Computer simulation of surface and film processes

NASA Technical Reports Server (NTRS)

Tiller, W. A.

1981-01-01

A molecular dynamics technique based upon Lennard-Jones type pair interactions is used to investigate time-dependent as well as equilibrium properties. The case study deals with systems containing Si and O atoms. In this case a more involved potential energy function (PEF) is employed and the system is simulated via a Monte-Carlo procedure. This furnishes the equilibrium properties of the system at its interfaces and surfaces as well as in the bulk.

Study on hydraulic property models for water retention and unsaturated hydraulic conductivity in MATSIRO with representation of water table dynamics

NASA Astrophysics Data System (ADS)

Yoshida, N.; Oki, T.

2016-12-01

Appropriate initial condition of soil moisture and water table depth are important factors to reduce uncertainty in hydrological simulations. Approaches to determine the initial water table depth have been developed because of difficulty to get information on global water table depth and soil moisture distributions. However, how is equilibrium soil moisture determined by climate conditions? We try to discuss this issue by using land surface model with representation of water table dynamics (MAT-GW). First, the global pattern of water table depth at equilibrium soil moisture in MAT-GW was verified. The water table depth in MAT-GW was deeper than the previous one at fundamentally arid region because the negative recharge and continuous baseflow made water table depth deeper. It indicated that the hydraulic conductivity used for estimating recharge and baseflow need to be reassessed in MAT-GW. In soil physics field, it is revealed that proper hydraulic property models for water retention and unsaturated hydraulic conductivity should be selected for each soil type. So, the effect of selecting hydraulic property models on terrestrial soil moisture and water table depth were examined.Clapp and Hornburger equation(CH eq.) and Van Genuchten equation(VG eq.) were used as representative hydraulic property models. Those models were integrated on MAT-GW and equilibrium soil moisture and water table depth with using each model were compared. The water table depth and soil moisture at grids which reached equilibrium in both simulations were analyzed. The equilibrium water table depth were deeper in VG eq. than CH eq. in most grids due to shape of hydraulic property models. Then, total soil moisture were smaller in VG eq. than CH eq. at almost all grids which water table depth reached equilibrium. It is interesting that spatial patterns which water table depth reached equilibrium or not were basically similar in both simulations but reverse patterns were shown in east and west part of America. Selection of each hydraulic property model based on soil types may compensate characteristic of models in initialization.

Effects of energy conservation on equilibrium properties of hot asymmetric nuclear matter

NASA Astrophysics Data System (ADS)

Zhang, Zhen; Ko, Che Ming

2018-01-01

Based on the relativistic Vlasov-Uehling-Uhlenbeck transport model, which includes relativistic scalar and vector potentials on baryons, we consider an N -Δ -π system in a box with periodic boundary conditions to study the effects of energy conservation in particle production and absorption processes on the equilibrium properties of the system. The density and temperature of the matter in the box are taken to be similar to the hot dense matter formed in heavy ion collisions at intermediate energies. We find that to maintain the equilibrium numbers of N ,Δ , and π , which depend on the mean-field potentials of N and Δ , we must include these potentials in the energy conservation condition that determines the momenta of outgoing particles after a scattering or decay process. We further find that the baryon scalar potentials mainly affect the Δ and pion equilibrium numbers, while the baryon vector potentials have considerable effect on the effective charged pion ratio at equilibrium. Our results thus indicate that it is essential to include in the transport model the effect of potentials in the energy conservation of a scattering or decay process, which is ignored in most transport models, for studying pion production in heavy ion collisions.

Thermodynamic and structure-property study of liquid-vapor equilibrium for aroma compounds.

PubMed

Tromelin, Anne; Andriot, Isabelle; Kopjar, Mirela; Guichard, Elisabeth

2010-04-14

Thermodynamic parameters (T, DeltaH degrees , DeltaS degrees , K) were collected from the literature and/or calculated for five esters, four ketones, two aldehydes, and three alcohols, pure compounds and compounds in aqueous solution. Examination of correlations between these parameters and the range values of DeltaH degrees and DeltaS degrees puts forward the key roles of enthalpy for vaporization of pure compounds and of entropy in liquid-vapor equilibrium of compounds in aqueous solution. A structure-property relationship (SPR) study was performed using molecular descriptors on aroma compounds to better understand their vaporization behavior. In addition to the role of polarity for vapor-liquid equilibrium of compounds in aqueous solution, the structure-property study points out the role of chain length and branching, illustrated by the correlation between the connectivity index CHI-V-1 and the difference between T and log K for vaporization of pure compounds and compounds in aqueous solution. Moreover, examination of the esters' enthalpy values allowed a probable conformation adopted by ethyl octanoate in aqueous solution to be proposed.

Thermodynamic and transport combustion properties of hydrocarbons with air. Part 2: Compositions corresponding to Kelvin temperature schedules in part 1

NASA Technical Reports Server (NTRS)

Gordon, S.

1982-01-01

The equilibrium compositions that correspond to the thermodynamic and transport combustion properties for a wide range of conditions for the reaction of hydrocarbons with air are presented. Initially 55 gaseous species and 3 coin condensed species were considered in the calculations. Only 17 of these 55 gaseous species had equilibrium mole fractions greater than 0.000005 for any of the conditions studied and therefore these were the only ones retained in the final tables.

Study on the Electronic Transport Properties of Zigzag GaN Nanotubes

NASA Astrophysics Data System (ADS)

Li, Enling; Wang, Xiqiang; Hou, Liping; Zhao, Danna; Dai, Yuanbin; Wang, Xuewen

2011-02-01

The electronic transport properties of zigzag GaN nanotubes (n, 0) (4 <= n <= 9) have been calculated using the density functional theory and non-equilibrium Green's functions method. Firstly, the density functional theory (DFT) is used to optimize and calculate the electronic structure of GaNNTs (n, 0) (4<=n<=9). Secondly, DFT and non-equilibrium Green function (NEGF) method are also used to predict the electronic transport properties of GaNNTs two-probe system. The results showed: there is a corresponding relation between the electronic transport properties and the valley of state density of each GaNNT. In addition, the volt-ampere curve of GaNNT is approximately linear.

The effects of intraspecific competition and stabilizing selection on a polygenic trait.

PubMed Central

Bürger, Reinhard; Gimelfarb, Alexander

2004-01-01

The equilibrium properties of an additive multilocus model of a quantitative trait under frequency- and density-dependent selection are investigated. Two opposing evolutionary forces are assumed to act: (i) stabilizing selection on the trait, which favors genotypes with an intermediate phenotype, and (ii) intraspecific competition mediated by that trait, which favors genotypes whose effect on the trait deviates most from that of the prevailing genotypes. Accordingly, fitnesses of genotypes have a frequency-independent component describing stabilizing selection and a frequency- and density-dependent component modeling competition. We study how the equilibrium structure, in particular, number, degree of polymorphism, and genetic variance of stable equilibria, is affected by the strength of frequency dependence, and what role the number of loci, the amount of recombination, and the demographic parameters play. To this end, we employ a statistical and numerical approach, complemented by analytical results, and explore how the equilibrium properties averaged over a large number of genetic systems with a given number of loci and average amount of recombination depend on the ecological and demographic parameters. We identify two parameter regions with a transitory region in between, in which the equilibrium properties of genetic systems are distinctively different. These regions depend on the strength of frequency dependence relative to pure stabilizing selection and on the demographic parameters, but not on the number of loci or the amount of recombination. We further study the shape of the fitness function observed at equilibrium and the extent to which the dynamics in this model are adaptive, and we present examples of equilibrium distributions of genotypic values under strong frequency dependence. Consequences for the maintenance of genetic variation, the detection of disruptive selection, and models of sympatric speciation are discussed. PMID:15280253

Computing Properties Of Chemical Mixtures At Equilibrium

NASA Technical Reports Server (NTRS)

Mcbride, B. J.; Gordon, S.

1995-01-01

Scientists and engineers need data on chemical equilibrium compositions to calculate theoretical thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93 is general program that calculates chemical equilibrium compositions and properties of mixtures for any chemical system for which thermodynamic data are available. Includes thermodynamic data for more than 1,300 gaseous and condensed species and thermal-transport data for 151 gases. Written in FORTRAN 77.

Tokamak plasma high field side response to an n = 3 magnetic perturbation: a comparison of 3D equilibrium solutions from seven different codes

NASA Astrophysics Data System (ADS)

Reiman, A.; Ferraro, N. M.; Turnbull, A.; Park, J. K.; Cerfon, A.; Evans, T. E.; Lanctot, M. J.; Lazarus, E. A.; Liu, Y.; McFadden, G.; Monticello, D.; Suzuki, Y.

2015-06-01

In comparing equilibrium solutions for a DIII-D shot that is amenable to analysis by both stellarator and tokamak three-dimensional (3D) equilibrium codes, a significant disagreement has been seen between solutions of the VMEC stellarator equilibrium code and solutions of tokamak perturbative 3D equilibrium codes. The source of that disagreement has been investigated, and that investigation has led to new insights into the domain of validity of the different equilibrium calculations, and to a finding that the manner in which localized screening currents at low order rational surfaces are handled can affect global properties of the equilibrium solution. The perturbative treatment has been found to break down at surprisingly small perturbation amplitudes due to overlap of the calculated perturbed flux surfaces, and that treatment is not valid in the pedestal region of the DIII-D shot studied. The perturbative treatment is valid, however, further into the interior of the plasma, and flux surface overlap does not account for the disagreement investigated here. Calculated equilibrium solutions for simple model cases and comparison of the 3D equilibrium solutions with those of other codes indicate that the disagreement arises from a difference in handling of localized currents at low order rational surfaces, with such currents being absent in VMEC and present in the perturbative codes. The significant differences in the global equilibrium solutions associated with the presence or absence of very localized screening currents at rational surfaces suggests that it may be possible to extract information about localized currents from appropriate measurements of global equilibrium plasma properties. That would require improved diagnostic capability on the high field side of the tokamak plasma, a region difficult to access with diagnostics.

Facile characterization of aptamer kinetic and equilibrium binding properties using surface plasmon resonance

PubMed Central

Chang, Andrew L.; McKeague, Maureen; Smolke, Christina D.

2015-01-01

Nucleic acid aptamers find widespread use as targeting and sensing agents in nature and biotechnology. Their ability to bind an extensive range of molecular targets, including small molecules, proteins, and ions, with high affinity and specificity enables their use in diverse diagnostic, therapeutic, imaging, and gene-regulatory applications. Here, we describe methods for characterizing aptamer kinetic and equilibrium binding properties using a surface plasmon resonance-based platform. This aptamer characterization platform is broadly useful for studying aptamer–ligand interactions, comparing aptamer properties, screening functional aptamers during in vitro selection processes, and prototyping aptamers for integration into nucleic acid devices. PMID:25432760

Role of cell division and self-propulsion in self-organization of 2D cell co-cultures

NASA Astrophysics Data System (ADS)

Das, Moumita; Dey, Supravat; Wu, Mingming; Ma, Minglin

Self-organization of cells is a key process in developmental and cancer biology. The differential adhesion hypothesis (DAH), which assumes cells as equilibrium liquid droplets and relates the self-assembly of cells to differences in inter-cellular adhesiveness, has been very successful in explaining cellular organization during morphogenesis where neighboring cells have the same non-equilibrium properties (motility, proliferation rate). However, recently it has been experimentally shown that for a co-culture of two different cell types proliferating at different rates, the resulting spatial morphologies cannot be explained using the DAH alone. Motivated by this, we develop and study a two-dimensional model of a cell co-culture that includes cell division and self-propulsion in addition to cell-cell adhesion, and systemically study how cells with significantly different adhesion, motility, and proliferation rate dynamically organize themselves in a spatiotemporal and context-dependent manner. Our results may help to understand how differential equilibrium and non-equilibrium properties cooperate and compete leading to different morphologies during tumor development, with important consequences for invasion and metastasis

Computer codes for the evaluation of thermodynamic and transport properties for equilibrium air to 30000 K

NASA Technical Reports Server (NTRS)

Thompson, Richard A.; Lee, Kam-Pui; Gupta, Roop N.

1991-01-01

The computer codes developed here provide self-consistent thermodynamic and transport properties for equilibrium air for temperatures from 500 to 30000 K over a temperature range of 10 (exp -4) to 10 (exp -2) atm. These properties are computed through the use of temperature dependent curve fits for discrete values of pressure. Interpolation is employed for intermediate values of pressure. The curve fits are based on mixture values calculated from an 11-species air model. Individual species properties used in the mixture relations are obtained from a recent study by the present authors. A review and discussion of the sources and accuracy of the curve fitted data used herein are given in NASA RP 1260.

Equilibrium and nonequilibrium properties of Boolean decision problems on scale-free graphs with competing interactions with external biases

NASA Astrophysics Data System (ADS)

Zhu, Zheng; Andresen, Juan Carlos; Janzen, Katharina; Katzgraber, Helmut G.

2013-03-01

We study the equilibrium and nonequilibrium properties of Boolean decision problems with competing interactions on scale-free graphs in a magnetic field. Previous studies at zero field have shown a remarkable equilibrium stability of Boolean variables (Ising spins) with competing interactions (spin glasses) on scale-free networks. When the exponent that describes the power-law decay of the connectivity of the network is strictly larger than 3, the system undergoes a spin-glass transition. However, when the exponent is equal to or less than 3, the glass phase is stable for all temperatures. First we perform finite-temperature Monte Carlo simulations in a field to test the robustness of the spin-glass phase and show, in agreement with analytical calculations, that the system exhibits a de Almeida-Thouless line. Furthermore, we study avalanches in the system at zero temperature to see if the system displays self-organized criticality. This would suggest that damage (avalanches) can spread across the whole system with nonzero probability, i.e., that Boolean decision problems on scale-free networks with competing interactions are fragile when not in thermal equilibrium.

New Equilibrium Models of Drug-Receptor Interactions Derived from Target-Mediated Drug Disposition.

PubMed

Peletier, Lambertus A; Gabrielsson, Johan

2018-05-14

In vivo analyses of pharmacological data are traditionally based on a closed system approach not incorporating turnover of target and ligand-target kinetics, but mainly focussing on ligand-target binding properties. This study incorporates information about target and ligand-target kinetics parallel to binding. In a previous paper, steady-state relationships between target- and ligand-target complex versus ligand exposure were derived and a new expression of in vivo potency was derived for a circulating target. This communication is extending the equilibrium relationships and in vivo potency expression for (i) two separate targets competing for one ligand, (ii) two different ligands competing for a single target and (iii) a single ligand-target interaction located in tissue. The derived expressions of the in vivo potencies will be useful both in drug-related discovery projects and mechanistic studies. The equilibrium states of two targets and one ligand may have implications in safety assessment, whilst the equilibrium states of two competing ligands for one target may cast light on when pharmacodynamic drug-drug interactions are important. The proposed equilibrium expressions for a peripherally located target may also be useful for small molecule interactions with extravascularly located targets. Including target turnover, ligand-target complex kinetics and binding properties in expressions of potency and efficacy will improve our understanding of within and between-individual (and across species) variability. The new expressions of potencies highlight the fact that the level of drug-induced target suppression is very much governed by target turnover properties rather than by the target expression level as such.

Stability and electronic properties of oxygen-doped ZnS polytypes: DFTB study

NASA Astrophysics Data System (ADS)

Popov, Ilya S.; Vorokh, Andrey S.; Enyashin, Andrey N.

2018-06-01

Synthesis from aqueous solutions is an affordable method for fabrication of II-VI semiconductors. However, application of this method often imposes a disorder of crystal lattice, manifesting as a rich variety of polytypes arising from wurtzite and zinc blende phases. The origin of this disordering still remains debatable. Here, the influence of the most likely impurity at water environment - substitutional oxygen - on the polytypic equilibrium of zinc sulphide is studied by means of density-functional tight-binding method. According to calculations, the inclusion of such oxygen does not affect the polytypic equilibrium. Apart of thermodynamic stability, the electronic and elastic properties of ZnS polytypes are studied as the function of oxygen distribution.

The magnetic non-equilibrium of buoyant flux tubes in the solar corona

NASA Technical Reports Server (NTRS)

Browning, P. K.; Priest, E. R.

1984-01-01

The magnetic field in the convection zone and photosphere of the sun exists mostly as concentrated tubes of magnetic flux. It is, therefore, necessary to study the basic properties of magnetic flux tubes to obtain a basis for understanding the behavior of the sun's magnetic field. The present investigation is concerned with the global equilibrium shape of a flux tube in the stratified solar atmosphere. A fundamental property of isolated flux tubes is magnetic buoyancy. Attention is given to flux tubes with external field, and twisted flux tubes. It is shown that the analysis of Parker (1975, 1979) and Spruit (1981) for calculating the equilibrium of a slender flux tube in a stratified atmosphere may be extended to more general situations. The slender tube approximation provides a method of solving the problem of modeling the overall curvature of flux tubes. It is found that for a twisted flux tube, there can be two possible equilibrium values of the height.

Mussel-inspired histidine-based transient network metal coordination hydrogels

PubMed Central

Fullenkamp, Dominic E.; He, Lihong; Barrett, Devin G.; Burghardt, Wesley R.; Messersmith, Phillip B.

