Single-molecule thermodynamics: the heat distribution function of a charged particle in a static magnetic field

Interest in the applicability of fluctuation theorems to the thermodynamics of single molecules in external potentials has recently led to calculations of the work and total entropy distributions of Brownian oscillators in static and time-dependent electromagnetic fields. These calculations, which are based on solutions to a Smoluchowski equation, are not easily extended to a consideration of the other thermodynamic quantity of interest in such systems-the heat exchanges of the particle alone-because of the nonlinear dependence of the heat on a particle's stochastic trajectory. In this paper, we show that a path integral approach provides an exact expression for the distribution of the heat fluctuations of a charged Brownian oscillator in a static magnetic field. This approach is an extension of a similar path integral approach applied earlier by our group to the calculation of the heat distribution function of a trapped Brownian particle, which was found, in the limit of long times, to be consistent with experimental data on the thermal interactions of single micron-sized colloids in a viscous solvent.

Collective Effects on Single Particle Orientational Relaxation in Slow Dipolar Liquids

Theoretical and computer simulation studies of orientational relaxation in dense molecular liquids are presented. The emphasis of the study is to understand the effects of collective orientational relaxation on the single-particle orientational dynamics. The theoretical analysis is based on a recently developed molecular hydrodynamic theory which allows a self-consistent description of both the collective and the single-particle orientational relaxation. The molecular hydrodynamic theory can be used to derive a relation between the memory function for the collective orientational correlation function and the frequency-dependent dielectric function. A novel feature of the present work is the demonstration that this collective memory function is significantly different from the single-particle rotational friction. However, a microscopic expression for the single-particle rotational friction can be derived from the molecular hydrodynamic theory where the collective memory function can be used to obtain the single-particle orientational friction. This procedure allows, us to calculate the single-particle orientational correlation function near the alpha-beta transition in the supercooled liquid. The calculated correlation function shows an interesting bimodal decay below the bifurcation temperature as the glass transition is approached from above. Brownian dynamics simulations have been carried out to check the validity of the above procedure of translating the memory function from the dielectric relaxation data. We have also investigated the following two issues important in understanding the orientational relaxation in slow liquids. First, we present an analysis of the ''orientational caging'' of translational motion. The value of the translational friction is found to be altered significantly by the orientational caging. Second, we address the question of the rank dependence of the dielectric friction using both simulation and the molecular hydrodynamic theory.

Partition function for hindered, one-and multi-dimensional rotors

Writing the hindered rotor (hr) partition function as the trace of (rho) over cap = e(-beta(H) over cap hr), we approximate it by the sum of contributions from a set of points in position space. The contribution of the density matrix from each point is approximated by performing a local harmonic expansion around it. The highlight of this method is that it can be easily extended to multidimensional systems. Local harmonic expansion leads to a breakdown of the method a low temperatures. In order to calculate the partition function at low temperatures, we suggest a matrix multiplication procedure. The results obtained using these methods closely agree with the exact partition function at all temperature ranges. Our method bypasses the evaluation of eigenvalues and eigenfunctions and evaluates the density matrix for internal rotation directly. We also suggest a procedure to account for the antisymmetry of the total wavefunction in the same. (C) 2012 Elsevier B.V. All rights reserved.

Ni Nano-particle Encapsulated in Hollow Carbon Sphere Electrocatalyst in Polymer Electrolyte Membrane Water Electrolyzer

The present study evaluates the synthesis by solvo-thermal method and electrocatalytic activity of nickel nano-particles encapsulated in hollow carbon sphere, in hydrogen and oxygen evolution reaction in PEM water electrolyzer. The XRD patterns have ascertained the formation of nickel metal with different planes in face centered cubic (fcc) and hexagonal closed pack (hcp) form. SEM and TEM images have confirmed the nickel nano-particles with diameter of 10-50 nm inside the 0.2 mu m sized hollow carbon spheres. The BET surface area values gradually decreased with greater encapsulation of nickel; although the electrochemical active surface area (ECSA) values have been calculated as quite higher. It confirms the well dispersion of nickel in the materials and induces their electrocatalytic performance through the active surface sites. The cyclic voltammetric studies have evaluated hydrogen desorption peaks as five times more intense in nickel encapsulated materials, in comparison to the pure hollow carbon spheres. The anodic peak current density value has reached the highest level of 1.9 A cm(-2) for HCSNi10, which gradually decreases with lesser amount of nickel in the electrocatalysts. These electrocatalysts have been proved electrochemically stable during their usage for 48 h long duration under potentiostatic condition. (C) 2015 Elsevier Ltd. All rights reserved.

