particles size less than 5 nm) for the case of semiconductors, which will not be discussed here. We shall primarily review the work done on metallic systems where the dispersed phases have low melting points and borrow extensively from the work done in our group. The phase transformations of the embedded particles show distinctive behavior and yield new insights. We shall first highlight briefly the strategy of synthesis of these materials by non-equilibrium processing techniques, which will be followed by examples where the effect of length scales on phase transformation behaviors like melting and solidification are discussed.

Universalities in vortex transport at the melting transition

We consider the jump in resistance at the melting transition, which is experimentally observed to be constant, independent of magnetic field (vortex density). We present an explanation of this effect based on vortex cuttings, and universalities of the structure factor at the freezing transition (the Hansen-Verlet criterion).

Non-resonant rf absorption evidence for reentrant melting of vortex lattice in Bi2Sr2CaCu2O8 single crystals

We have studied the magnetic field dependent rf (20 MHz) losses in Bi2Sr2CaCu2O8 single crystals in the low field and high temperature regime. Above HCl the dissipation begins to decrease as the field is increased and exhibits a minimum at HM>HCl. For H>HM the loss increases monotonically. We attribute the decrease in loss above HCl to the stiffening of the vortex lines due to the attractive electromagnetic interaction between the 2D vortices (that comprise the vortex line at low fields) in adjacent CuO bilayers. The minimum at HM implies that the vortex lines are stiffest and hence represents a transition into vortex solid state from the narrow vortex liquid in the vicinity of HCl. The increase in loss for H>HM marks the melting of the vortex lattice and hence a second transition into vortex liquid regime. We discuss our results in the light of recent theory of reentrant melting of the vortex lattice by G. Blatter et al. (Phys. Rev. B 54, 72 (1996)).

Thermodynamic Models for the Size-dependent Melting of Nanoparticles: Different Hypotheses

A careful comparison of the experimental results reported in the literature reveals different variations of the melting temperature even for the same materials. Though there are different theoretical models, thermodynamic model has been extensively used to understand different variations of size-dependent melting of nanoparticles. There are different hypotheses such as homogeneous melting (HMH), liquid nucleation and growth (LNG) and liquid skin melting (LSM) to resolve different variations of melting temperature as reported in the literature. HMH and LNG account for the linear variation where as LSM is applied to understand the nonlinear behaviour in the plot of melting temperature against reciprocal of particle size. However, a bird's eye view reveals that either HMH or LSM has been extensively used by experimentalists. It has also been observed that not a single hypothesis can explain the size-dependent melting in the complete range. Therefore we describe an approach which can predict the plausible hypothesis for a given data set of the size-dependent melting temperature. A variety of data have been analyzed to ascertain the hypothesis and to test the approach.

Simulation of Influence of Bilayer Melting on Dynamics and Thermodynamics of Interfacial Water

We investigate the effect of bilayer melting transition on thermodynamics and dynamics of interfacial water using molecular dynamics simulation with the two-phase thermodynamic model. We show that the diffusivity of interface water depicts a dynamic crossover at the chain melting transition following an Arrhenius behavior until the transition temperature. The corresponding change in the diffusion coefficient from the bulk to the interface water is comparable with experimental observations found recently for water near 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) vesicles Phys. Chem. Chem. Phys. 13, 7732 (2011)]. The entropy and potential energy of interfacial water show distinct changes at the bilayer melting transition, indicating a strong correlation in the thermodynamic state of water and the accompanying first-order phase transition of the bilayer membrane. DOI: 10.1103/PhysRevLett.110.018303

Anisotropy induced crossover from weakly to strongly first order melting of two dimensional solids

Melting and freezing transitions in two dimensional (2D) systems are known to show highly unusual characteristics. Most of the earlier studies considered atomic systems: the melting of 2D molecular solids is still largely unexplored. In order to understand the role of anisotropy as well as multiple energy and length scales present in molecular systems, here we report computer simulation studies of melting of 2D molecular systems. We computed a limited portion of the solid-liquid phase diagram. We find that the interplay between the strength of isotropic and anisotropic interactions can give rise to rich phase diagram consisting of isotropic liquid and two crystalline phases-honeycomb and oblique. The nature of the transition depends on the relative strength of the anisotropic interaction and a strongly first order melting turns into a weakly first order transition on increasing the strength of the isotropic interaction. This crossover can be attributed to an increase in stiffness of the solid phase free energy minimum on increasing the strength of the anisotropic interaction. The defects involved in melting of molecular systems are quite different from those known for the atomic systems.

Remote sensing study of snowline altitude at the end of melting season, Chandra-Bhaga basin, Himachal Pradesh, 1980-2007

Glaciers have a direct relation with climate change. The equilibrium line altitude (ELA) is the most useful parameter to study the effect of climate change on glaciers. The ELA is a theoretical snowline at which the glacier mass balance is zero. Snowline altitude (SLA) at the end of melting season is generally regarded as the ELA. Glaciers of Chandra-Bhaga basin in Lahaul-Spiti district of Himachal Pradesh were chosen to study the ELA, using satellite images from 1980 to 2007. A total of 19 glaciers from the Chandra-Bhaga basin were identified and selected to carry out the study of ELA variation over 27 years. This study reveals that the mean SLA of the sub-basin has increased from 5009 +/- 61m to 5401 +/- 21m from 1980 to 2007. The study is in agreement with the reported increase in the temperature and decrease in winter snowfall of North-West Himalaya in the last century.