2013-01-01

Transient network hydrogels cross-linked through histidine-divalent cation coordination bonds were studied by conventional rheologic methods using histidine-modified star poly(ethylene glycol) (PEG) polymers. These materials were inspired by the mussel, which is thought to use histidine-metal coordination bonds to impart self-healing properties in the mussel byssal thread. Hydrogel viscoelastic mechanical properties were studied as a function of metal, pH, concentration, and ionic strength. The equilibrium metal-binding constants were determined by dilute solution potentiometric titration of monofunctional histidine-modified methoxy-PEG and were found to be consistent with binding constants of small molecule analogs previously studied. pH-dependent speciation curves were then calculated using the equilibrium constants determined by potentiometric titration, providing insight into the pH dependence of histidine-metal ion coordination and guiding the design of metal coordination hydrogels. Gel relaxation dynamics were found to be uncorrelated with the equilibrium constants measured, but were correlated to the expected coordination bond dissociation rate constants. PMID:23441102

Computing Equilibrium Chemical Compositions

NASA Technical Reports Server (NTRS)

Mcbride, Bonnie J.; Gordon, Sanford

1995-01-01

Chemical Equilibrium With Transport Properties, 1993 (CET93) computer program provides data on chemical-equilibrium compositions. Aids calculation of thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93/PC is version of CET93 specifically designed to run within 640K memory limit of MS-DOS operating system. CET93/PC written in FORTRAN.

Multi-equilibrium property of metabolic networks: SSI module.

PubMed

Lei, Hong-Bo; Zhang, Ji-Feng; Chen, Luonan

2011-06-20

Revealing the multi-equilibrium property of a metabolic network is a fundamental and important topic in systems biology. Due to the complexity of the metabolic network, it is generally a difficult task to study the problem as a whole from both analytical and numerical viewpoint. On the other hand, the structure-oriented modularization idea is a good choice to overcome such a difficulty, i.e. decomposing the network into several basic building blocks and then studying the whole network through investigating the dynamical characteristics of the basic building blocks and their interactions. Single substrate and single product with inhibition (SSI) metabolic module is one type of the basic building blocks of metabolic networks, and its multi-equilibrium property has important influence on that of the whole metabolic networks. In this paper, we describe what the SSI metabolic module is, characterize the rates of the metabolic reactions by Hill kinetics and give a unified model for SSI modules by using a set of nonlinear ordinary differential equations with multi-variables. Specifically, a sufficient and necessary condition is first given to describe the injectivity of a class of nonlinear systems, and then, the sufficient condition is used to study the multi-equilibrium property of SSI modules. As a main theoretical result, for the SSI modules in which each reaction has no more than one inhibitor, a sufficient condition is derived to rule out multiple equilibria, i.e. the Jacobian matrix of its rate function is nonsingular everywhere. In summary, we describe SSI modules and give a general modeling framework based on Hill kinetics, and provide a sufficient condition for ruling out multiple equilibria of a key type of SSI module.

Multi-equilibrium property of metabolic networks: SSI module

PubMed Central

2011-01-01

Background Revealing the multi-equilibrium property of a metabolic network is a fundamental and important topic in systems biology. Due to the complexity of the metabolic network, it is generally a difficult task to study the problem as a whole from both analytical and numerical viewpoint. On the other hand, the structure-oriented modularization idea is a good choice to overcome such a difficulty, i.e. decomposing the network into several basic building blocks and then studying the whole network through investigating the dynamical characteristics of the basic building blocks and their interactions. Single substrate and single product with inhibition (SSI) metabolic module is one type of the basic building blocks of metabolic networks, and its multi-equilibrium property has important influence on that of the whole metabolic networks. Results In this paper, we describe what the SSI metabolic module is, characterize the rates of the metabolic reactions by Hill kinetics and give a unified model for SSI modules by using a set of nonlinear ordinary differential equations with multi-variables. Specifically, a sufficient and necessary condition is first given to describe the injectivity of a class of nonlinear systems, and then, the sufficient condition is used to study the multi-equilibrium property of SSI modules. As a main theoretical result, for the SSI modules in which each reaction has no more than one inhibitor, a sufficient condition is derived to rule out multiple equilibria, i.e. the Jacobian matrix of its rate function is nonsingular everywhere. Conclusions In summary, we describe SSI modules and give a general modeling framework based on Hill kinetics, and provide a sufficient condition for ruling out multiple equilibria of a key type of SSI module. PMID:21689474

CET89 - CHEMICAL EQUILIBRIUM WITH TRANSPORT PROPERTIES, 1989

NASA Technical Reports Server (NTRS)

Mcbride, B.

1994-01-01

Scientists and engineers need chemical equilibrium composition data to calculate the theoretical thermodynamic properties of a chemical system. This information is essential in the design and analysis of equipment such as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical processing equipment. The substantial amount of numerical computation required to obtain equilibrium compositions and transport properties for complex chemical systems led scientists at NASA's Lewis Research Center to develop CET89, a program designed to calculate the thermodynamic and transport properties of these systems. CET89 is a general program which will calculate chemical equilibrium compositions and mixture properties for any chemical system with available thermodynamic data. Generally, mixtures may include condensed and gaseous products. CET89 performs the following operations: it 1) obtains chemical equilibrium compositions for assigned thermodynamic states, 2) calculates dilute-gas transport properties of complex chemical mixtures, 3) obtains Chapman-Jouguet detonation properties for gaseous species, 4) calculates incident and reflected shock properties in terms of assigned velocities, and 5) calculates theoretical rocket performance for both equilibrium and frozen compositions during expansion. The rocket performance function allows the option of assuming either a finite area or an infinite area combustor. CET89 accommodates problems involving up to 24 reactants, 20 elements, and 600 products (400 of which may be condensed). The program includes a library of thermodynamic and transport properties in the form of least squares coefficients for possible reaction products. It includes thermodynamic data for over 1300 gaseous and condensed species and transport data for 151 gases. The subroutines UTHERM and UTRAN convert thermodynamic and transport data to unformatted form for faster processing. The program conforms to the FORTRAN 77 standard, except for some input in NAMELIST format. It requires about 423 KB memory, and is designed to be used on mainframe, workstation, and mini computers. Due to its memory requirements, this program does not readily lend itself to implementation on MS-DOS based machines.

Price game and chaos control among three oligarchs with different rationalities in property insurance market.

PubMed

Ma, Junhai; Zhang, Junling

2012-12-01

Combining with the actual competition in Chinese property insurance market and assuming that the property insurance companies take the marginal utility maximization as the basis of decision-making when they play price games, we first established the price game model with three oligarchs who have different rationalities. Then, we discussed the existence and stability of equilibrium points. Third, we studied the theoretical value of Lyapunov exponent at Nash equilibrium point and its change process with the main parameters' changes though having numerical simulation for the system such as the bifurcation, chaos attractors, and so on. Finally, we analyzed the influences which the changes of different parameters have on the profits and utilities of oligarchs and their corresponding competition advantage. Based on this, we used the variable feedback control method to control the chaos of the system and stabilized the chaos state to Nash equilibrium point again. The results have significant theoretical and practical application value.

Price game and chaos control among three oligarchs with different rationalities in property insurance market

NASA Astrophysics Data System (ADS)

Ma, Junhai; Zhang, Junling

2012-12-01

Combining with the actual competition in Chinese property insurance market and assuming that the property insurance companies take the marginal utility maximization as the basis of decision-making when they play price games, we first established the price game model with three oligarchs who have different rationalities. Then, we discussed the existence and stability of equilibrium points. Third, we studied the theoretical value of Lyapunov exponent at Nash equilibrium point and its change process with the main parameters' changes though having numerical simulation for the system such as the bifurcation, chaos attractors, and so on. Finally, we analyzed the influences which the changes of different parameters have on the profits and utilities of oligarchs and their corresponding competition advantage. Based on this, we used the variable feedback control method to control the chaos of the system and stabilized the chaos state to Nash equilibrium point again. The results have significant theoretical and practical application value.

An equilibrium-preserving discretization for the nonlinear Rosenbluth-Fokker-Planck operator in arbitrary multi-dimensional geometry

NASA Astrophysics Data System (ADS)

Taitano, W. T.; Chacón, L.; Simakov, A. N.

2017-06-01

The Fokker-Planck collision operator is an advection-diffusion operator which describe dynamical systems such as weakly coupled plasmas [1,2], photonics in high temperature environment [3,4], biological [5], and even social systems [6]. For plasmas in the continuum, the Fokker-Planck collision operator supports such important physical properties as conservation of number, momentum, and energy, as well as positivity. It also obeys the Boltzmann's H-theorem [7-11], i.e., the operator increases the system entropy while simultaneously driving the distribution function towards a Maxwellian. In the discrete, when these properties are not ensured, numerical simulations can either fail catastrophically or suffer from significant numerical pollution [12,13]. There is strong emphasis in the literature on developing numerical techniques to solve the Fokker-Planck equation while preserving these properties [12-24]. In this short note, we focus on the analytical equilibrium preserving property, meaning that the Fokker-Planck collision operator vanishes when acting on an analytical Maxwellian distribution function. The equilibrium preservation property is especially important, for example, when one is attempting to capture subtle transport physics. Since transport arises from small O (ɛ) corrections to the equilibrium [25] (where ɛ is a small expansion parameter), numerical truncation error present in the equilibrium solution may dominate, overwhelming transport dynamics.

Development and Assessment of a Computer-Based Equation of State for Equilibrium Air

DTIC Science & Technology

2013-09-01

for very low energies. However, the ideal gas EOS is appropriate for atmospheric flight at subsonic, transonic, and low supersonic flight speeds...Flow Properties About Blunt Bodies Moving at Supersonic Speeds in an Equilibrium Gas ,” NASA TR R-204, July 1964. 21. Tannehill, John C., and Mugge...changes are made. 15. Subject Terms Air, thermodynamic properties, equation of state, chemical equilibrium, real- gas 16. SECURITY CLASSIFICATION

Adsorption properties of biologically active derivatives of quaternary ammonium surfactants and their mixtures at aqueous/air interface. I. Equilibrium surface tension, surfactant aggregation and wettability.

PubMed

Rojewska, Monika; Biadasz, Andrzej; Kotkowiak, Michał; Olejnik, Anna; Rychlik, Joanna; Dudkowiak, Alina; Prochaska, Krystyna

2013-10-01

The adsorption properties of surfactant mixtures containing two types of quaternary derivatives of lysosomotropic substances: alkyl N,N-dimethylalaninates methobromides and alkyl N,N-dimethylglycinates methobromides were studied. Quantitative and qualitative description of the adsorption process was carried out on the basis of experimentally obtained equilibrium surface tension isotherms. The results indicated that most of the systems studied revealed synergistic effect both in adsorption and wetting properties. In vitro studies on human cancer cells were undertaken and the data obtained showed that the mixtures suppressed the cancer cells' proliferation more effectively than individual components. Results of preliminary research on the interaction of catanionic mixtures with phospholipids suggested a possibility of a strong penetration of cell membranes by the mixtures investigated. Copyright © 2013 Elsevier B.V. All rights reserved.

Thermodynamic properties of methane hydrate in quartz powder.

PubMed

Voronov, Vitaly P; Gorodetskii, Evgeny E; Safonov, Sergey S

2007-10-04

Using the experimental method of precision adiabatic calorimetry, the thermodynamic (equilibrium) properties of methane hydrate in quartz sand with a grain size of 90-100 microm have been studied in the temperature range of 260-290 K and at pressures up to 10 MPa. The equilibrium curves for the water-methane hydrate-gas and ice-methane hydrate-gas transitions, hydration number, latent heat of hydrate decomposition along the equilibrium three-phase curves, and the specific heat capacity of the hydrate have been obtained. It has been experimentally shown that the equilibrium three-phase curves of the methane hydrate in porous media are shifted to the lower temperature and high pressure with respect to the equilibrium curves of the bulk hydrate. In these experiments, we have found that the specific heat capacity of the hydrate, within the accuracy of our measurements, coincides with the heat capacity of ice. The latent heat of the hydrate dissociation for the ice-hydrate-gas transition is equal to 143 +/- 10 J/g, whereas, for the transition from hydrate to water and gas, the latent heat is 415 +/- 15 J/g. The hydration number has been evaluated in the different hydrate conditions and has been found to be equal to n = 6.16 +/- 0.06. In addition, the influence of the water saturation of the porous media and its distribution over the porous space on the measured parameters has been experimentally studied.

Chemical and physical properties affecting strontium distribution coefficients of surficial-sediment samples at the Idaho National Engineering and Environmental Laboratory, Idaho

USGS Publications Warehouse

Liszewski, M.J.; Rosentreter, J.J.; Miller, Karl E.; Bartholomay, R.C.

2000-01-01

The U.S. Geological Survey and Idaho State University, in cooperation with the U.S. Department of Energy, conducted a study to determine strontium distribution coefficients (K(d)s) of surficial sediments at the Idaho National Engineering and Environmental Laboratory (INEEL). Batch experiments using synthesized aqueous solutions were used to determine K(d)s, which describe the distribution of a solute between the solution and solid phase, of 20 surficial-sediment samples from the INEEL. The K(d)s for the 20 surficial-sediment samples ranged from 36 to 275 ml/g. Many properties of both the synthesized aqueous solutions and sediments used in the experiments also were determined. Solution properties determined were initial and equilibrium concentrations of calcium, magnesium, and strontium, pH and specific conductance, and initial concentrations of potassium and sodium. Sediment properties determined were grain-size distribution, bulk mineralogy, whole-rock major-oxide and strontium and barium concentrations, and Brunauer-Emmett-Teller (BET) surface area. Solution and sediment properties were correlated with strontium K(d)s of the 20 surficial sediments using Pearson correlation coefficients. Solution properties with the strongest correlations with strontium K(d)s were equilibrium pH and equilibrium calcium concentration correlation coefficients, 0.6598 and -0.6518, respectively. Sediment properties with the strongest correlations with strontium K(d)s were manganese oxide (MnO), BET surface area, and the >4.75-mm-grain-size fraction correlation coefficients, 0.7054, 0.7022, and -0.6660, respectively. Effects of solution properties on strontium K(d)s were interpreted as being due to competition among similarly charged and sized cations in solution for strontium-sorption sites; effects of sediment properties on strontium K(d)s were interpreted as being surface-area related. Multivariate analyses of these solution and sediment properties resulted in r2 values of 0.8071 when all five properties were used and 0.8043 when three properties, equilibrium pH, MnO, and BET surface area, were used.

Equilibrium properties of the Skylab CMG rotation law

NASA Technical Reports Server (NTRS)

Elrod, B. D.; Anderson, G. M.

1972-01-01

The equilibrium properties of the control moment gyroscopes of the Skylab are discussed. A rotation law is developed to produce gimbal rates which distribute the angular momentum contributions among the control moment gyroscopes to avoid gimbal stop encounters. The implications for gimbal angle management under various angular momentum situations are described. Conditions were obtained for the existence of equilibria and corresponding stability properties.

Emergence of an enslaved phononic bandgap in a non-equilibrium pseudo-crystal.

PubMed

Bachelard, Nicolas; Ropp, Chad; Dubois, Marc; Zhao, Rongkuo; Wang, Yuan; Zhang, Xiang

2017-08-01

Material systems that reside far from thermodynamic equilibrium have the potential to exhibit dynamic properties and behaviours resembling those of living organisms. Here we realize a non-equilibrium material characterized by a bandgap whose edge is enslaved to the wavelength of an external coherent drive. The structure dynamically self-assembles into an unconventional pseudo-crystal geometry that equally distributes momentum across elements. The emergent bandgap is bestowed with lifelike properties, such as the ability to self-heal to perturbations and adapt to sudden changes in the drive. We derive an exact analytical solution for both the spatial organization and the bandgap features, revealing the mechanism for enslavement. This work presents a framework for conceiving lifelike non-equilibrium materials and emphasizes the potential for the dynamic imprinting of material properties through external degrees of freedom.

Emergence of an enslaved phononic bandgap in a non-equilibrium pseudo-crystal

NASA Astrophysics Data System (ADS)

Bachelard, Nicolas; Ropp, Chad; Dubois, Marc; Zhao, Rongkuo; Wang, Yuan; Zhang, Xiang

2017-08-01

Material systems that reside far from thermodynamic equilibrium have the potential to exhibit dynamic properties and behaviours resembling those of living organisms. Here we realize a non-equilibrium material characterized by a bandgap whose edge is enslaved to the wavelength of an external coherent drive. The structure dynamically self-assembles into an unconventional pseudo-crystal geometry that equally distributes momentum across elements. The emergent bandgap is bestowed with lifelike properties, such as the ability to self-heal to perturbations and adapt to sudden changes in the drive. We derive an exact analytical solution for both the spatial organization and the bandgap features, revealing the mechanism for enslavement. This work presents a framework for conceiving lifelike non-equilibrium materials and emphasizes the potential for the dynamic imprinting of material properties through external degrees of freedom.

Comparative study of the molecularly imprinted polymers prepared by reversible addition-fragmentation chain transfer "bulk" polymerization and traditional radical "bulk" polymerization.

PubMed

Ma, Yue; Pan, Guoqing; Zhang, Ying; Guo, Xianzhi; Zhang, Huiqi

2013-05-01

Bisphenol A (BPA) and propranolol-imprinted polymers have been prepared via both reversible addition-fragmentation chain transfer "bulk" polymerization (RAFTBP) and traditional radical "bulk" polymerization (TRBP) under similar reaction conditions, and their equilibrium binding properties were compared in detail for the first time. The chemical compositions, specific surface areas, equilibrium bindings, and selectivity of the obtained molecularly imprinted polymers (MIPs) were systematically characterized. The experimental results showed that the MIPs with molecular imprinting effects and quite fast binding kinetics could be readily prepared via RAFTBP, but they did not show improved template binding properties in comparison with those prepared via TRBP, which is in sharp contrast to many previous reports. This could be attributed to the heavily interrupted equilibrium between the dormant species and active radicals in the RAFT mechanism because of the occurrence of fast gelation during RAFTBP. The findings presented here strongly demonstrates that the application of controlled radical polymerizations (CRPs) in molecular imprinting does not always benefit the binding properties of the resultant MIPs, which is of significant importance for the rational use of CRPs in generating MIPs with improved properties. Copyright © 2013 John Wiley & Sons, Ltd.