A Few Case Studies on the Correlation of Particle Network and Its Stability on the Ionic Conductivity of Solid-Liquid Composite Electrolytes

We discuss here the crucial role of the particle network and its stability on the long-range ion transport in solid liquid composite electrolytes. The solid liquid composite electrolytes chosen for the study here comprise nanometer sized silica (SiO2) particles having various surface chemical functionalities dispersed in nonaqueous lithium salt solutions, viz, lithium perchlorate (LiClO4) in two different polyethylene glycol based solvents. These systems constitute representative examples of an independent class of soft matter electrolytes known as ``soggy sand'' electrolytes, which have tremendous potential in diverse electrochemical devices. The oxide additive acts as a heterogeneous dopant creating free charge carriers and enhancing the local ion transport. For long-range transport, however, a stable spanning particle network is needed. Systematic experimental investigations here reveal that the spatial and time dependent characteristics of the particle network in the liquid solution are nontrivial. The network characteristics are predominantly determined by the chemical makeup of the electrolyte components and the chemical interactions between them. It is noteworthy that in this study the steady state macroscopic ionic conductivity and viscosity of the solid liquid composite electrolyte are observed to be greatly determined by the additive oxide surface chemical functionality, solvent chemical composition, and solvent dielectric constant.

Particle Size-Dependent Charge Ordering and Magnetic Properties in Pr0.55Ca0.45MnO3

A series of Pr0.55Ca0.45MnO3 compounds with average particle size ranging from 2000 to 30 nm have been synthesized by the sol-gel method and their charge ordering (CO) and magnetic properties are investigated. It is observed that with particle size decreasing, the CO transition is gradually suppressed and finally disappears upon particle size down to 35 nm, while the ferromagnetism (FM) emerges and exhibits a nonmonotonous variation with a maximum at 45 nm samples. The FM components in all samples never reach long-range ordering but rather only show short-range clusters. A new explanation considering the coupling between lattice, charge, and spin in the system is raised to understand the suppression of the CO state, Both the competition between the CO/AFM and FM states and the core-shell model are employed to explain the variation of the FM phase. These results may provide a deeper insight into the physics of particle size effect on the charge ordering manganite.

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Superfine mineral materials are mainly resulted from the pulverization of natural mineral resources, and are a type of new materials that can replace traditional materials and enjoy the most extensive application and the highest degree of consumption in the present day market. As a result, superfine mineral materials have a very broad and promising prospect in terms of market potential. Superfine pulverization technology is the only way for the in-depth processing of most of the traditional materials, and is also one of the major means for which mineral materials can realize their application. China is rich in natural resources such as heavy calcite, kaolin, wollastonite, etc., which enjoy a very wide market of application in paper making, rubber, plastics, painting, coating, medicine, environment-friendly recycle paper and fine chemical industries, for example. However, because the processing of these resources is generally at the low level, economic benefit and scale for the processing of these resources have not been realized to their full potential even up to now. Big difference in product indices and superfine processing equipment and technologies between China and advanced western countries still exists. Based on resource assessment and market potential analysis, an in-depth study was carried out in this paper about the superfine pulverization technology and superfine pulverized mineral materials from the point of mineralogical features, determination of processing technologies, analytical methods and applications, by utilizing a variety of modern analytical methods in mineralogy, superfine pulverization technology, macromolecular chemistry, material science and physical chemistry together with computer technology and so on. The focus was placed on the innovative study about the in-depth processing technology and the processing apparatus for kaolin and heavy calcite as well as the application of superfine products. The main contents and the major achievements of this study are listed as follows: 1. Superfine pulverization processing of mineral materials shall be integrated with the study of their crystal structures and chemical composition. And special attention shall be put on the post-processing technologies, rather than on the indices for particle size, of these materials, based on their fields of application. Both technical feasibility and economic feasibility shall be taken into account for the study about superfine pulverization technologies, since these two kinds of feasibilities serve as the premise for the industrialized application of superfine pulverized mineral materials. Based on this principle, preposed chemical treatment method, technology of synchronized superfine pulverization and gradation, processing technology and apparatus of integrated modification and depolymerization were utilized in this study, and narrow distribution in terms of particle size, good dispersibility, good application effects, low consumption as well as high effectiveness of superfine products were achieved in this study. Heavy calcite and kaolin are two kinds of superfine mineral materials that enjoy the highest consumption in the industry. Heavy calcite is mainly applied in paper making, coating and plastics industries, the hard kaolin in northern China is mainly used in macromolecular materials and chemical industries, while the soft kaolin in southern China is mainly used for paper making. On the other hand, superfine pulverized heavy calcite and kaolin can both be used as the functional additives to cement, a kind of material that enjoys the biggest consumption in the world. A variety of analytical methods and instruments such as transmission and scanning electron microscopy, X-ray diffraction analysis, infrared analysis, laser particle size analysis and so on were applied for the elucidation of the properties and the mechanisms for the functions of superfine mineral materials as used in plastics and high-performance cement. Detection of superfine mineral materials is closely related to the post-processing and application of these materials. Traditional detection and analytical methods for superfine mineral materials include optical microscopy, infrared spectral analysis and a series of microbeam techniques such as transmission and scanning electron microscopy, X-ray diffraction analysis, and so on. In addition to these traditional methods, super-weak luminescent photon detection technology of high precision, high sensitivity and high signal to noise ratio was also utilized by the author for the first time in the study of superfine mineral materials, in an attempt to explore a completely new method and means for the study of the characterization of superfine materials. The experimental results are really exciting! The innovation of this study is represented in the following aspects: 1. In this study, preposed chemical treatment method, technology of synchronized superfine pulverization and gradation, processing technology and apparatus of integrated modification and depolymerization were utilized in an innovative way, and narrow distribution in terms of particle size, good dispersibility, good application effects, low consumption as well as high effectiveness of superfine products were achieved in the industrialized production process*. Moreover, a new modification technology and related directions for producing the chemicals were invented, and the modification technology was even awarded a patent. 2. The detection technology of super-weak luminescent photon of high precision, high sensitivity and high signal to noise ratio was utilized for the first time in this study to explore the superfine mineral materials, and the experimental results can be compared with those acquired with scanning electron microscopy and has demonstrated its unique advantages. It can be expected that further study may possibly help to result in a completely new method and means for the characterization of superfine materials. 3. During the heating of kaolinite and its decomposition into pianlinite, the diffraction peaks disappear gradually. First comes the disappearance of the reflection of the basal plane (001), and then comes the slow disappearance of the (hkl) diffraction peaks. And this was first discovered during the experiments by the author, and it has never before reported by other scholars. 4. The first discovery of the functions that superfine mineral materials can be used as dispersants in plastics, and the first discovery of the comprehensive functions that superfine mineral materials can also be used as activators, water-reducing agents and aggregates in high-performance cement were made in this study, together with a detailed discussion. This study was jointly supported by two key grants from Guangdong Province for Scientific and Technological Research in the 10th Five-year Plan Period (1,200,000 yuan for Preparation technology, apparatus and post-processing research by using sub-micron superfine pulverization machinery method, and 300,000 yuan for Method and instruments for biological photon technology in the characterization of nanometer materials), and two grants from Guangdong Province for 100 projects for scientific and technological innovation (700,000 yuan for Pilot experimentation of superfine and modified heavy calcite used in paper-making, rubber and plastics industry, and 400,000 yuan for Study of superfine, modified wollastonite of large length-to-diameter ratio).