Melting and solidification behavior of Pb-Sn embedded alloy nano-particles

Nano-sized bimetallic dispersoids consisting of (Pb) and beta-(Sn) phases of eutectic composition (Pb26.1Sn73.9) embedded in aluminum and Al-Cu-Fe quasicrystalline matrices have been prepared by rapid solidification processing. The two phases, face centered cubic (Pb) and body center tetragonal, beta-(Sn) solid solution co-exist in all the embedded nanoparticles at room temperature. The phases bear crystallographic orientation relationship with the matrix. In situ TEM study has been carried out for the alloy particles to study the melting and the solidification behavior. The detailed microscopic observations indicate formation of a single-phase metastable fcc (Pb) in the nano-particles prior to the melting during heating. Solidification of these particles begins with nucleation of fcc (Pb), which phase separates into fcc (Pb) and beta-(Sn) lamellae in the solid state. In situ X-ray diffraction study is carried out to obtain lattice parameter of metastable fcc (Pb) and thereby an estimate of amount of Sn dissolved in the metastable (Pb) prior to the melting. The results are discussed in terms of a metastable phase diagram between fcc Pb and fcc Sn and invoking the size effect on the metastable phase diagram. The size factor is found to play a critical role in deciding the pathway of phase transformation as well as the extension of solid solubility of Sn in fcc (Pb) in the nano-particles.

Energy funneling and macromolecular conformational dynamics: a 2D Raman correlation study of PEG melting

Cascading energy landscapes through funneling has been postulated as a mechanistic route for achieving the lowest energy configuration of a macromolecular system (such as proteins and polymers). In particular, understanding the molecular mechanism for the melting and crystallization of polymers is a challenging fundamental question. The structural modifications that lead to the melting of poly(ethylene glycol) (PEG) are investigated here. Specific Raman bands corresponding to different configurations of the PEG chain have been identified, and the molecular structural dynamics of PEG melting have been addressed using a combination of Raman spectroscopy, 2D Raman correlation and density functional theory (DFT) calculations. The melting dynamics of PEG have been unambiguously explained along the C-O bond rotation coordinate.

Comparative Study of Protein Unfolding in Aqueous Urea and Dimethyl Sulfoxide Solutions: Surface Polarity, Solvent Specificity, and Sequence of Secondary Structure Melting

Elucidation of possible pathways between folded (native) and unfolded states of a protein is a challenging task, as the intermediates are often hard to detect. Here, we alter the solvent environment in a controlled manner by choosing two different cosolvents of water, urea, and dimethyl sulfoxide (DMSO) and study unfolding of four different proteins to understand the respective sequence of melting by computer simulation methods. We indeed find interesting differences in the sequence of melting of alpha helices and beta sheets in these two solvents. For example, in 8 M urea solution, beta-sheet parts of a protein are found to unfold preferentially, followed by the unfolding of alpha helices. In contrast, 8 M DMSO solution unfolds alpha helices first, followed by the separation of beta sheets for the majority of proteins. Sequence of unfolding events in four different alpha/beta proteins and also in chicken villin head piece (HP-36) both in urea and DMSO solutions demonstrate that the unfolding pathways are determined jointly by relative exposure of polar and nonpolar residues of a protein and the mode of molecular action of a solvent on that protein.

Nonequilibrium ``Melting'' of a Charge Density Wave Insulator via an Ultrafast Laser Pulse

We employ an exact solution of the simplest model for pump-probe time-resolved photoemission spectroscopy in charge-density-wave systems to show how, in nonequilibrium, the gap in the density of states disappears while the charge density remains modulated, and then the gap reforms after the pulse has passed. This nonequilibrium scenario qualitatively describes the common short-time experimental features in TaS2 and TbTe3, indicating a quasiuniversality for nonequilibrium ``melting'' with qualitative features that can be easily understood within a simple picture.

Sign changes of Fourier coefficients of Hilbert modular forms

Sign changes of Fourier coefficients of various modular forms have been studied. In this paper, we analyze some sign change properties of Fourier coefficients of Hilbert modular forms, under the assumption that all the coefficients are real. The quantitative results on the number of sign changes in short intervals are also discussed. (C) 2014 Elsevier Inc. All rights reserved.

Succinate esters: odd-even effects in melting points

Dialkyl succinates show a pattern of alternating behavior in their melting points, as the number of C atoms in the alkane side chain increases, unlike in the dialkyl oxalates Joseph et al. (2011). Acta Cryst. B67, 525-534]. Dialkyl succinates with odd numbers of C atoms in the alkyl side chain show higher melting points than the immediately adjacent analogues with even numbers. The crystal structures and their molecular packing have been analyzed for a series of dialkyl succinates with 1 - 4 C atoms in the alkyl side chain. The energy difference (Delta E) between the optimized and observed molecular conformations, density, Kitaigorodskii packing index (KPI) and C-H center dot center dot center dot O interactions are considered to rationalize this behavior. In contrast to the dialkyl oxalates where a larger number of moderately strong C-H center dot center dot center dot O interactions were characteristic of oxalates with elevated melting points, here the molecular packing and the density play a major role in raising the melting point. On moving from oxalate to succinate esters the introduction of the C2 spacer adds two activated H atoms to the asymmetric unit, resulting in the formation of stronger C-H center dot center dot center dot O hydrogen bonds in all succinates. As a result the crystallinity of long-chain alkyl substituted esters improves enormously in the presence of hydrogen bonds from activated donors.