Effects of crowders on the equilibrium and kinetic properties of protein aggregation

NASA Astrophysics Data System (ADS)

Bridstrup, John; Yuan, Jian-Min

2016-08-01

The equilibrium and kinetic properties of protein aggregation systems in the presence of crowders are investigated using simple, illuminating models based on mass-action laws. Our model yields analytic results for equilibrium properties of protein aggregates, which fit experimental data of actin and ApoC-II with crowders reasonably well. When the effects of crowders on rate constants are considered, our kinetic model is in good agreement with experimental results for actin with dextran as the crowder. Furthermore, the model shows that as crowder volume fraction increases, the length distribution of fibrils becomes narrower and shifts to shorter values due to volume exclusion.

Thermodynamic model effects on the design and optimization of natural gas plants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Diaz, S.; Zabaloy, M.; Brignole, E.A.

1999-07-01

The design and optimization of natural gas plants is carried out on the basis of process simulators. The physical property package is generally based on cubic equations of state. By rigorous thermodynamics phase equilibrium conditions, thermodynamic functions, equilibrium phase separations, work and heat are computed. The aim of this work is to analyze the NGL turboexpansion process and identify possible process computations that are more sensitive to model predictions accuracy. Three equations of state, PR, SRK and Peneloux modification, are used to study the effect of property predictions on process calculations and plant optimization. It is shown that turboexpander plantsmore » have moderate sensitivity with respect to phase equilibrium computations, but higher accuracy is required for the prediction of enthalpy and turboexpansion work. The effect of modeling CO{sub 2} solubility is also critical in mixtures with high CO{sub 2} content in the feed.« less

Equilibrium and nonequilibrium models on Solomon networks

NASA Astrophysics Data System (ADS)

Lima, F. W. S.

2016-05-01

We investigate the critical properties of the equilibrium and nonequilibrium systems on Solomon networks. The equilibrium and nonequilibrium systems studied here are the Ising and Majority-vote models, respectively. These systems are simulated by applying the Monte Carlo method. We calculate the critical points, as well as the critical exponents ratio γ/ν, β/ν and 1/ν. We find that both systems present identical exponents on Solomon networks and are of different universality class as the regular two-dimensional ferromagnetic model. Our results are in agreement with the Grinstein criterion for models with up and down symmetry on regular lattices.

Sorption equilibrium, thermodynamics and pH-indicator properties of cresyl violet dye/bentonite composite system.

PubMed

Georgieva, Nedyalka; Yaneva, Zvezdelina; Dermendzhieva, Diyana

2017-09-01

The aim of the present study was to develop cresyl violet (CV)/bentonite composite system, to investigate the equilibrium sorption of the fluorescent dye on bentonite, to determine the characteristic equilibrium and thermodynamic parameters of the system by appropriate empirical isotherm models and to assess its pH-indicator properties. The absorption characteristics of CV solutions were investigated by UV/VIS spectrophotometer. Equilibrium experiments were conducted and the experimental data were modelled by six mathematical isotherm models. The analyses of the experimental data showed that bentonite exhibited significantly high capacity - 169.92 mg/g, towards CV. The encapsulation efficiency was 85%. The Langmuir, Flory-Huggins and El-Awady models best represented the experimental results. The free Gibbs energy of adsorption (ΔG o ) was calculated on the basis of the values of the equilibrium coefficients determined by the proposed models. The values of ΔG determined by the Langmuir, Temkin and Flory-Huggins models are within the range -20 to -40 kJ/mol, which indicates that the adsorption process is spontaneous and chemisorption takes place due to charge sharing or transfer from the dye molecules to the sorbent surface as a coordinate type of bond. The investigations of the obtained CV/bentonite hybrid systems for application as pH-markers showed satisfactory results.

Optical Properties in Non-equilibrium Phase Transitions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ao, T; Ping, Y; Widmann, K

An open question about the dynamical behavior of materials is how phase transition occurs in highly non-equilibrium systems. One important class of study is the excitation of a solid by an ultrafast, intense laser. The preferential heating of electrons by the laser field gives rise to initial states dominated by hot electrons in a cold lattice. Using a femtosecond laser pump-probe approach, we have followed the temporal evolution of the optical properties of such a system. The results show interesting correlation to non-thermal melting and lattice disordering processes. They also reveal a liquid-plasma transition when the lattice energy density reachesmore » a critical value.« less

Asymptotic analysis of discrete schemes for non-equilibrium radiation diffusion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cui, Xia, E-mail: cui_xia@iapcm.ac.cn; Yuan, Guang-wei; Shen, Zhi-jun

Motivated by providing well-behaved fully discrete schemes in practice, this paper extends the asymptotic analysis on time integration methods for non-equilibrium radiation diffusion in [2] to space discretizations. Therein studies were carried out on a two-temperature model with Larsen's flux-limited diffusion operator, both the implicitly balanced (IB) and linearly implicit (LI) methods were shown asymptotic-preserving. In this paper, we focus on asymptotic analysis for space discrete schemes in dimensions one and two. First, in construction of the schemes, in contrast to traditional first-order approximations, asymmetric second-order accurate spatial approximations are devised for flux-limiters on boundary, and discrete schemes with second-ordermore » accuracy on global spatial domain are acquired consequently. Then by employing formal asymptotic analysis, the first-order asymptotic-preserving property for these schemes and furthermore for the fully discrete schemes is shown. Finally, with the help of manufactured solutions, numerical tests are performed, which demonstrate quantitatively the fully discrete schemes with IB time evolution indeed have the accuracy and asymptotic convergence as theory predicts, hence are well qualified for both non-equilibrium and equilibrium radiation diffusion. - Highlights: • Provide AP fully discrete schemes for non-equilibrium radiation diffusion. • Propose second order accurate schemes by asymmetric approach for boundary flux-limiter. • Show first order AP property of spatially and fully discrete schemes with IB evolution. • Devise subtle artificial solutions; verify accuracy and AP property quantitatively. • Ideas can be generalized to 3-dimensional problems and higher order implicit schemes.« less

A Computational Study of the Rheology and Structure of Surfactant Covered Droplets

NASA Astrophysics Data System (ADS)

Maia, Joao; Boromand, Arman; Jamali, Safa

2015-11-01

The use of different types of surface-active agents is ubiquitous practice in different industrial applications ranging from cosmetic and food industries to polymeric nano-composite and blends. This allows stable multiphasic systems like foams and emulsions to be produced. Stability and shelf-life of those products are directly determined by the efficiency of the surfactant molecules. Although the effect of molecular configuration of the surface-active molecules on the planar interfaces has been studied both experimentally and computationally, it remains challenging to track the efficiency and effectiveness of different surfactant molecules on curved interfaces. In this study we address this gap by using Dissipative Particle Dynamics, to study the effectiveness and efficiency of different surfactant molecules (linear vs. branched) on a curved interface in equilibrium and far from equilibrium. In particular, we are interested to relate interfacial properties of the surface covered droplets and its dynamics to the molecular configuration of the surface active molecules under equilibrium and far from equilibrium condition.

An improved correlation to predict molecular weight between crosslinks based on equilibrium degree of swelling of hydrogel networks.

PubMed

Jimenez-Vergara, Andrea C; Lewis, John; Hahn, Mariah S; Munoz-Pinto, Dany J

2018-04-01

Accurate characterization of hydrogel diffusional properties is of substantial importance for a range of biotechnological applications. The diffusional capacity of hydrogels has commonly been estimated using the average molecular weight between crosslinks (M c ), which is calculated based on the equilibrium degree of swelling. However, the existing correlation linking M c and equilibrium swelling fails to accurately reflect the diffusional properties of highly crosslinked hydrogel networks. Also, as demonstrated herein, the current model fails to accurately predict the diffusional properties of hydrogels when polymer concentration and molecular weight are varied simultaneously. To address these limitations, we evaluated the diffusional properties of 48 distinct hydrogel formulations using two different photoinitiator systems, employing molecular size exclusion as an alternative methodology to calculate average hydrogel mesh size. The resulting data were then utilized to develop a revised correlation between M c and hydrogel equilibrium swelling that substantially reduces the limitations associated with the current correlation. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1339-1348, 2018. © 2017 Wiley Periodicals, Inc.

Revealing missing charges with generalised quantum fluctuation relations.

PubMed

Mur-Petit, J; Relaño, A; Molina, R A; Jaksch, D

2018-05-22

The non-equilibrium dynamics of quantum many-body systems is one of the most fascinating problems in physics. Open questions range from how they relax to equilibrium to how to extract useful work from them. A critical point lies in assessing whether a system has conserved quantities (or 'charges'), as these can drastically influence its dynamics. Here we propose a general protocol to reveal the existence of charges based on a set of exact relations between out-of-equilibrium fluctuations and equilibrium properties of a quantum system. We apply these generalised quantum fluctuation relations to a driven quantum simulator, demonstrating their relevance to obtain unbiased temperature estimates from non-equilibrium measurements. Our findings will help guide research on the interplay of quantum and thermal fluctuations in quantum simulation, in studying the transition from integrability to chaos and in the design of new quantum devices.

First-principles study of the structural and elastic properties of AuxV1-x and AuxNb1-x alloys

NASA Astrophysics Data System (ADS)

Al-Zoubi, N.

2018-04-01

Ab initio total energy calculations, based on the Exact Muffin-Tin Orbitals (EMTO) method in combination with the coherent potential approximation (CPA), are used to calculate the total energy of AuxV1-x and AuxNb1-x random alloys along the Bain path that connects the body-centred cubic (bcc) and face-centred cubic (fcc) structures as a function of composition x (0 ≤ x ≤ 1). The equilibrium Wigner-Seitz radius and the elastic properties of both systems are determined as a function of composition. Our theoretical prediction in case of pure elements (x = 0 or x = 1) are in good agreement with the available experimental data. For the Au-V system, the equilibrium Wigner-Seitz radius increase as x increases, while for the Au-Nb system, the equilibrium Wigner-Seitz radius is almost constant. The bulk modulus B and C44 for both alloys exhibit nearly parabolic trend. On the other hand, the tetragonal shear elastic constant C‧ decreases as x increases and correlates reasonably well with the structural energy difference between fcc and bcc structures. Our results offer a consistent starting point for further theoretical and experimental studies of the elastic and micromechanical properties of Au-V and Au-Nb systems.

Table and Charts of Equilibrium Normal-shock Properties for Pure Hydrogen with Velocities to 70 km/sec. Revised.

NASA Technical Reports Server (NTRS)

Miller, C. G., III; Wilder, S. E.

1976-01-01

Errors found in the original edition are corrected. Refinement was made in procedures for solving the conservation relations for an incident (moving), standing, and reflected normal shock, as well as in computational methods for determining thermochemical-equilibrium hydrogen properties. A six-species hydrogen model replaces the original four-species model, and the heat of formation and spectroscopic constants used in this six-species model are listed in appendix A. In appendix B, comparisons are made between a number of methods for determining equilibrium thermodynamic properties for hydrogen for several values of pressure and temperatures to 50000 K. A comparison is also performed between the present method and a second method for determining thermodynamic properties and flow velocity behind an incident shock into pure hydrogen and behind a reflected shock.

Coupling between magnetic and optical properties of stable Au-Fe solid solution nanoparticles

NASA Astrophysics Data System (ADS)

de Julián Fernández, C.; Mattei, G.; Paz, E.; Novak, R. L.; Cavigli, L.; Bogani, L.; Palomares, F. J.; Mazzoldi, P.; Caneschi, A.

2010-04-01

Au-Fe nanoparticles constitute one of the simplest prototypes of a multifunctional nanomaterial that can exhibit both magnetic and optical (plasmonic) properties. This solid solution, not feasible in the bulk phase diagram in thermal equilibrium, can be formed as a nanostructure by out-of-equilibrium processes. Here, the novel magnetic, optical and magneto-optical properties of ion-implanted Au-Fe solid solution nanoparticles dispersed in a SiO2 matrix are investigated and correlated. The surface plasmon resonance of the Au-Fe nanoparticles with almost equicomposition is strongly damped when compared to pure Au and to Au-rich Au-Fe nanoparticles. In all cases, the Au atoms are magnetically polarized, as measured by x-ray magnetic circular dichroism, and ferromagnetically coupled with Fe atoms. Although the chemical stability of Au-Fe nanoparticles is larger than that of Fe nanoparticles, both the magnetic moment per Fe atom and the order temperature are smaller. These results suggest that electronic and magnetic properties are more influenced by the hybridization of the electronic bands in the Au-Fe solid solution than by size effects. On the other hand, the magneto-optical transitions allowed in the vis-nIR spectral regions are very similar. In addition, we also observe, after studying the properties of thermally treated samples, that the Au-Fe alloy is stabilized, not by surface effects, but by the combination of the out-of-equilibrium nature of the ion implantation technique and by changes in the properties due to size effects.

Coupling between magnetic and optical properties of stable Au-Fe solid solution nanoparticles.

PubMed

de Julián Fernández, C; Mattei, G; Paz, E; Novak, R L; Cavigli, L; Bogani, L; Palomares, F J; Mazzoldi, P; Caneschi, A

2010-04-23

Au-Fe nanoparticles constitute one of the simplest prototypes of a multifunctional nanomaterial that can exhibit both magnetic and optical (plasmonic) properties. This solid solution, not feasible in the bulk phase diagram in thermal equilibrium, can be formed as a nanostructure by out-of-equilibrium processes. Here, the novel magnetic, optical and magneto-optical properties of ion-implanted Au-Fe solid solution nanoparticles dispersed in a SiO(2) matrix are investigated and correlated. The surface plasmon resonance of the Au-Fe nanoparticles with almost equicomposition is strongly damped when compared to pure Au and to Au-rich Au-Fe nanoparticles. In all cases, the Au atoms are magnetically polarized, as measured by x-ray magnetic circular dichroism, and ferromagnetically coupled with Fe atoms. Although the chemical stability of Au-Fe nanoparticles is larger than that of Fe nanoparticles, both the magnetic moment per Fe atom and the order temperature are smaller. These results suggest that electronic and magnetic properties are more influenced by the hybridization of the electronic bands in the Au-Fe solid solution than by size effects. On the other hand, the magneto-optical transitions allowed in the vis-nIR spectral regions are very similar. In addition, we also observe, after studying the properties of thermally treated samples, that the Au-Fe alloy is stabilized, not by surface effects, but by the combination of the out-of-equilibrium nature of the ion implantation technique and by changes in the properties due to size effects.

Phase Transitions and Scaling in Systems Far from Equilibrium

NASA Astrophysics Data System (ADS)

Täuber, Uwe C.

2017-03-01

Scaling ideas and renormalization group approaches proved crucial for a deep understanding and classification of critical phenomena in thermal equilibrium. Over the past decades, these powerful conceptual and mathematical tools were extended to continuous phase transitions separating distinct nonequilibrium stationary states in driven classical and quantum systems. In concordance with detailed numerical simulations and laboratory experiments, several prominent dynamical universality classes have emerged that govern large-scale, long-time scaling properties both near and far from thermal equilibrium. These pertain to genuine specific critical points as well as entire parameter space regions for steady states that display generic scale invariance. The exploration of nonstationary relaxation properties and associated physical aging scaling constitutes a complementary potent means to characterize cooperative dynamics in complex out-of-equilibrium systems. This review describes dynamic scaling features through paradigmatic examples that include near-equilibrium critical dynamics, driven lattice gases and growing interfaces, correlation-dominated reaction-diffusion systems, and basic epidemic models.

On Social Optima of Non-Cooperative Mean Field Games

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Sen; Zhang, Wei; Zhao, Lin

This paper studies the social optima in noncooperative mean-field games for a large population of agents with heterogeneous stochastic dynamic systems. Each agent seeks to maximize an individual utility functional, and utility functionals of different agents are coupled through a mean field term that depends on the mean of the population states/controls. The paper has the following contributions. First, we derive a set of control strategies for the agents that possess *-Nash equilibrium property, and converge to the mean-field Nash equilibrium as the population size goes to infinity. Second, we study the social optimal in the mean field game. Wemore » derive the conditions, termed the socially optimal conditions, under which the *-Nash equilibrium of the mean field game maximizes the social welfare. Third, a primal-dual algorithm is proposed to compute the *-Nash equilibrium of the mean field game. Since the *-Nash equilibrium of the mean field game is socially optimal, we can compute the equilibrium by solving the social welfare maximization problem, which can be addressed by a decentralized primal-dual algorithm. Numerical simulations are presented to demonstrate the effectiveness of the proposed approach.« less

The deconfining phase transition in and out of equilibrium

NASA Astrophysics Data System (ADS)

Bazavov, Oleksiy

Recent experiments carried out at the Relativistic Heavy Ion Collider at the Brookhaven National Laboratory provide strong evidence that a matter can be driven from a confined, low-temperature phase, observed in our every day world into a deconfined high-temperature phase of liberated quarks and gluons. The equilibrium and dynamical properties of the deconfining phase transition are thus of great theoretical interest, since they also provide an information about the first femtoseconds of the evolution of our Universe, when the hot primordial soup while cooling has undergone a chain of phase transitions. The aspects of the deconfining phase transition studied in this work include: the dynamics of the SU(3) gauge theory after the heating quench (which models rapid heating in the heavy-ion collisions), equilibrium properties of the phase transition in the SU(3) gauge theory with boundaries at low temperature (small volumes at RHIC suggest that boundary effects cannot be neglected and periodic boundary conditions normally used in lattice simulations do not correspond to the experimental situation), and a study of the order of the transition in U(1) gauge theory.

High enthalpy hypersonic boundary layer flow

NASA Technical Reports Server (NTRS)

Yanow, G.