The effect of Rh particle size on the catalytic performance of porous silica supported rhodium catalysts for CO hydrogenation

Silica-supported Rh catalysts with different Rh particle dimensions were investigated for CO hydrogenation. The catalysts were characterized by various techniques such as TEM, H-2-TPR and N-2 adsorption to study the catalyst morphology, the size distributions of Rh particles and the silica pores. It was found that the distribution and the size of Rh particles were affected by the silica pores, and the metal grains were enclosed in the pores of the support, and thereby their growth was limited. The catalytic activity and selectivity to C-2-oxygenates for CO hydrogenation were found to be significantly controlled by the Rh particle sizes, and the higher activity and selectivity to C2-oxygenates were obtained over bigger Rh particles, within the range of the reported particle sizes.

SERS enhancement by aggregated Au colloids: effect of particle size

Aggregated Au colloids have been widely used as SERS enhancing media for many years but to date there has been no systematic investigation of the effect of the particle size on the enhancements given by simple aggregated Au colloid solutions. Previous systematic studies on isolated particles in solution or multiple particles deposited onto surfaces reported widely different optimum particle sizes for the same excitation wavelength and also disagreed on the extent to which surface plasmon absorption spectra were a good predictor of enhancement factors. In this work the spectroscopic properties of a range of samples of monodisperse Au colloids with diameters ranging from 21 to 146 nm have been investigated in solution. The UV/visible absorption spectra of the colloids show complex changes as a function of aggregating salt (MgSO4) concentration which diminish when the colloid is fully aggregated. Under these conditions, the relative SERS enhancements provided by the variously sized colloids vary very significantly across the size range. The largest signals in the raw data are observed for 46 nm colloids but correction for the total surface area available to generate enhancement shows that particles with 74 nm diameter give the largest enhancement per unit surface area. The observed enhancements do not correlate with absorbance at the excitation wavelength but the large differences between differently sized colloids demonstrate that even in the randomly aggregated particle assemblies studied here, inhomogeneous broadening does not mask the underlying changes due to differences in particle diameter.

Thermodynamic functions of element 105 in neutral and ionized states

The basic thermodynamic functions, the entropy, free energy, and enthalpy, for element 105 (hahnium) in electronic configurations d^3 s^2, d^3 sp, and d^4s^1 and for its +5 ionized state (5f^14) have been calculated as a function of temperature. The data are based on the results of the calculations of the corresponding electronic states of element 105 using the multiconfiguration Dirac-Fock method.