1972-01-01

A theoretical and experimental study of an ionizing laminar boundary layer formed by a very high enthalpy flow (in excess of 12 eV per atom or 7000 cal/gm) with allowance for the presence of helium driver gas is described. The theoretical investigation has shown that the use of variable transport properties and their respective derivatives is very important in the solution of equilibrium boundary layer equations of high enthalpy flow. The effect of low level helium contamination on the surface heat transfer rate is minimal. The variation of ionization is much smaller in a chemically frozen boundary layer solution than in an equilibrium boundary layer calculation and consequently, the variation of the transport properties in the case of the former was not essential in the integration. The experiments have been conducted in a free piston shock tunnel, and a detailed study of its nozzle operation, including the effects of low levels of helium driver gas contamination has been made. Neither the extreme solutions of an equilibrium nor of a frozen boundary layer will adequately predict surface heat transfer rate in very high enthalpy flows.

FORTRAN 4 computer program for calculation of thermodynamic and transport properties of complex chemical systems

NASA Technical Reports Server (NTRS)

Svehla, R. A.; Mcbride, B. J.

1973-01-01

A FORTRAN IV computer program for the calculation of the thermodynamic and transport properties of complex mixtures is described. The program has the capability of performing calculations such as:(1) chemical equilibrium for assigned thermodynamic states, (2) theoretical rocket performance for both equilibrium and frozen compositions during expansion, (3) incident and reflected shock properties, and (4) Chapman-Jouguet detonation properties. Condensed species, as well as gaseous species, are considered in the thermodynamic calculation; but only the gaseous species are considered in the transport calculations.

Surface modification of carbon nanotubes using 3-aminopropyltriethoxysilane to improve mechanical properties of nanocomposite based polymer matrix: Experimental and Density functional theory study

NASA Astrophysics Data System (ADS)

Hamed Mashhadzadeh, A.; Fereidoon, Ab.; Ghorbanzadeh Ahangari, M.

2017-10-01

In current study we combined theoretical and experimental studies to evaluate the effect of functionalization and silanization on mechanical behavior of polymer-based/CNT nanocomposites. Epoxy was selected as thermoset polymer, polypropylene and poly vinyl chloride were selected as thermoplastic polymers. The whole procedure is divided to two sections . At first we applied density functional theory (DFT) to analyze the effect of functionalization on equilibrium distance and adsorption energy of unmodified, functionalized by sbnd OH group and silanized epoxy/CNT, PP/CNT and PVC/CNT nanocomposites and the results showed that functionalization increased adsorption energy and reduced the equilibrium distance in all studied nanocomposites and silanization had higher effect comparing to OH functionalizing. Then we prepared experimental samples of all mentioned nanocomposites and tested their tensile and flexural strength properties. The obtained results showed that functionalization increased the studied mechanical properties in all evaluated nanocomposites. Finally we compared the results of experimental and theoretical sections with each other and estimated a suitable agreement between these parts.

Mechanical Behaviour of Bolted Joints Under Impact Rates of Loading

DTIC Science & Technology

2012-01-01

Joints in Glass Fibre / Epoxy Laminates. Composites, Volume 16. No 2. Kolsky, H. (1949). An Investigation of the Mechanical Properties of Materials at...and equations 2.1 and 2, Figures 2.3, 2.4, and 2.5 were constructed to determine optimal specimen properties for later testing of bolted joints of...9.5 l/d=11.5 UNCLASSIFIED UNCLASSIFIED 2.5 Discussion Ideal specimen properties are high total equilibrium times, low equilibrium start times and

Assortative mating and mutation diffusion in spatial evolutionary systems

NASA Astrophysics Data System (ADS)

Paley, C. J.; Taraskin, S. N.; Elliott, S. R.

2010-04-01

The influence of spatial structure on the equilibrium properties of a sexual population model defined on networks is studied numerically. Using a small-world-like topology of the networks as an investigative tool, the contributions to the fitness of assortative mating and of global mutant spread properties are considered. Simple measures of nearest-neighbor correlations and speed of spread of mutants through the system have been used to confirm that both of these dynamics are important contributory factors to the fitness. It is found that assortative mating increases the fitness of populations. Quick global spread of favorable mutations is shown to be a key factor increasing the equilibrium fitness of populations.

Effects of temperature, pH, and ionic strength on the adsorption of nanoparticles at liquid-liquid interfaces

NASA Astrophysics Data System (ADS)

Ferdous, Sultana; Ioannidis, Marios A.; Henneke, Dale E.

2012-05-01

The effects of temperature, pH and sodium chloride (NaCl) concentration on the equilibrium and dynamic interfacial tension (IFT) of 4.4-nm gold nanoparticles capped with n-dodecanethiol at hydrocarbon-water interfaces was studied. The pendant drop technique was used to study the adsorption properties of these nanoparticles at the hexane-water and nonane-water interfaces. The physical size of the gold nanoparticles was determined by TEM image analysis. The interfacial properties of mixtures of these nanoparticles, having different sizes and capping agents, were then studied. The addition of NaCl was found to cause a decrease of the equilibrium and dynamic IFT greater than that which accompanies the adsorption of nanoparticles at the interface in the absence of NaCl. Although IFT values for acidic and neutral conditions were found to be similar, a noticeable decrease in the IFT was found for more basic conditions. Increasing the temperature of the system was found to cause an increase in both dynamic and equilibrium IFT values. These findings have implications for the self-assembly of functionalized gold nanoparticles at liquid-liquid interfaces.

Computer Program for Calculation of Complex Chemical Equilibrium Compositions, Rocket Performance, Incident and Reflected Shocks, and Chapman-Jouguet Detonations. Interim Revision, March 1976

NASA Technical Reports Server (NTRS)

Gordon, S.; Mcbride, B. J.

1976-01-01

A detailed description of the equations and computer program for computations involving chemical equilibria in complex systems is given. A free-energy minimization technique is used. The program permits calculations such as (1) chemical equilibrium for assigned thermodynamic states (T,P), (H,P), (S,P), (T,V), (U,V), or (S,V), (2) theoretical rocket performance for both equilibrium and frozen compositions during expansion, (3) incident and reflected shock properties, and (4) Chapman-Jouguet detonation properties. The program considers condensed species as well as gaseous species.

Comparison of Themodynamic and Transport Property Models for Computing Equilibrium High Enthalpy Flows

NASA Astrophysics Data System (ADS)

Ramasahayam, Veda Krishna Vyas; Diwakar, Anant; Bodi, Kowsik

2017-11-01

To study the flow of high temperature air in vibrational and chemical equilibrium, accurate models for thermodynamic state and transport phenomena are required. In the present work, the performance of a state equation model and two mixing rules for determining equilibrium air thermodynamic and transport properties are compared with that of curve fits. The thermodynamic state model considers 11 species which computes flow chemistry by an iterative process and the mixing rules considered for viscosity are Wilke and Armaly-Sutton. The curve fits of Srinivasan, which are based on Grabau type transition functions, are chosen for comparison. A two-dimensional Navier-Stokes solver is developed to simulate high enthalpy flows with numerical fluxes computed by AUSM+-up. The accuracy of state equation model and curve fits for thermodynamic properties is determined using hypersonic inviscid flow over a circular cylinder. The performance of mixing rules and curve fits for viscosity are compared using hypersonic laminar boundary layer prediction on a flat plate. It is observed that steady state solutions from state equation model and curve fits match with each other. Though curve fits are significantly faster the state equation model is more general and can be adapted to any flow composition.

Investigation of CNTD Mechanism and its Effect on Microstructural Properties.

DTIC Science & Technology

1980-10-01

Equilibrium Degree of Completion of SiCl4 Reduction 31 as a Function of Temperature, Pressure and Degree ofDilution. 9. Equilibrium Degree of Completion...Disproportionation Study with SiCl4 . A) 500/2500X B) 600/3000X 11. Morphology of Deposit Made in the Silicon Halide 39 Disproportionation Study with SiHCl 3. A...at a constant ratio of SiCl4 to NH 3 of 0.2 (except run #29, see Table A-1 Appendix I). The active gas partial pressure was calculated according to the

Geometrical Description of Chemical Equilibrium and Le Cha^telier's Principle: Two-Component Systems

ERIC Educational Resources Information Center

Novak, Igor

2018-01-01

Chemical equilibrium is one of the most important concepts in chemistry. The changes in properties of the chemical system at equilibrium induced by variations in pressure, volume, temperature, and concentration are always included in classroom teaching and discussions. This work introduces a novel, geometrical approach to understanding the…

Composition and Thermodynamic Properties of Air in Chemical Equilibrium

NASA Technical Reports Server (NTRS)

Moeckel, W E; Weston, Kenneth C

1958-01-01

Charts have been prepared relating the thermodynamic properties of air in chemical equilibrium for temperatures to 15,000 degrees k and for pressures 10(-5) to 10 (plus 4) atmospheres. Also included are charts showing the composition of air, the isentropic exponent, and the speed of sound. These charts are based on thermodynamic data calculated by the National Bureau of Standards.

Quantifying differences in the impact of variable chemistry on equilibrium uranium(VI) adsorption properties of aquifer sediments

USGS Publications Warehouse

Stoliker, Deborah L.; Kent, Douglas B.; Zachara, John M.

2011-01-01

Uranium adsorption-desorption on sediment samples collected from the Hanford 300-Area, Richland, WA varied extensively over a range of field-relevant chemical conditions, complicating assessment of possible differences in equilibrium adsorption properties. Adsorption equilibrium was achieved in 500-1000 h although dissolved uranium concentrations increased over thousands of hours owing to changes in aqueous chemical composition driven by sediment-water reactions. A nonelectrostatic surface complexation reaction, >SOH + UO22+ + 2CO32- = >SOUO2(CO3HCO3)2-, provided the best fit to experimental data for each sediment sample resulting in a range of conditional equilibrium constants (logKc) from 21.49 to 21.76. Potential differences in uranium adsorption properties could be assessed in plots based on the generalized mass-action expressions yielding linear trends displaced vertically by differences in logKc values. Using this approach, logKc values for seven sediment samples were not significantly different. However, a significant difference in adsorption properties between one sediment sample and the fines (Kc uncertainty were improved by capturing all data points within experimental errors. The mass-action expression plots demonstrate that applying models outside the range of conditions used in model calibration greatly increases potential errors.

Invariant structures of magnetic flux tubes

NASA Astrophysics Data System (ADS)

Solovev, A. A.

1982-04-01

The basic properties of a screened magnetic flux tube possessing a finite radius of curvature are discussed in order to complement the findings of Parker (1974, 1976) and improve their accuracy. Conditions of equilibrium, twisting equilibrium, and twisting oscillations are discussed, showing that a twisted magnetic loop or arch is capable of executing elastic oscillations about an equilibrium state. This property can in particular be used in the theory of solar flares. Invariant structures of a force-free magnetic tube are analyzed, showing that invariant structures of the field preserve their form when the geometrical parameters of the flux tube are changed. In a quasi-equilibrium transition of the tube from one state to another the length and pitch of the tube spiral change in proportion to the radius of its cross section.

Equilibrium time correlation functions and the dynamics of fluctuations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luban, Marshall; Luscombe, James H.

1999-12-01

Equilibrium time correlation functions are of great importance because they probe the equilibrium dynamical response to external perturbations. We discuss the properties of time correlation functions for several systems that are simple enough to illustrate the calculational steps involved. The discussion underscores the need for avoiding language which misleadingly suggests that thermal equilibrium is associated with a quiescent or moribund state of the system. (c) 1999 American Association of Physics Teachers.

Investigation of the Hydrochlorination of SiCl4

NASA Technical Reports Server (NTRS)

Mui, J. Y. P.

1983-01-01

The hydrochlorination of silicon tetrachloride with hydrogen and metallurgical grade (m.g.) silicon metal, 3 SiCl4 + 2 H2 + Si yields 4 SiHCl3 was shown to be an efficient process to produce trichlorosilane. A research and development program was carried out to study the hydrochlorination reaction over a wide range of reaction conditions. Equilibrium constant and reaction kinetics measurements were made to provide the basis for a theoretical study on the hydrochlorination process. Thermodynamic properties of the hydrochlorination reaction were also measured. The effects of temperature, pressure, and concentration on the equilibrium constant, K sub p, were studied.

Measuring the Thermodynamics of the Alloy/Scale Interface

NASA Technical Reports Server (NTRS)

Copland, Evan

2004-01-01

A method is proposed for the direct measurement of the thermodynamic properties of the alloy and oxide compound at the alloy/scale interface observed during steady-state oxidation. The thermodynamic properties of the alloy/scale interface define the driving force for solid-state transport in the alloy and oxide compound. Accurate knowledge of thermodynamic properties of the interface will advance our understanding of oxidation behavior. The method is based on the concept of local equilibrium and assumes that an alloy+scale equilibrium very closely approximates the alloy/scale interface observed during steady-state oxidation. The thermodynamics activities of this alloy+scale equilibrium are measured directly by Knudsen effusion-cell mass spectrometer (KEMS) using the vapor pressure technique. The theory and some practical considerations of this method are discussed in terms of beta-NiAl oxidation.

Examples of equilibrium and non-equilibrium behavior in evolutionary systems

NASA Astrophysics Data System (ADS)

Soulier, Arne

With this thesis, we want to shed some light into the darkness of our understanding of simply defined statistical mechanics systems and the surprisingly complex dynamical behavior they exhibit. We will do so by presenting in turn one equilibrium and then one non-equilibrium system with evolutionary dynamics. In part 1, we will present the seceder-model, a newly developed system that cannot equilibrate. We will then study several properties of the system and obtain an idea of the richness of the dynamics of the seceder model, which is particular impressive given the minimal amount of modeling necessary in its setup. In part 2, we will present extensions to the directed polymer in random media problem on a hypercube and its connection to the Eigen model of evolution. Our main interest will be the influence of time-dependent and time-independent changes in the fitness landscape viewed by an evolving population. This part contains the equilibrium dynamics. The stochastic models and the topic of evolution and non-equilibrium in general will allow us to point out similarities to the various lines of thought in game theory.

Oxygen transport properties estimation by DSMC-CT simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruno, Domenico; Frezzotti, Aldo; Ghiroldi, Gian Pietro

Coupling DSMC simulations with classical trajectories calculations is emerging as a powerful tool to improve predictive capabilities of computational rarefied gas dynamics. The considerable increase of computational effort outlined in the early application of the method (Koura,1997) can be compensated by running simulations on massively parallel computers. In particular, GPU acceleration has been found quite effective in reducing computing time (Ferrigni,2012; Norman et al.,2013) of DSMC-CT simulations. The aim of the present work is to study rarefied Oxygen flows by modeling binary collisions through an accurate potential energy surface, obtained by molecular beams scattering (Aquilanti, et al.,1999). The accuracy ofmore » the method is assessed by calculating molecular Oxygen shear viscosity and heat conductivity following three different DSMC-CT simulation methods. In the first one, transport properties are obtained from DSMC-CT simulations of spontaneous fluctuation of an equilibrium state (Bruno et al, Phys. Fluids, 23, 093104, 2011). In the second method, the collision trajectory calculation is incorporated in a Monte Carlo integration procedure to evaluate the Taxman’s expressions for the transport properties of polyatomic gases (Taxman,1959). In the third, non-equilibrium zero and one-dimensional rarefied gas dynamic simulations are adopted and the transport properties are computed from the non-equilibrium fluxes of momentum and energy. The three methods provide close values of the transport properties, their estimated statistical error not exceeding 3%. The experimental values are slightly underestimated, the percentage deviation being, again, few percent.« less

Effects of physical aging on long-term behavior of composites

NASA Technical Reports Server (NTRS)

Brinson, L. Catherine

1993-01-01

The HSCT plane, envisioned to have a lifetime of over 60,000 flight hours and to travel at speeds in excess of Mach 2, is the source of intensive study at NASA. In particular, polymer matrix composites are being strongly considered for use in primary and secondary structures due to their high strength to weight ratio and the options of property tailoring. However, an added difficulty in the use of polymer based materials is that their properties change significantly over time, especially at the elevated temperatures that will be experienced during flight, and prediction of properties based on irregular thermal and mechanical loading is extremely difficult. This study focused on one aspect of long-term polymer composite behavior: physical aging. When a polymer is cooled to below its glass transition temperature, the material is not in thermodynamic equilibrium and the free volume and enthalpy evolve over time to approach their equilibrium values. During this time, the mechanical properties change significantly and this change is termed physical aging. This work begins with a review of the concepts of physical aging on a pure polymer system. The effective time theory, which can be used to predict long term behavior based on short term data, is mathematically formalized. The effects of aging to equilibrium are proven and discussed. The theory developed for polymers is then applied first to a unidirectional composite, then to a general laminate. Comparison to experimental data is excellent. It is shown that the effects of aging on the long-term properties of composites can be counter-intuitive, stressing the importance of the development and use of a predictive theory to analyze structures.

Equilibrium and nonequilibrium models on solomon networks with two square lattices

NASA Astrophysics Data System (ADS)

Lima, F. W. S.

We investigate the critical properties of the equilibrium and nonequilibrium two-dimensional (2D) systems on Solomon networks with both nearest and random neighbors. The equilibrium and nonequilibrium 2D systems studied here by Monte Carlo simulations are the Ising and Majority-vote 2D models, respectively. We calculate the critical points as well as the critical exponent ratios γ/ν, β/ν, and 1/ν. We find that numerically both systems present the same exponents on Solomon networks (2D) and are of different universality class than the regular 2D ferromagnetic model. Our results are in agreement with the Grinstein criterion for models with up and down symmetry on regular lattices.

Characteristics of ring type traveling wave ultrasonic motor in vacuum.

PubMed

Qu, Jianjun; Zhou, Ningning; Tian, Xiu; Jin, Long; Xu, Zhike

2009-03-01

The characteristics of ultrasonic motor strongly depend on the properties of stator/rotor contact interface which are affected by ambient environment. With the developed apparatus, load properties of two ring type traveling wave ultrasonic motors in atmosphere, low vacuum and high vacuum were studied, respectively. Wear of friction material, variations of vacuum degree and the temperature of motor during the experiment were also measured. The results show that load properties of motor A in vacuum were poorer than those in atmosphere, when load torque M(f) was less than 0.55 N m. Compared to motor A, load properties of motor B were affected a little by environmental pressure. Wear of friction material in vacuum was more severe than wear in atmosphere. The temperature of motor in vacuum rose more quickly than it in atmosphere and had not reached equilibrium in 2 h experiment. However, the temperature of motor in atmosphere had reached equilibrium in about forth minutes. Furthermore, outgas was also observed during experiment under vacuum conditions.

Emergent thermodynamics in a system of macroscopic, chaotic surface waves

NASA Astrophysics Data System (ADS)

Welch, Kyle J.

The properties of conventional materials are inextricably linked with their molecular composition; to make water flow like wine would require changing its molecular identity. To circumvent this restriction, I have constructed and characterized a two-dimensional metafluid, so-called because its constitutive dynamics are derived not from atoms and molecules but from macroscopic, chaotic surface waves excited on a vertically agitated fluid. Unlike in conventional fluids, the viscosity and temperature of this metafluid are independently tunable. Despite this unconventional property, our system is surprisingly consistent with equilibrium thermodynamics, despite being constructed from macroscopic, non-equilibrium elements. As a programmable material, our metafluid represents a new platform on which to study complex phenomena such as self-assembly and pattern formation. We demonstrate one such application in our study of short-chain polymer analogs embedded in our system.

Kinetic characteristic of phenanthrene sorption in aged soil amended with biochar

NASA Astrophysics Data System (ADS)

Kim, Chanyang; Kim, Yong-Seong; Hyun, Seunghun

2015-04-01

Biochar has been recently highlighted as an amendment that affects yield of the crops by increasing pH, cation exchange capacity and water retention, and reduces the lability of contaminants by increasing sorption capacity in the soil system. Biochar's physico-chemical properties, high CEC, surfaces containing abundant micropores and macropores, and various types of functional groups, play important roles in enhancing sorption capacity of contaminants. Aging through a natural weathering process might change physico-chemical properties of biochar amended in soils, which can affect the sorption behavior of contaminants. Thus, in this study, the sorption characteristics of phenanthrene (PHE) on biochar-amended soils were studied with various types of chars depending on aging time. To do this, 1) soil was amended with sludge waste char (SWC), wood char (WC), and municipal waste char (MWC) during 0, 6, and 12 month. Chars were applied to soil at 1% and 2.5% (w/w) ratio. 2) Several batch kinetic and equilibrium studies were conducted. One-compartment first order and two-compartment first order model apportioning the fraction of fast and slow sorbing were selected for kinetic models. Where, qt is PHE concentration in biochar-amended soils at each time t, qeis PHE concentration in biochar-amended soils at equilibrium. ff is fastly sorbing fraction and (1-ff) is slowly sorbing fraction. k is sorption rate constant from one-compartment first order model, k1 and k2 are sorption rate constant from two-compartment first order model, t is time (hr). The equilibrium sorption data were fitted with Fruendlich and Langmuir equation. 3) Change in physico-chemical properties of biochar-amended soils was investigated with aging time. Batch equilibrium sorption results suggested that sorbed amount of PHE on WC was greater than SWC and MWC. The more char contents added to soil, the greater sorption capacity of PHE. Sorption equilibrium was reached after 4 hours and equilibrium pH ranged from 6.5 to 8.0. Sorption capacity was reduced with aging time. From kinetic results, two-compartment first order model was more suitable than one-compartment first order model. Fast sorption site of biochar-amended soils dominated total sorption process (i.e., Fraction of fast sorption site ranged from 0.55 to 0.96). Reduced sorption capacity with aging time could be attributed to changes in physico-chemical properties of biochar-amended soils (e.g., reduced pores and increased hydrophilic carboxyl and carbonyl functional groups). Verification is FI-IR and SSA. It is assumed that biochar is a suitable material for PHE contaminated soil in order to reduce the lability of PHE. However, aging effects would lessen biochar benefit for reducing the sorption capacity of PHE by forming hydrophilic functional group and reducing pores.

Topological nature of the inertiality of a nonequilibrium system far from equilibrium

NASA Astrophysics Data System (ADS)

Saikhanov, M. B.

2017-04-01

We consider inertial and topological properties of a nonequilibrium system far from the equilibrium. We show that from the topological standpoint, the layered structure of the energy levels of a nonequilibrium system leads to the concept of connectivity. We state an assumption on the key role of the dimension of the hypersurface of the full entropy production in the study of the inertiality of an irreversible process in a nonequilibrium system including in the region of unstable states.

Local equilibrium and the second law of thermodynamics for irreversible systems with thermodynamic inertia.

PubMed

Glavatskiy, K S

2015-10-28

Validity of local equilibrium has been questioned for non-equilibrium systems which are characterized by delayed response. In particular, for systems with non-zero thermodynamic inertia, the assumption of local equilibrium leads to negative values of the entropy production, which is in contradiction with the second law of thermodynamics. In this paper, we address this question by suggesting a variational formulation of irreversible evolution of a system with non-zero thermodynamic inertia. We introduce the Lagrangian, which depends on the properties of the normal and the so-called "mirror-image" systems. We show that the standard evolution equations, in particular, the Maxwell-Cattaneo-Vernotte equation, can be derived from the variational procedure without going beyond the assumption of local equilibrium. We also argue that the second law of thermodynamics in non-equilibrium should be understood as a consequence of the variational procedure and the property of local equilibrium. For systems with instantaneous response this leads to the standard requirement of the local instantaneous entropy production being always positive. However, if a system is characterized by delayed response, the formulation of the second law of thermodynamics should be altered. In particular, the quantity, which is always positive, is not the instantaneous entropy production, but the entropy production averaged over a proper time interval.

Equilibrium and out-of-equilibrium mechanics of living mammalian cytoplasm

NASA Astrophysics Data System (ADS)

Gupta, Satish Kumar; Guo, Ming

2017-10-01

Living cells are intrinsically non-equilibrium systems. They are driven out of equilibrium by the activity of the molecular motors and other enzymatic processes. This activity along with the ever present thermal agitation results in intracellular fluctuations inside the cytoplasm. In analogy to Brownian motion, the material property of the cytoplasm also influences the characteristics of these fluctuations. In this paper, through a combination of experimentation and theoretical analysis, we show that intracellular fluctuations are indeed due to non-thermal forces at relatively long time-scales, however, are dominated solely by thermal forces at relatively short time-scales. Thus, the cytoplasm of living mammalian cells behaves as an equilibrium material at short time-scales. The mean square displacement of these intracellular fluctuations scales inversely with the cytoplasmic shear modulus in this short time-scale equilibrium regime, and is inversely proportional to the square of the cytoplasmic shear modulus in the long time-scale out-of-equilibrium regime. Furthermore, we deploy passive microrheology based on these fluctuations to extract the mechanical property of the cytoplasm at the high-frequency regime. We show that the cytoplasm of living mammalian cells is a weak elastic gel in this regime; this is in an excellent agreement with an independent micromechanical measurement using optical tweezers.

Molecular simulation of the thermodynamic, structural, and vapor-liquid equilibrium properties of neon

NASA Astrophysics Data System (ADS)

Vlasiuk, Maryna; Frascoli, Federico; Sadus, Richard J.

2016-09-01

The thermodynamic, structural, and vapor-liquid equilibrium properties of neon are comprehensively studied using ab initio, empirical, and semi-classical intermolecular potentials and classical Monte Carlo simulations. Path integral Monte Carlo simulations for isochoric heat capacity and structural properties are also reported for two empirical potentials and one ab initio potential. The isobaric and isochoric heat capacities, thermal expansion coefficient, thermal pressure coefficient, isothermal and adiabatic compressibilities, Joule-Thomson coefficient, and the speed of sound are reported and compared with experimental data for the entire range of liquid densities from the triple point to the critical point. Lustig's thermodynamic approach is formally extended for temperature-dependent intermolecular potentials. Quantum effects are incorporated using the Feynman-Hibbs quantum correction, which results in significant improvement in the accuracy of predicted thermodynamic properties. The new Feynman-Hibbs version of the Hellmann-Bich-Vogel potential predicts the isochoric heat capacity to an accuracy of 1.4% over the entire range of liquid densities. It also predicts other thermodynamic properties more accurately than alternative intermolecular potentials.

Equilibrium properties of dense hydrogen isotope gases based on the theory of simple fluids.

PubMed

Kowalczyk, Piotr; MacElroy, J M D

2006-08-03

We present a new method for the prediction of the equilibrium properties of dense gases containing hydrogen isotopes. The proposed approach combines the Feynman-Hibbs effective potential method and a deconvolution scheme introduced by Weeks et al. The resulting equations of state and the chemical potentials as functions of pressure for each of the hydrogen isotope gases depend on a single set of Lennard-Jones parameters. In addition to its simplicity, the proposed method with optimized Lennard-Jones potential parameters accurately describes the equilibrium properties of hydrogen isotope fluids in the regime of moderate temperatures and pressures. The present approach should find applications in the nonlocal density functional theory of inhomogeneous quantum fluids and should also be of particular relevance to hydrogen (clean energy) storage and to the separation of quantum isotopes by novel nanomaterials.

Population annealing simulations of a binary hard-sphere mixture

NASA Astrophysics Data System (ADS)

Callaham, Jared; Machta, Jonathan

2017-06-01

Population annealing is a sequential Monte Carlo scheme well suited to simulating equilibrium states of systems with rough free energy landscapes. Here we use population annealing to study a binary mixture of hard spheres. Population annealing is a parallel version of simulated annealing with an extra resampling step that ensures that a population of replicas of the system represents the equilibrium ensemble at every packing fraction in an annealing schedule. The algorithm and its equilibration properties are described, and results are presented for a glass-forming fluid composed of a 50/50 mixture of hard spheres with diameter ratio of 1.4:1. For this system, we obtain precise results for the equation of state in the glassy regime up to packing fractions φ ≈0.60 and study deviations from the Boublik-Mansoori-Carnahan-Starling-Leland equation of state. For higher packing fractions, the algorithm falls out of equilibrium and a free volume fit predicts jamming at packing fraction φ ≈0.667 . We conclude that population annealing is an effective tool for studying equilibrium glassy fluids and the jamming transition.

[Simulation of effects of soil properties and plants on soil water-salt movement with reclaimed water irrigation by ENVIRO-GRO model].

PubMed

Lü, Si-Dan; Chen, Wei-Ping; Wang, Mei-E

2012-12-01

In order to promote safe irrigation with reclaimed water and prevent soil salinisation, the dynamic transport of salts in urban soils of Beijing under irrigation of reclaimed water was simulated by ENVIRO-GRO model in this study. The accumulation trends and profile distribution of soil salinity were predicted. Simultaneously, the effects of different soil properties and plants on soil water-salt movement and salt accumulation were investigated. Results indicated that soil salinity in the profiles reached uniform equilibrium conditions by repeated simulation, with different initial soil salinity. Under the conditions of loam and clay loam soil, salinity in the profiles increased over time until reaching equilibrium conditions, while under the condition of sandy loam soil, salinity in the profiles decreased over time until reaching equilibrium conditions. The saturated soil salinity (EC(e)) under equilibrium conditions followed an order of sandy loam < loam < clay loam. Salt accumulations in Japan euonymus and Chinese pine were less than that in Blue grass. The temporal and spatial distributions of soil salinity were also different in these three types of plants. In addition, the growth of the plants was not influenced by soil salinity (except clay loam), but mild soil salinization occurred under all conditions (except sandy loam).

Equilibrium paths analysis of materials with rheological properties by using the chaos theory

NASA Astrophysics Data System (ADS)

Bednarek, Paweł; Rządkowski, Jan

2018-01-01

The numerical equilibrium path analysis of the material with random rheological properties by using standard procedures and specialist computer programs was not successful. The proper solution for the analysed heuristic model of the material was obtained on the base of chaos theory elements and neural networks. The paper deals with mathematical reasons of used computer programs and also are elaborated the properties of the attractor used in analysis. There are presented results of conducted numerical analysis both in a numerical and in graphical form for the used procedures.

Fluids by design using chaotic surface waves to create a metafluid that is Newtonian, thermal, and entirely tunable

PubMed Central

Welch, Kyle J.; Liebman-Peláez, Alexander; Corwin, Eric I.

2016-01-01

In conventional fluids, viscosity depends on temperature according to a strict relationship. To change this relationship, one must change the molecular nature of the fluid. Here, we create a metafluid whose properties are derived not from the properties of molecules but rather from chaotic waves excited on the surface of vertically agitated water. By making direct rheological measurements of the flow properties of our metafluid, we show that it has independently tunable viscosity and temperature, a quality that no conventional fluid possesses. We go on to show that the metafluid obeys the Einstein relation, which relates many-body response (viscosity) to single-particle dynamics (diffusion) and is a fundamental result in equilibrium thermal systems. Thus, our metafluid is wholly consistent with equilibrium thermal physics, despite being markedly nonequilibrium. Taken together, our results demonstrate a type of material that retains equilibrium physics while simultaneously allowing for direct programmatic control over material properties. PMID:27621467

Prethermalized states of quenched spinor condensates

NASA Astrophysics Data System (ADS)

Chakram, Srivatsan; Patil, Yogesh Sharad; Vengalattore, Mukund

2015-05-01

Due to the interplay between spin and charge degrees of freedom, spinor Bose condensates exhibit a rich tapestry of magnetically ordered phases and topological defects. The non-equilibrium properties of these fluids have been the topic of recent interest. We have previously shown that quenched spinor condensates exhibit robust prethermalized states characterized by asymptotic correlations that differ from thermodynamic predictions. These non-equilibrium states arise due to the disparate energy scales between the phonon and magnon excitations. The identification of a microscopic origin of prethermalization makes this system a promising platform for studies of prethermalization and possible universal scaling relations that characterize these nonequilibrium many-body states. We elaborate on our studies of prethermalized spinor condensates and the prospects of observing a dynamical Kosterlitz-Thouless transition in this system. This work is supported by the ARO MURI on non-equilibrium dynamics.

Classical evolution of fractal measures on the lattice

NASA Astrophysics Data System (ADS)

Antoniou, N. G.; Diakonos, F. K.; Saridakis, E. N.; Tsolias, G. A.

2007-04-01

We consider the classical evolution of a lattice of nonlinear coupled oscillators for a special case of initial conditions resembling the equilibrium state of a macroscopic thermal system at the critical point. The displacements of the oscillators define initially a fractal measure on the lattice associated with the scaling properties of the order parameter fluctuations in the corresponding critical system. Assuming a sudden symmetry breaking (quench), leading to a change in the equilibrium position of each oscillator, we investigate in some detail the deformation of the initial fractal geometry as time evolves. In particular, we show that traces of the critical fractal measure can be sustained for large times, and we extract the properties of the chain that determine the associated time scales. Our analysis applies generally to critical systems for which, after a slow developing phase where equilibrium conditions are justified, a rapid evolution, induced by a sudden symmetry breaking, emerges on time scales much shorter than the corresponding relaxation or observation time. In particular, it can be used in the fireball evolution in a heavy-ion collision experiment, where the QCD critical point emerges, or in the study of evolving fractals of astrophysical and cosmological scales, and may lead to determination of the initial critical properties of the Universe through observations in the symmetry-broken phase.

Reaction-diffusion systems coupled at the boundary and the Morse-Smale property

NASA Astrophysics Data System (ADS)

Broche, Rita de Cássia D. S.; de Oliveira, Luiz Augusto F.

We study an one-dimensional nonlinear reaction-diffusion system coupled on the boundary. Such system comes from modeling problems of temperature distribution on two bars of same length, jointed together, with different diffusion coefficients. We prove the transversality property of unstable and stable manifolds assuming all equilibrium points are hyperbolic. To this end, we write the system as an equation with noncontinuous diffusion coefficient. We then study the nonincreasing property of the number of zeros of a linearized nonautonomous equation as well as the Sturm-Liouville properties of the solutions of a linear elliptic problem.

Non-equilibrium freezing behaviour of aqueous systems.

PubMed

MacKenzie, A P

1977-03-29

The tendencies to non-equilibrium freezing behaviour commonly noted in representative aqueous systems derive from bulk and surface properties according to the circumstances. Supercooling and supersaturation are limited by heterogeneous nucleation in the presence of solid impurities. Homogeneous nucleation has been observed in aqueous systems freed from interfering solids. Once initiated, crystal growth is ofter slowed and, very frequently, terminated with increasing viscosity. Nor does ice first formed always succeed in assuming its most stable crystalline form. Many of the more significant measurements on a given systeatter permitting the simultaneous representation of thermodynamic and non-equilibrium properties. The diagram incorporated equilibrium melting points, heterogeneous nucleation temperatures, homogeneous nucleation temperatures, glass transition and devitrification temperatures, recrystallization temperatures, and, where appropriate, solute solubilities and eutectic temperatures. Taken together, the findings on modle systems aid the identification of the kinetic and thermodynamic factors responsible for the freezing-thawing survival of living cells.

Computer program to solve two-dimensional shock-wave interference problems with an equilibrium chemically reacting air model

NASA Technical Reports Server (NTRS)

Glass, Christopher E.

1990-01-01

The computer program EASI, an acronym for Equilibrium Air Shock Interference, was developed to calculate the inviscid flowfield, the maximum surface pressure, and the maximum heat flux produced by six shock wave interference patterns on a 2-D, cylindrical configuration. Thermodynamic properties of the inviscid flowfield are determined using either an 11-specie, 7-reaction equilibrium chemically reacting air model or a calorically perfect air model. The inviscid flowfield is solved using the integral form of the conservation equations. Surface heating calculations at the impingement point for the equilibrium chemically reacting air model use variable transport properties and specific heat. However, for the calorically perfect air model, heating rate calculations use a constant Prandtl number. Sample calculations of the six shock wave interference patterns, a listing of the computer program, and flowcharts of the programming logic are included.