Silica-encapsulated nanomagnetic particle as a new recoverable biocatalyst carrier

Enzymes are versatile biocatalysts with major advantages of ultrahigh reaction selectivity and specificity under mild conditions, which currently find increasing applications. However, their applications are often hampered by difficulties in recovery and recycling. As a result, we carried out detailed investigations on the synthesis and characterization of silica-encapsulated iron oxide magnetic nanoparticles of controlled dimension as an enzyme carrier. It is shown that the relatively smaller sized silica-coated magnetic nanoparticle prepared by the microemlusion technique can a carry bulky enzyme, beta-lactamase, via chemical linkages on the silica overlayer without severely blocking the enzymatic active center ( which is commonly encountered in conventional solid supports). An activity study by Michalis-Menten kinetics reflects that this new type of immobilization allows enzyme isolation with accessibility as good as free enzyme. The recovery and reusability of the nanoparticle-supported enzyme upon application of magnetic separation are also demonstrated.

New Molecular Species of Potential Interest to Atmospheric Chemistry: Isomers on the [H, S(2), Br] Potential Energy Surface

This work reports a state-of-the-art theoretical characterization of four new sulfur-bromine species and five transition states on the [H, S(2), Br] potential energy surface. Our highest level theoretical approach employed the method coupled cluster singles and doubles with perturbative contributions of connected triples, CCSD(T), along with the series of correlation-consistent basis sets and with extrapolation to the complete basis set (CBS) limit in the optimization of the geometrical parameters and to quantify the energetic quantities. The structural and vibrational frequencies here reported are unique and represent the most accurate investigation to date of these species. The global minimum corresponds to a skewed structure HSSBr with a disulfide bond; this is followed by a pyramidal-like structure, SSHBr, 18.85 kcal/mol above the minimum. Much higher in energy, we found another skewed structure, HSBrS (50.29 kcal/mol), with one S-Br dative-type bond, and another pyramidal-like one, HBrSS (109.80 kcal/mol), with two S-Br dative-type bonds. The interconversion of HSSBr into SSHBr can occur via a transfer of either the hydrogen or the bromine atom but involves a very high barrier of about 43 kcal/mol. These molecules are potentially a new route of coupling the sulfur and bromine chemistry in the atmosphere, and conditions of high concentration of H(2)S like in volcanic eruptions might contribute to their formation. We note that HSSBr can act as a reservoir molecule for the reaction between the radicals HSS and Br. Also, an assessment of the methods DFT/B3LYP/CBS and MP2/CBS relative to CCSD(T)/CBS provides insights on the expected performance of these methods on the characterization of polysulfides and also of more complex systems containing disulfide bridges.

Effect of sonication on the particle size of montmorillonite clays

This paper reports on the effect of sonication on SAz-1 and SWy-1 montmorillonite suspensions. Changes in the size of the particles of these materials and modifications of their properties have been investigated. The variation of the particle size has been analyzed by DLS (dynamic light scattering). In all cases the clay particles show a bimodal distribution. Sonication resulted in a decrease of the larger modal diameter, as well as a reduction of its volume percentage. Simultaneously, the proportion of the smallest particles increases. After 60 min of sonication, SAz-1 presented a very broad particle size distribution with a modal diameter of 283 nm. On the other hand, the SWy-1 sonicated for 60 min presents a bimodal distribution of particles at 140 and 454 nm. Changes in the properties of the clay suspensions due to sonication were evaluated spectroscopically from dye-clay interactions, using Methylene Blue. The acidic sites present in the interlamellar region, which are responsible for dye protonation, disappeared after sonication of the clay. The changes in the size of the scattering particles and the lack of acidic sites after sonication suggest that sonication induces delamination of the clay particles. (c) 2008 Elsevier Inc. All rights reserved.

Quantum states, thermodynamic limits, and entropy in M theory

We discuss the matching of the BPS part of the spectrum for a (super) membrane, which gives the possibility of getting the membrane's results via string calculations. In the small coupling limit of M theory the entropy of the system coincides with the standard entropy of type IIB string theory (including the logarithmic correction term). The thermodynamic behavior at a large coupling constant is computed by considering M theory on a manifold with a topology T-2 x R-9. We argue that the finite temperature partition functions (brane Laurent series for p not equal 1) associated with the BPS p-brane spectrum can be analytically continued to well-defined functionals. It means that a finite temperature can be introduced in brane theory, which behaves like finite temperature field theory. In the limit p --> 0 (point particle limit) it gives rise to the standard behavior of thermodynamic quantities.

Thermal phase transitions for Dicke-type models in the ultrastrong-coupling limit

Funda����o de Amparo �� Pesquisa do Estado de S��o Paulo (FAPESP)