Computer program to solve two-dimensional shock-wave interference problems with an equilibrium chemically reacting air model

NASA Astrophysics Data System (ADS)

Glass, Christopher E.

1990-08-01

The computer program EASI, an acronym for Equilibrium Air Shock Interference, was developed to calculate the inviscid flowfield, the maximum surface pressure, and the maximum heat flux produced by six shock wave interference patterns on a 2-D, cylindrical configuration. Thermodynamic properties of the inviscid flowfield are determined using either an 11-specie, 7-reaction equilibrium chemically reacting air model or a calorically perfect air model. The inviscid flowfield is solved using the integral form of the conservation equations. Surface heating calculations at the impingement point for the equilibrium chemically reacting air model use variable transport properties and specific heat. However, for the calorically perfect air model, heating rate calculations use a constant Prandtl number. Sample calculations of the six shock wave interference patterns, a listing of the computer program, and flowcharts of the programming logic are included.

Chemical properties of ground water and their corrosion and encrustation effects on wells

USGS Publications Warehouse

Barnes, Ivan; Clarke, Frank Eldridge

1969-01-01

Well waters in Egypt, Nigeria, and West Pakistan were studied for their chemical properties and corrosive or encrusting behavior. From the chemical composition of the waters, reaction states with reference to equilibrium were tested for 29 possible coexisting oxides, carbonates, sulfides, and elements. Of the 29 solids considered, only calcite, CaCO3, and ferric hydroxide, Fe(OH)3, showed any correlation with the corrosiveness of the waters to mild steel (iron metal). All 39 of the waters tested were out of equilibrium with iron metal, but those waters in equilibrium or supersaturated with both calcite and ferric hydroxide were the least corrosive. Supersaturation with other solid phases apparently was unrelated to corrosion. A number of solids may form surface deposits in wells and lead to decreased yields by fouling well intakes (screens and gravel packs) or increasing friction losses in casings. Calcite, CaCO3; ferric hydroxide, Fe(OH)3; magnetite, Fe3O4; siderite, FeCO3; hausmannite, Mn304 (tetragonal); manganese spinel, Mn3O4 (isometric); three iron sulfides mackinawite, FeS (tetragonal); greigite, Fe3S4 (isometric); and smythite, Fe3S4 (rhombohedral)-copper hydroxide, Co(OH)2; and manganese hydroxide, Mn(OH)2, were all at least tentatively identified in the deposits sampled. Of geochemical interest is the demonstration that simple stable equilibrium models fail in nearly every case to predict compositions of water yielded by the wells studied. Only one stable phase (calcite) was found to exhibit behavior approximately predictable from stable equilibrium considerations. No other stable phase was found to behave as would be predicted from equilibrium considerations. All the solids found to precipitate (except calcite) are metastable in that they are not the least soluble phases possible in the systems studied. In terms of metastable equilibrium, siderite and ferric hydroxide behave approximately as would be predicted from equilibrium considerations, but both are metastable and the presence of neither would be anticipated if only the most stable phases were considered. The behaviors of none of the other solids would be predictable from either stable or metastable equilibrium considerations. An unanswered problem raised by the study reported here is how, or by what paths, truly stable phases form if first precipitates are generally metastable.The utility of the findings in well design and operation is in no way impaired by the general lack of equilibrium. Conditions leading to either corrosion (which is related to lack of supersaturation with protective phases), or encrustation (supersaturation with phases that were found to precipitate), or both, apparently can be identified. The application of the methods described can be of great importance in developing unexploited ground-water resources in that certain practical problems can be identified before extensive well construction and unnecessary well failure.

Reduced Nucleus Pulposus Glycosaminoglycan Content Alters Intervertebral Disc Dynamic Viscoelastic Mechanics

PubMed Central

Boxberger, John I.; Orlansky, Amy S.; Sen, Sounok; Elliott, Dawn M.

2009-01-01

The intervertebral disc functions over a range of dynamic loading regimes including axial loads applied across a spectrum of frequencies at varying compressive loads. Biochemical changes occurring in early degeneration, including reduced nucleus pulposus glycosaminoglycan content, may alter disc mechanical behavior and thus may contribute to the progression of degeneration. The objective of this study was to determine disc dynamic viscoelastic properties under several equilibrium loads and loading frequencies, and further, to determine how reduced nucleus glycosaminglycan content alters dynamic mechanics. We hypothesized (1) that dynamic stiffness would be elevated with increasing equilibrium load and increasing frequency, (2) that the disc would behave more elastically at higher frequencies, and finally, (3) that dynamic stiffness would be reduced at low equilibrium loads under all frequencies due to nucleus glycosaminoglycan loss. We mechanically tested control and chondroitinase-ABC injected rat lumbar motion segments at several equilibrium loads using oscillatory loading at frequencies ranging from 0.05 to 5 Hz. The rat lumbar disc behaved non-linearly with higher dynamic stiffness at elevated compressive loads irrespective of frequency. Phase angle was not affected by equilibrium load, although it decreased as frequency was increased. Reduced glycosaminoglycan decreased dynamic stiffness at low loads but not at high equilibrium loads and led to increased phase angle at all loads and frequencies. The findings of this study demonstrate the effect of equilibrium load and loading frequencies on dynamic disc mechanics and indicate possible mechanical mechanisms through which disc degeneration can progress. PMID:19539936

Bethe lattice approach and relaxation dynamics study of spin-crossover materials

NASA Astrophysics Data System (ADS)

Oke, Toussaint Djidjoho; Hontinfinde, Félix; Boukheddaden, Kamel

2015-07-01

Dynamical properties of Prussian blue analogs and spin-crossover materials are investigated in the framework of a Blume-Emery-Griffiths (BEG) spin-1 model, where states ±1 and 0 represent the high-spin (HS) state and the low-spin state, respectively. The quadrupolar interaction depends on the temperature in the form . Magnetic interactions are controlled by a factor such that for (), magnetic ordering is not expected. The model is exactly solved using the Bethe lattice approach for the equilibrium properties. The results are closer to those calculated by numerical simulations with suitable Arrhenius-type transition rates. The study of relaxation processes of non-equilibrium HS states revealed one-step nonlinear sigmoidal relaxation curves of the HS fraction at low temperatures. We found that increasing the magnetic interactions leads to the appearance of a plateau in the thermal hysteresis as well as in the relaxation curves of the HS fraction at low temperature.

An alternative extragradient projection method for quasi-equilibrium problems.

PubMed

Chen, Haibin; Wang, Yiju; Xu, Yi

2018-01-01

For the quasi-equilibrium problem where the players' costs and their strategies both depend on the rival's decisions, an alternative extragradient projection method for solving it is designed. Different from the classical extragradient projection method whose generated sequence has the contraction property with respect to the solution set, the newly designed method possesses an expansion property with respect to a given initial point. The global convergence of the method is established under the assumptions of pseudomonotonicity of the equilibrium function and of continuity of the underlying multi-valued mapping. Furthermore, we show that the generated sequence converges to the nearest point in the solution set to the initial point. Numerical experiments show the efficiency of the method.

Confinement properties of tokamak plasmas with extended regions of low magnetic shear

NASA Astrophysics Data System (ADS)

Graves, J. P.; Cooper, W. A.; Kleiner, A.; Raghunathan, M.; Neto, E.; Nicolas, T.; Lanthaler, S.; Patten, H.; Pfefferle, D.; Brunetti, D.; Lutjens, H.

2017-10-01

Extended regions of low magnetic shear can be advantageous to tokamak plasmas. But the core and edge can be susceptible to non-resonant ideal fluctuations due to the weakened restoring force associated with magnetic field line bending. This contribution shows how saturated non-linear phenomenology, such as 1 / 1 Long Lived Modes, and Edge Harmonic Oscillations associated with QH-modes, can be modelled accurately using the non-linear stability code XTOR, the free boundary 3D equilibrium code VMEC, and non-linear analytic theory. That the equilibrium approach is valid is particularly valuable because it enables advanced particle confinement studies to be undertaken in the ordinarily difficult environment of strongly 3D magnetic fields. The VENUS-LEVIS code exploits the Fourier description of the VMEC equilibrium fields, such that full Lorenzian and guiding centre approximated differential operators in curvilinear angular coordinates can be evaluated analytically. Consequently, the confinement properties of minority ions such as energetic particles and high Z impurities can be calculated accurately over slowing down timescales in experimentally relevant 3D plasmas.

Dynamical properties of a minimally parameterized mathematical model for metronomic chemotherapy.

PubMed

Schättler, Heinz; Ledzewicz, Urszula; Amini, Behrooz

2016-04-01

A minimally parameterized mathematical model for low-dose metronomic chemotherapy is formulated that takes into account angiogenic signaling between the tumor and its vasculature and tumor inhibiting effects of tumor-immune system interactions. The dynamical equations combine a model for tumor development under angiogenic signaling formulated by Hahnfeldt et al. with a model for tumor-immune system interactions by Stepanova. The dynamical properties of the model are analyzed. Depending on the parameter values, the system encompasses a variety of medically realistic scenarios that range from cases when (i) low-dose metronomic chemotherapy is able to eradicate the tumor (all trajectories converge to a tumor-free equilibrium point) to situations when (ii) tumor dormancy is induced (a unique, globally asymptotically stable benign equilibrium point exists) to (iii) multi-stable situations that have both persistent benign and malignant behaviors separated by the stable manifold of an unstable equilibrium point and finally to (iv) situations when tumor growth cannot be overcome by low-dose metronomic chemotherapy. The model forms a basis for a more general study of chemotherapy when the main components of a tumor's microenvironment are taken into account.

Group Contribution Methods for Phase Equilibrium Calculations.

PubMed

Gmehling, Jürgen; Constantinescu, Dana; Schmid, Bastian

2015-01-01

The development and design of chemical processes are carried out by solving the balance equations of a mathematical model for sections of or the whole chemical plant with the help of process simulators. For process simulation, besides kinetic data for the chemical reaction, various pure component and mixture properties are required. Because of the great importance of separation processes for a chemical plant in particular, a reliable knowledge of the phase equilibrium behavior is required. The phase equilibrium behavior can be calculated with the help of modern equations of state or g(E)-models using only binary parameters. But unfortunately, only a very small part of the experimental data for fitting the required binary model parameters is available, so very often these models cannot be applied directly. To solve this problem, powerful predictive thermodynamic models have been developed. Group contribution methods allow the prediction of the required phase equilibrium data using only a limited number of group interaction parameters. A prerequisite for fitting the required group interaction parameters is a comprehensive database. That is why for the development of powerful group contribution methods almost all published pure component properties, phase equilibrium data, excess properties, etc., were stored in computerized form in the Dortmund Data Bank. In this review, the present status, weaknesses, advantages and disadvantages, possible applications, and typical results of the different group contribution methods for the calculation of phase equilibria are presented.

Dissipative exciton transfer in donor-bridge-acceptor systems: numerical renormalization group calculation of equilibrium properties.

PubMed

Tornow, Sabine; Tong, Ning-Hua; Bulla, Ralf

2006-07-05

We present a detailed model study of exciton transfer processes in donor-bridge-acceptor (DBA) systems. Using a model which includes the intermolecular Coulomb interaction and the coupling to a dissipative environment we calculate the phase diagram, the absorption spectrum as well as dynamic equilibrium properties with the numerical renormalization group. This method is non-perturbative and therefore allows one to cover the full parameter space, especially the case when the intermolecular Coulomb interaction is of the same order as the coupling to the environment and perturbation theory cannot be applied. For DBA systems with up to six sites we found a transition to the localized phase (self-trapping) depending on the coupling to the dissipative environment. We discuss various criteria which favour delocalized exciton transfer.

Local equilibrium and the second law of thermodynamics for irreversible systems with thermodynamic inertia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glavatskiy, K. S.

Validity of local equilibrium has been questioned for non-equilibrium systems which are characterized by delayed response. In particular, for systems with non-zero thermodynamic inertia, the assumption of local equilibrium leads to negative values of the entropy production, which is in contradiction with the second law of thermodynamics. In this paper, we address this question by suggesting a variational formulation of irreversible evolution of a system with non-zero thermodynamic inertia. We introduce the Lagrangian, which depends on the properties of the normal and the so-called “mirror-image” systems. We show that the standard evolution equations, in particular, the Maxwell-Cattaneo-Vernotte equation, can bemore » derived from the variational procedure without going beyond the assumption of local equilibrium. We also argue that the second law of thermodynamics in non-equilibrium should be understood as a consequence of the variational procedure and the property of local equilibrium. For systems with instantaneous response this leads to the standard requirement of the local instantaneous entropy production being always positive. However, if a system is characterized by delayed response, the formulation of the second law of thermodynamics should be altered. In particular, the quantity, which is always positive, is not the instantaneous entropy production, but the entropy production averaged over a proper time interval.« less

Weak interactions, omnivory and emergent food-web properties.

PubMed

Emmerson, Mark; Yearsley, Jon M

2004-02-22

Empirical studies have shown that, in real ecosystems, species-interaction strengths are generally skewed in their distribution towards weak interactions. Some theoretical work also suggests that weak interactions, especially in omnivorous links, are important for the local stability of a community at equilibrium. However, the majority of theoretical studies use uniform distributions of interaction strengths to generate artificial communities for study. We investigate the effects of the underlying interaction-strength distribution upon the return time, permanence and feasibility of simple Lotka-Volterra equilibrium communities. We show that a skew towards weak interactions promotes local and global stability only when omnivory is present. It is found that skewed interaction strengths are an emergent property of stable omnivorous communities, and that this skew towards weak interactions creates a dynamic constraint maintaining omnivory. Omnivory is more likely to occur when omnivorous interactions are skewed towards weak interactions. However, a skew towards weak interactions increases the return time to equilibrium, delays the recovery of ecosystems and hence decreases the stability of a community. When no skew is imposed, the set of stable omnivorous communities shows an emergent distribution of skewed interaction strengths. Our results apply to both local and global concepts of stability and are robust to the definition of a feasible community. These results are discussed in the light of empirical data and other theoretical studies, in conjunction with their broader implications for community assembly.

A New Chaotic Flow with Hidden Attractor: The First Hyperjerk System with No Equilibrium

NASA Astrophysics Data System (ADS)

Ren, Shuili; Panahi, Shirin; Rajagopal, Karthikeyan; Akgul, Akif; Pham, Viet-Thanh; Jafari, Sajad

2018-02-01

Discovering unknown aspects of non-equilibrium systems with hidden strange attractors is an attractive research topic. A novel quadratic hyperjerk system is introduced in this paper. It is noteworthy that this non-equilibrium system can generate hidden chaotic attractors. The essential properties of such systems are investigated by means of equilibrium points, phase portrait, bifurcation diagram, and Lyapunov exponents. In addition, a fractional-order differential equation of this new system is presented. Moreover, an electronic circuit is also designed and implemented to verify the feasibility of the theoretical model.

The role of non-equilibrium fluxes in the relaxation processes of the linear chemical master equation

NASA Astrophysics Data System (ADS)

de Oliveira, Luciana Renata; Bazzani, Armando; Giampieri, Enrico; Castellani, Gastone C.

2014-08-01

We propose a non-equilibrium thermodynamical description in terms of the Chemical Master Equation (CME) to characterize the dynamics of a chemical cycle chain reaction among m different species. These systems can be closed or open for energy and molecules exchange with the environment, which determines how they relax to the stationary state. Closed systems reach an equilibrium state (characterized by the detailed balance condition (D.B.)), while open systems will reach a non-equilibrium steady state (NESS). The principal difference between D.B. and NESS is due to the presence of chemical fluxes. In the D.B. condition the fluxes are absent while for the NESS case, the chemical fluxes are necessary for the state maintaining. All the biological systems are characterized by their "far from equilibrium behavior," hence the NESS is a good candidate for a realistic description of the dynamical and thermodynamical properties of living organisms. In this work we consider a CME written in terms of a discrete Kolmogorov forward equation, which lead us to write explicitly the non-equilibrium chemical fluxes. For systems in NESS, we show that there is a non-conservative "external vector field" whose is linearly proportional to the chemical fluxes. We also demonstrate that the modulation of these external fields does not change their stationary distributions, which ensure us to study the same system and outline the differences in the system's behavior when it switches from the D.B. regime to NESS. We were interested to see how the non-equilibrium fluxes influence the relaxation process during the reaching of the stationary distribution. By performing analytical and numerical analysis, our central result is that the presence of the non-equilibrium chemical fluxes reduces the characteristic relaxation time with respect to the D.B. condition. Within a biochemical and biological perspective, this result can be related to the "plasticity property" of biological systems and to their capabilities to switch from one state to another as is observed during synaptic plasticity, cell fate determination, and differentiation.

The role of non-equilibrium fluxes in the relaxation processes of the linear chemical master equation.

PubMed

de Oliveira, Luciana Renata; Bazzani, Armando; Giampieri, Enrico; Castellani, Gastone C

2014-08-14

We propose a non-equilibrium thermodynamical description in terms of the Chemical Master Equation (CME) to characterize the dynamics of a chemical cycle chain reaction among m different species. These systems can be closed or open for energy and molecules exchange with the environment, which determines how they relax to the stationary state. Closed systems reach an equilibrium state (characterized by the detailed balance condition (D.B.)), while open systems will reach a non-equilibrium steady state (NESS). The principal difference between D.B. and NESS is due to the presence of chemical fluxes. In the D.B. condition the fluxes are absent while for the NESS case, the chemical fluxes are necessary for the state maintaining. All the biological systems are characterized by their "far from equilibrium behavior," hence the NESS is a good candidate for a realistic description of the dynamical and thermodynamical properties of living organisms. In this work we consider a CME written in terms of a discrete Kolmogorov forward equation, which lead us to write explicitly the non-equilibrium chemical fluxes. For systems in NESS, we show that there is a non-conservative "external vector field" whose is linearly proportional to the chemical fluxes. We also demonstrate that the modulation of these external fields does not change their stationary distributions, which ensure us to study the same system and outline the differences in the system's behavior when it switches from the D.B. regime to NESS. We were interested to see how the non-equilibrium fluxes influence the relaxation process during the reaching of the stationary distribution. By performing analytical and numerical analysis, our central result is that the presence of the non-equilibrium chemical fluxes reduces the characteristic relaxation time with respect to the D.B. condition. Within a biochemical and biological perspective, this result can be related to the "plasticity property" of biological systems and to their capabilities to switch from one state to another as is observed during synaptic plasticity, cell fate determination, and differentiation.

Integer channels in nonuniform non-equilibrium 2D systems

NASA Astrophysics Data System (ADS)

Shikin, V.

2018-01-01

We discuss the non-equilibrium properties of integer channels in nonuniform 2D electron (hole) systems in the presence of a strong magnetic field. The results are applied to a qualitative explanation of the Corbino disk current-voltage characteristics (IVC) in the quantum Hall effect (QHE) regime. Special consideration is paid to the so-called "QHE breakdown" effect, which is readily observed in both the Hall bar and Corbino geometries of the tested cells. The QHE breakdown is especially evident in the Corbino samples, allowing for a more in-depth study of these effects.

Isobaric molecular dynamics version of the generalized replica exchange method (gREM): Liquid–vapor equilibrium

DOE PAGES

Malolepsza, Edyta; Secor, Maxim; Keyes, Tom

2015-09-23

A prescription for sampling isobaric generalized ensembles with molecular dynamics is presented and applied to the generalized replica exchange method (gREM), which was designed for simulating first-order phase transitions. The properties of the isobaric gREM ensemble are discussed and a study is presented of the liquid-vapor equilibrium of the guest molecules given for gas hydrate formation with the mW water model. As a result, phase diagrams, critical parameters, and a law of corresponding states are obtained.

Temperature anisotropy at equilibrium reveals nonlocal entropic contributions to interfacial properties.

PubMed

Wilhelmsen, Øivind; Trinh, Thuat T; Lervik, Anders

2018-01-01

Density gradient theory for fluids has played a key role in the study of interfacial phenomena for a century. In this work, we revisit its fundamentals by examining the vapor-liquid interface of argon, represented by the cut and shifted Lennard-Jones fluid. The starting point has traditionally been a Helmholtz energy functional using mass densities as arguments. By using rather the internal energy as starting point and including the entropy density as an additional argument, following thereby the phenomenological approach from classical thermodynamics, the extended theory suggests that the configurational part of the temperature has different contributions from the parallel and perpendicular directions at the interface, even at equilibrium. We find a similar anisotropy by examining the configurational temperature in molecular dynamics simulations and obtain a qualitative agreement between theory and simulations. The extended theory shows that the temperature anisotropy originates in nonlocal entropic contributions, which are currently missing from the classical theory. The nonlocal entropic contributions discussed in this work are likely to play a role in the description of both equilibrium and nonequilibrium properties of interfaces. At equilibrium, they influence the temperature- and curvature-dependence of the surface tension. Across the vapor-liquid interface of the Lennard Jones fluid, we find that the maximum in the temperature anisotropy coincides precisely with the maximum in the thermal resistivity relative to the equimolar surface, where the integral of the thermal resistivity gives the Kapitza resistance. This links the temperature anisotropy at equilibrium to the Kapitza resistance of the vapor-liquid interface at nonequilibrium.

Temperature anisotropy at equilibrium reveals nonlocal entropic contributions to interfacial properties

NASA Astrophysics Data System (ADS)

Wilhelmsen, Øivind; Trinh, Thuat T.; Lervik, Anders

2018-01-01

Density gradient theory for fluids has played a key role in the study of interfacial phenomena for a century. In this work, we revisit its fundamentals by examining the vapor-liquid interface of argon, represented by the cut and shifted Lennard-Jones fluid. The starting point has traditionally been a Helmholtz energy functional using mass densities as arguments. By using rather the internal energy as starting point and including the entropy density as an additional argument, following thereby the phenomenological approach from classical thermodynamics, the extended theory suggests that the configurational part of the temperature has different contributions from the parallel and perpendicular directions at the interface, even at equilibrium. We find a similar anisotropy by examining the configurational temperature in molecular dynamics simulations and obtain a qualitative agreement between theory and simulations. The extended theory shows that the temperature anisotropy originates in nonlocal entropic contributions, which are currently missing from the classical theory. The nonlocal entropic contributions discussed in this work are likely to play a role in the description of both equilibrium and nonequilibrium properties of interfaces. At equilibrium, they influence the temperature- and curvature-dependence of the surface tension. Across the vapor-liquid interface of the Lennard Jones fluid, we find that the maximum in the temperature anisotropy coincides precisely with the maximum in the thermal resistivity relative to the equimolar surface, where the integral of the thermal resistivity gives the Kapitza resistance. This links the temperature anisotropy at equilibrium to the Kapitza resistance of the vapor-liquid interface at nonequilibrium.

Supramolecular Polymers Based on Non-Coplanar AAA-DDD Hydrogen-Bonded Complexes.

PubMed

Mendez, Iamnica J Linares; Wang, Hong-Bo; Yuan, Ying-Xue; Wisner, James A

2018-03-01

Non-coplanar triple-hydrogen-bond arrays are connected as telechelic groups to alkyl chains and their properties as AA/BB type supramolecular polymers are examined. Viscosity studies at three temperatures are used to study the ring-chain equilibrium and determine the critical concentrations where polymer chains are formed. It is observed that neither the temperature range studied nor the alkyl chain length of one component significantly affect the polymerization properties in this system. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantifying Differences in the Impact of Variable Chemistry on Equilibrium Uranium(VI) Adsorption Properties of Aquifer Sediments

PubMed Central

2011-01-01

Uranium adsorption–desorption on sediment samples collected from the Hanford 300-Area, Richland, WA varied extensively over a range of field-relevant chemical conditions, complicating assessment of possible differences in equilibrium adsorption properties. Adsorption equilibrium was achieved in 500–1000 h although dissolved uranium concentrations increased over thousands of hours owing to changes in aqueous chemical composition driven by sediment-water reactions. A nonelectrostatic surface complexation reaction, >SOH + UO22+ + 2CO32- = >SOUO2(CO3HCO3)2–, provided the best fit to experimental data for each sediment sample resulting in a range of conditional equilibrium constants (logKc) from 21.49 to 21.76. Potential differences in uranium adsorption properties could be assessed in plots based on the generalized mass-action expressions yielding linear trends displaced vertically by differences in logKc values. Using this approach, logKc values for seven sediment samples were not significantly different. However, a significant difference in adsorption properties between one sediment sample and the fines (<0.063 mm) of another could be demonstrated despite the fines requiring a different reaction stoichiometry. Estimates of logKc uncertainty were improved by capturing all data points within experimental errors. The mass-action expression plots demonstrate that applying models outside the range of conditions used in model calibration greatly increases potential errors. PMID:21923109

Quantifying differences in the impact of variable chemistry on equilibrium Uranium(VI) adsorption properties of aquifer sediments.

PubMed

Stoliker, Deborah L; Kent, Douglas B; Zachara, John M

2011-10-15

Uranium adsorption-desorption on sediment samples collected from the Hanford 300-Area, Richland, WA varied extensively over a range of field-relevant chemical conditions, complicating assessment of possible differences in equilibrium adsorption properties. Adsorption equilibrium was achieved in 500-1000 h although dissolved uranium concentrations increased over thousands of hours owing to changes in aqueous chemical composition driven by sediment-water reactions. A nonelectrostatic surface complexation reaction, >SOH + UO₂²⁺ + 2CO₃²⁻ = >SOUO₂(CO₃HCO₃)²⁻, provided the best fit to experimental data for each sediment sample resulting in a range of conditional equilibrium constants (logK(c)) from 21.49 to 21.76. Potential differences in uranium adsorption properties could be assessed in plots based on the generalized mass-action expressions yielding linear trends displaced vertically by differences in logK(c) values. Using this approach, logK(c) values for seven sediment samples were not significantly different. However, a significant difference in adsorption properties between one sediment sample and the fines (< 0.063 mm) of another could be demonstrated despite the fines requiring a different reaction stoichiometry. Estimates of logK(c) uncertainty were improved by capturing all data points within experimental errors. The mass-action expression plots demonstrate that applying models outside the range of conditions used in model calibration greatly increases potential errors.

Correlation-induced superconductivity dynamically stabilized and enhanced by laser irradiation.

PubMed

Ido, Kota; Ohgoe, Takahiro; Imada, Masatoshi

2017-08-01

Studies on out-of-equilibrium dynamics have paved a way to realize a new state of matter. Superconductor-like properties above room temperatures recently suggested to be in copper oxides achieved by selectively exciting vibrational phonon modes by laser have inspired studies on an alternative and general strategy to be pursued for high-temperature superconductivity. We show that the superconductivity can be enhanced by irradiating laser to correlated electron systems owing to two mechanisms: First, the effective attractive interaction of carriers is enhanced by the dynamical localization mechanism, which drives the system into strong coupling regions. Second, the irradiation allows reaching uniform and enhanced superconductivity dynamically stabilized without deteriorating into equilibrium inhomogeneities that suppress superconductivity. The dynamical superconductivity is subject to the Higgs oscillations during and after the irradiation. Our finding sheds light on a way to enhance superconductivity that is inaccessible in equilibrium in strongly correlated electron systems.

A dynamic analysis of the motion of a low-wing general aviation aircraft about its calculated equilibrium flat spin mode

NASA Technical Reports Server (NTRS)

Tischler, M. B.; Barlow, J. B.

1980-01-01

The properties of the flat spin mode of a general aviation configuration have been studied through analysis of rotary balance data, numerical simulation, and analytical study of the equilibrium state. The equilibrium state is predicted well from rotary balance data. The variations of yawing moment and pitching moment as functions of sideslip have been shown to be of great importance in obtaining accurate modeling. These dependencies are not presently available with sufficient accuracy from previous tests or theories. The stability of the flat spin mode has been examined extensively using numerical linearization, classical perturbation methods, and reduced order modeling. The stability exhibited by the time histories and the eigenvalue analyses is shown to be strongly dependent on certain static cross derivatives and more so on the dynamic derivatives. Explicit stability criteria are obtained from the reduced order models.

Influence of condensed species on thermo-physical properties of LTE and non-LTE SF6-Cu mixture

NASA Astrophysics Data System (ADS)

Chen, Zhexin; Wu, Yi; Yang, Fei; Sun, Hao; Rong, Mingzhe; Wang, Chunlin

2017-10-01

SF6-Cu mixture is frequently formed in high-voltage circuit breakers due to the electrode erosion and metal vapor diffusion. During the interruption process, the multiphase effect and deviation from local thermal equilibrium (non-LTE assumption) can both affect the thermo-physical of the arc plasma and further influence the performance of circuit breaker. In this paper, thermo-physical properties, namely composition, thermodynamic properties and transport coefficients are calculated for multiphase SF6-Cu mixture with and without LTE assumption. The composition is confirmed by combining classical two-temperature mass action law with phase equilibrium condition deduced from second law of thermodynamics. The thermodynamic properties and transport coefficients are calculated using the multiphase composition result. The influence of condensed species on thermo-physical properties is discussed at different temperature, pressure (0.1-10 atm), non-equilibrium degrees (1-10), and copper molar proportions (0-50%). It is found that the multiphase effect has significant influence on specific enthalpy, specific heat and heavy species thermal conductivity in both LTE and non-LTE SF6-Cu system. This paper provides a more accurate database for computational fluid dynamic calculation.

The Study of Equilibrium factor between Radon-222 and its Daughters in Bangkok Atmosphere by Gamma-ray Spectrometry

NASA Astrophysics Data System (ADS)

Rujiwarodom, Rachanee

2010-05-01

To study the Equilibrium between radon-222 and its daughters in Bangkok atmosphere by Gamma-ray spectrometry, air sample were collected on 48 activated charcoal canister and 360 glass fiber filters by using a high volume jet-air sampler during December 2007 to November 2008.The Spectra of gamma-ray were measured by using a HPGe (Hyper Pure Germanium Detector). In the condition of secular equilibrium obtaining between Radon-222 and its decay products, radon-222 on activated charcoal canister and its daughters on glass fiber filters collected in the same time interval were calculated. The equilibrium factor (F) in the open air had a value of 0.38 at the minimum ,and 0.75 at the maximum. The average value of equilibrium factor (F) was 0.56±0.12. Based on the results, F had variations with a maximum value in the night to the early morning and decreased in the afternoon. In addition, F was higher in the winter than in the summer. This finding corresponds with the properties of the Earth atmosphere. The equilibrium factor (F) also depended on the concentration of dust in the atmosphere. People living in Bangkok were exposed to average value of 30 Bq/m3 of Radon-222 in the atmosphere. The equilibrium factor (0.56±0.12) and the average value of Radon-222 showed that people were exposed to alpha energy from radon-222 and its daughters decay at 0.005 WL(Working Level) which is lower than the safety standard at 0.02 WL. Keywords: Radon, Radon daughters , equilibrium factor, Gamma -ray spectrum analysis ,Bangkok ,Thailand

Sedimentation equilibrium analysis of protein interactions with global implicit mass conservation constraints and systematic noise decomposition.

PubMed

Vistica, Jennifer; Dam, Julie; Balbo, Andrea; Yikilmaz, Emine; Mariuzza, Roy A; Rouault, Tracey A; Schuck, Peter

2004-03-15

Sedimentation equilibrium is a powerful tool for the characterization of protein self-association and heterogeneous protein interactions. Frequently, it is applied in a configuration with relatively long solution columns and with equilibrium profiles being acquired sequentially at several rotor speeds. The present study proposes computational tools, implemented in the software SEDPHAT, for the global analysis of equilibrium data at multiple rotor speeds with multiple concentrations and multiple optical detection methods. The detailed global modeling of such equilibrium data can be a nontrivial computational problem. It was shown previously that mass conservation constraints can significantly improve and extend the analysis of heterogeneous protein interactions. Here, a method for using conservation of mass constraints for the macromolecular redistribution is proposed in which the effective loading concentrations are calculated from the sedimentation equilibrium profiles. The approach is similar to that described by Roark (Biophys. Chem. 5 (1976) 185-196), but its utility is extended by determining the bottom position of the solution columns from the macromolecular redistribution. For analyzing heterogeneous associations at multiple protein concentrations, additional constraints that relate the effective loading concentrations of the different components or their molar ratio in the global analysis are introduced. Equilibrium profiles at multiple rotor speeds also permit the algebraic determination of radial-dependent baseline profiles, which can govern interference optical ultracentrifugation data, but usually also occur, to a smaller extent, in absorbance optical data. Finally, the global analysis of equilibrium profiles at multiple rotor speeds with implicit mass conservation and computation of the bottom of the solution column provides an unbiased scale for determining molar mass distributions of noninteracting species. The properties of these tools are studied with theoretical and experimental data sets.

Experimental determination of solubilities of magnesium borates: Solubility constants of boracite [Mg 3B 7O 13Cl(cr)] and aksaite [MgB 6O 7(OH) 6 ·2H 2O(cr)

DOE PAGES

Xiong, Yongliang; Kirkes, Leslie Dawn; Knox, Jandi; ...

2018-02-03

In this work, solubility measurements regarding boracite [Mg 3B 7O 13Cl(cr)] and aksaite [MgB 6O 7(OH) 6·2H 2O(cr)] from the direction of supersaturation were conducted at 22.5 ± 0.5 °C. The equilibrium constant (log 10K 0) for boracite in terms of the following reaction, Mg 3B 7O 13Cl(cr) + 15H 2O(l) ⇌ 3Mg 2+ + 7B(OH) 4 – + Cl – + 2H + is determined as -29.49 ± 0.39 (2σ) in this study. The equilibrium constant for aksaite according to the following reaction, MgB 6O 7(OH) 6•2H 2O(cr) + 9H 2O(l) ⇌ Mg 2+ + 6B(OH) 4 – + 4H + is determined as -44.41 ± 0.41 (2σ) in this work. This work recommends a set of thermodynamic properties for aksaite at 25 °C and 1 bar as follows: ΔHmore » $$0\\atop{f}$$ =-6063.70 ± 4.85 kJ·mol -1, ΔG =-5492.55 ± 2.32 kJ·mol -1, and S 0 = 344.62 ± 1.85 J·mol -1·K -1. Among them, ΔG$$0\\atop{f}$$ is derived from the equilibrium constant for aksaite determined by this study; ΔH$$0\\atop{f}$$ is from the literature, determined by calorimetry; and S 0 is computed in the present work from ΔG$$0\\atop{f}$$ and ΔH$$0\\atop{f}$$. This investigation also recommends a set of thermodynamic properties for boracite at 25 °C and 1 bar as follows: ΔH$$0\\atop{f}$$ =-6575.02 ± 2.25 kJ·mol -1, ΔG$$0\\atop{f}$$ =-6178.35 ± 2.25 kJ·mol -1, and S 0 = 253.6 ± 0.5 J·mol -1·K -1. Among them, ΔG$$0\\atop{f}$$ is derived from the equilibrium constant for boracite determined by this study; S 0 is from the literature, determined by calorimetry; and ΔH$$0\\atop{f}$$ is computed in this work from ΔG$$0\\atop{f}$$ and S 0. The thermodynamic properties determined in this study can find applications in many fields. For instance, in the field of material science, boracite has many useful properties including ferroelectric and ferroelastic properties. The equilibrium constant of boracite determined in this work will provide guidance for economic synthesis of boracite in an aqueous medium. Similarly, in the field of nuclear waste management, iodide boracite [Mg 3B 7O 13I(cr)] is proposed as a waste form for radioactive 129I. Therefore, the solubility constant for chloride boracite [Mg 3B 7O 13Cl(cr)] will provide the guidance for the performance of iodide boracite in geological repositories. Boracite/aksaite themselves in geological repositories in salt formations may be solubility-controlling phase(s) for borate. Finally, solubility constants of boracite and aksaite will enable researchers to predict borate concentrations in equilibrium with boracite/aksaite in salt formations.« less

Experimental determination of solubilities of magnesium borates: Solubility constants of boracite [Mg 3B 7O 13Cl(cr)] and aksaite [MgB 6O 7(OH) 6 ·2H 2O(cr)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiong, Yongliang; Kirkes, Leslie Dawn; Knox, Jandi

In this work, solubility measurements regarding boracite [Mg 3B 7O 13Cl(cr)] and aksaite [MgB 6O 7(OH) 6·2H 2O(cr)] from the direction of supersaturation were conducted at 22.5 ± 0.5 °C. The equilibrium constant (log 10K 0) for boracite in terms of the following reaction, Mg 3B 7O 13Cl(cr) + 15H 2O(l) ⇌ 3Mg 2+ + 7B(OH) 4 – + Cl – + 2H + is determined as -29.49 ± 0.39 (2σ) in this study. The equilibrium constant for aksaite according to the following reaction, MgB 6O 7(OH) 6•2H 2O(cr) + 9H 2O(l) ⇌ Mg 2+ + 6B(OH) 4 – + 4H + is determined as -44.41 ± 0.41 (2σ) in this work. This work recommends a set of thermodynamic properties for aksaite at 25 °C and 1 bar as follows: ΔHmore » $$0\\atop{f}$$ =-6063.70 ± 4.85 kJ·mol -1, ΔG =-5492.55 ± 2.32 kJ·mol -1, and S 0 = 344.62 ± 1.85 J·mol -1·K -1. Among them, ΔG$$0\\atop{f}$$ is derived from the equilibrium constant for aksaite determined by this study; ΔH$$0\\atop{f}$$ is from the literature, determined by calorimetry; and S 0 is computed in the present work from ΔG$$0\\atop{f}$$ and ΔH$$0\\atop{f}$$. This investigation also recommends a set of thermodynamic properties for boracite at 25 °C and 1 bar as follows: ΔH$$0\\atop{f}$$ =-6575.02 ± 2.25 kJ·mol -1, ΔG$$0\\atop{f}$$ =-6178.35 ± 2.25 kJ·mol -1, and S 0 = 253.6 ± 0.5 J·mol -1·K -1. Among them, ΔG$$0\\atop{f}$$ is derived from the equilibrium constant for boracite determined by this study; S 0 is from the literature, determined by calorimetry; and ΔH$$0\\atop{f}$$ is computed in this work from ΔG$$0\\atop{f}$$ and S 0. The thermodynamic properties determined in this study can find applications in many fields. For instance, in the field of material science, boracite has many useful properties including ferroelectric and ferroelastic properties. The equilibrium constant of boracite determined in this work will provide guidance for economic synthesis of boracite in an aqueous medium. Similarly, in the field of nuclear waste management, iodide boracite [Mg 3B 7O 13I(cr)] is proposed as a waste form for radioactive 129I. Therefore, the solubility constant for chloride boracite [Mg 3B 7O 13Cl(cr)] will provide the guidance for the performance of iodide boracite in geological repositories. Boracite/aksaite themselves in geological repositories in salt formations may be solubility-controlling phase(s) for borate. Finally, solubility constants of boracite and aksaite will enable researchers to predict borate concentrations in equilibrium with boracite/aksaite in salt formations.« less

Punctuated equilibrium dynamics in human communications

NASA Astrophysics Data System (ADS)

Peng, Dan; Han, Xiao-Pu; Wei, Zong-Wen; Wang, Bing-Hong

2015-10-01

A minimal model based on network incorporating individual interactions is proposed to study the non-Poisson statistical properties of human behavior: individuals in system interact with their neighbors, the probability of an individual acting correlates to its activity, and all the individuals involved in action will change their activities randomly. The model reproduces varieties of spatial-temporal patterns observed in empirical studies of human daily communications, providing insight into various human activities and embracing a range of realistic social interacting systems, particularly, intriguing bimodal phenomenon. This model bridges priority queueing theory and punctuated equilibrium dynamics, and our modeling and analysis is likely to shed light on non-Poisson phenomena in many complex systems.

Complete stability of delayed recurrent neural networks with Gaussian activation functions.

PubMed

Liu, Peng; Zeng, Zhigang; Wang, Jun

2017-01-01

This paper addresses the complete stability of delayed recurrent neural networks with Gaussian activation functions. By means of the geometrical properties of Gaussian function and algebraic properties of nonsingular M-matrix, some sufficient conditions are obtained to ensure that for an n-neuron neural network, there are exactly 3 k equilibrium points with 0≤k≤n, among which 2 k and 3 k -2 k equilibrium points are locally exponentially stable and unstable, respectively. Moreover, it concludes that all the states converge to one of the equilibrium points; i.e., the neural networks are completely stable. The derived conditions herein can be easily tested. Finally, a numerical example is given to illustrate the theoretical results. Copyright © 2016 Elsevier Ltd. All rights reserved.

Consequences of Molecular-Scale Non-Equilibrium Activity on the Dynamics and Mechanics of Self-Assembled Actin-Based Structures and Materials

NASA Astrophysics Data System (ADS)

Marshall Mccall, Patrick

Living cells are hierarchically self-organized forms of active soft matter: molecules on the nanometer scale form functional structures and organelles on the micron scale, which then compose cells on the scale of 10s of microns. While the biological functions of intracellular organelles are defined by the composition and properties of the structures themselves, how those bulk properties emerge from the properties and interactions of individual molecules remains poorly understood. Actin, a globular protein which self-assembles into dynamic semi-flexible polymers, is the basic structural material of cells and the major component of many functional organelles. In this thesis, I have used purified actin as a model system to explore the interplay between molecular-scale dynamics and organelle-scale functionality, with particular focus on the role of molecular-scale non-equilibrium activity. One of the most canonical forms of molecular-scale non-equilibrium activity is that of mechanoenzymes, also called motor proteins. These proteins utilized the free energy liberated by hydrolysis of ATP to perform mechanical work, thereby introducing non-equilibrium "active" stresses on the molecular scale. Combining experiments with mathematical modeling, we demonstrate in this thesis that non-equilibrium motor activity is sufficient to drive self-organization and pattern formation of the multimeric actin-binding motor protein Myosin II on 1D reconstituted actomyosin bundles. Like myosin, actin is itself an ATPase. However, nono-equilibrium ATP hydrolysis on actin is known to regulate the stability and assembly kinetics of actin filaments rather than generate active stresses per se. At the level of single actin filaments, the inhomogeneous nucleotide composition generated along the filament length by hydrolysis directs binding of regulatory proteins like cofilin, which mediate filament disassembly and thereby accelerate actin filament turnover. The concequences of this non-equilibrium turnover on the steady-state properties of collections of filaments remained unclear. Here, I reconstituted tunable, non-equilibrium actin turnover dynamics in entangled solutions of actin filaments as a model of the actin cortex of living cells. We found that this non-equilibrium turnover decouples solution mechanics from microstructure, enabling structurally indistinguishable materials to behave effectively as either viscous fluids or elastic gels. Additionally, we employed computer simulations to identify the dynamical regime in which actin turnover controls the effective viscosity of 2D cross-linked actin networks in the presence of motors. Additionally, I examine in this thesis the localization and self-assembly of actin filaments in condensed liquid phases called polyelectrolyte coacervates as a model membrane-less organelle. We find that concentration of actin through spontaneous partitioning preferentially to the coacervate phase accelerates the assembly of filaments. These filaments then localize to the coacervate-bulk interface, generating particles with visco-elastic shells surrounding liquid cores. In this case, the properties of the condensed phase enable regulation of actin assembly dynamics.

Loop Electrostatics Asymmetry Modulates the Preexisting Conformational Equilibrium in Thrombin.

PubMed

Pozzi, Nicola; Zerbetto, Mirco; Acquasaliente, Laura; Tescari, Simone; Frezzato, Diego; Polimeno, Antonino; Gohara, David W; Di Cera, Enrico; De Filippis, Vincenzo

2016-07-19

Thrombin exists as an ensemble of active (E) and inactive (E*) conformations that differ in their accessibility to the active site. Here we show that redistribution of the E*-E equilibrium can be achieved by perturbing the electrostatic properties of the enzyme. Removal of the negative charge of the catalytic Asp102 or Asp189 in the primary specificity site destabilizes the E form and causes a shift in the 215-217 segment that compromises substrate entrance. Solution studies and existing structures of D102N document stabilization of the E* form. A new high-resolution structure of D189A also reveals the mutant in the collapsed E* form. These findings establish a new paradigm for the control of the E*-E equilibrium in the trypsin fold.

Small-Molecule Photostabilizing Agents are Modifiers of Lipid Bilayer Properties

PubMed Central

Alejo, Jose L.; Blanchard, Scott C.; Andersen, Olaf S.

2013-01-01

Small-molecule photostabilizing or protective agents (PAs) provide essential support for the stability demands on fluorescent dyes in single-molecule spectroscopy and fluorescence microscopy. These agents are employed also in studies of cell membranes and model systems mimicking lipid bilayer environments, but there is little information about their possible effects on membrane structure and physical properties. Given the impact of amphipathic small molecules on bilayer properties such as elasticity and intrinsic curvature, we investigated the effects of six commonly used PAs—cyclooctatetraene (COT), para-nitrobenzyl alcohol (NBA), Trolox (TX), 1,4-diazabicyclo[2.2.2]octane (DABCO), para-nitrobenzoic acid (pNBA), and n-propyl gallate (nPG)—on bilayer properties using a gramicidin A (gA)-based fluorescence quench assay to probe for PA-induced changes in the gramicidin monomer↔dimer equilibrium. The experiments were done using fluorophore-loaded large unilamellar vesicles that had been doped with gA, and changes in the gA monomer↔dimer equilibrium were assayed using a gA channel-permeable fluorescence quencher (Tl+). Changes in bilayer properties caused by, e.g., PA adsorption at the bilayer/solution interface that alter the equilibrium constant for gA channel formation, and thus the number of conducting gA channels in the large unilamellar vesicle membrane, will be detectable as changes in the rate of Tl+ influx—the fluorescence quench rate. Over the experimentally relevant millimolar concentration range, TX, NBA, and pNBA, caused comparable increases in gA channel activity. COT, also in the millimolar range, caused a slight decrease in gA channel activity. nPG increased channel activity at submillimolar concentrations. DABCO did not alter gA activity. Five of the six tested PAs thus alter lipid bilayer properties at experimentally relevant concentrations, which becomes important for the design and analysis of fluorescence studies in cells and model membrane systems. We therefore tested combinations of COT, NBA, and TX; the combinations altered the fluorescence quench rate less than would be predicted assuming their effects on bilayer properties were additive. The combination of equimolar concentrations of COT and NBA caused minimal changes in the fluorescence quench rate. PMID:23746513

Generalized thermodynamic relations for a system experiencing heat and mass diffusion in the far-from-equilibrium realm based on steepest entropy ascent.

PubMed

Li, Guanchen; von Spakovsky, Michael R

2016-09-01

This paper presents a nonequilibrium thermodynamic model for the relaxation of a local, isolated system in nonequilibrium using the principle of steepest entropy ascent (SEA), which can be expressed as a variational principle in thermodynamic state space. The model is able to arrive at the Onsager relations for such a system. Since no assumption of local equilibrium is made, the conjugate fluxes and forces are intrinsic to the subspaces of the system's state space and are defined using the concepts of hypoequilibrium state and nonequilibrium intensive properties, which describe the nonmutual equilibrium status between subspaces of the thermodynamic state space. The Onsager relations are shown to be a thermodynamic kinematic feature of the system independent of the specific details of the micromechanical dynamics. Two kinds of relaxation processes are studied with different constraints (i.e., conservation laws) corresponding to heat and mass diffusion. Linear behavior in the near-equilibrium region as well as nonlinear behavior in the far-from-equilibrium region are discussed. Thermodynamic relations in the equilibrium and near-equilibrium realm, including the Gibbs relation, the Clausius inequality, and the Onsager relations, are generalized to the far-from-equilibrium realm. The variational principle in the space spanned by the intrinsic conjugate fluxes and forces is expressed via the quadratic dissipation potential. As an application, the model is applied to the heat and mass diffusion of a system represented by a single-particle ensemble, which can also be applied to a simple system of many particles. Phenomenological transport coefficients are also derived in the near-equilibrium realm.

Chemical equilibrium. [maximizing entropy of gas system to derive relations between thermodynamic variables

NASA Technical Reports Server (NTRS)

1976-01-01

The entropy of a gas system with the number of particles subject to external control is maximized to derive relations between the thermodynamic variables that obtain at equilibrium. These relations are described in terms of the chemical potential, defined as equivalent partial derivatives of entropy, energy, enthalpy, free energy, or free enthalpy. At equilibrium, the change in total chemical potential must vanish. This fact is used to derive the equilibrium constants for chemical reactions in terms of the partition functions of the species involved in the reaction. Thus the equilibrium constants can be determined accurately, just as other thermodynamic properties, from a knowledge of the energy levels and degeneracies for the gas species involved. These equilibrium constants permit one to calculate the equilibrium concentrations or partial pressures of chemically reacting species that occur in gas mixtures at any given condition of pressure and temperature or volume and temperature.

On the quantum Landau collision operator and electron collisions in dense plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daligault, Jérôme, E-mail: daligaul@lanl.gov

2016-03-15

The quantum Landau collision operator, which extends the widely used Landau/Fokker-Planck collision operator to include quantum statistical effects, is discussed. The quantum extension can serve as a reference model for including electron collisions in non-equilibrium dense plasmas, in which the quantum nature of electrons cannot be neglected. In this paper, the properties of the Landau collision operator that have been useful in traditional plasma kinetic theory and plasma transport theory are extended to the quantum case. We outline basic properties in connection with the conservation laws, the H-theorem, and the global and local equilibrium distributions. We discuss the Fokker-Planck formmore » of the operator in terms of three potentials that extend the usual two Rosenbluth potentials. We establish practical closed-form expressions for these potentials under local thermal equilibrium conditions in terms of Fermi-Dirac and Bose-Einstein integrals. We study the properties of linearized quantum Landau operator, and extend two popular approximations used in plasma physics to include collisions in kinetic simulations. We apply the quantum Landau operator to the classic test-particle problem to illustrate the physical effects embodied in the quantum extension. We present useful closed-form expressions for the electron-ion momentum and energy transfer rates. Throughout the paper, similarities and differences between the quantum and classical Landau collision operators are emphasized.« less

Modified TOV in gravity’s rainbow: properties of neutron stars and dynamical stability conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hendi, S.H.; Research Institute for Astronomy and Astrophysics of Maragha; Bordbar, G.H.

In this paper, we consider a spherical symmetric metric to extract the hydrostatic equilibrium equation of stars in (3+1)-dimensional gravity’s rainbow in the presence of cosmological constant. Then, we generalize the hydrostatic equilibrium equation to d-dimensions and obtain the hydrostatic equilibrium equation for this gravity. Also, we obtain the maximum mass of neutron star using the modern equations of state of neutron star matter derived from the microscopic calculations. It is notable that, in this paper, we consider the effects of rainbow functions on the diagrams related to the mass-central mass density (M-ρ{sub c}) relation and also the mass-radius (M-R)more » relation of neutron star. We also study the effects of rainbow functions on the other properties of neutron star such as the Schwarzschild radius, average density, strength of gravity and gravitational redshift. Then, we apply the cosmological constant to this theory to obtain the diagrams of M-ρ{sub c} (or M-R) and other properties of these stars. Next, we investigate the dynamical stability condition for these stars in gravity’s rainbow and show that these stars have dynamical stability. We also obtain a relation between mass of neutron stars and Planck mass. In addition, we compare obtained results of this theory with the observational data.« less

On the quantum Landau collision operator and electron collisions in dense plasmas

NASA Astrophysics Data System (ADS)

Daligault, Jérôme

2016-03-01

The quantum Landau collision operator, which extends the widely used Landau/Fokker-Planck collision operator to include quantum statistical effects, is discussed. The quantum extension can serve as a reference model for including electron collisions in non-equilibrium dense plasmas, in which the quantum nature of electrons cannot be neglected. In this paper, the properties of the Landau collision operator that have been useful in traditional plasma kinetic theory and plasma transport theory are extended to the quantum case. We outline basic properties in connection with the conservation laws, the H-theorem, and the global and local equilibrium distributions. We discuss the Fokker-Planck form of the operator in terms of three potentials that extend the usual two Rosenbluth potentials. We establish practical closed-form expressions for these potentials under local thermal equilibrium conditions in terms of Fermi-Dirac and Bose-Einstein integrals. We study the properties of linearized quantum Landau operator, and extend two popular approximations used in plasma physics to include collisions in kinetic simulations. We apply the quantum Landau operator to the classic test-particle problem to illustrate the physical effects embodied in the quantum extension. We present useful closed-form expressions for the electron-ion momentum and energy transfer rates. Throughout the paper, similarities and differences between the quantum and classical Landau collision operators are emphasized.

Synthesis and amphiphilic properties of decanoyl esters of tri- and tetraethylene glycol.

PubMed

Zhu, Ying; Molinier, Valérie; Queste, Sébastien; Aubry, Jean-Marie

2007-08-15

Well-defined decanoyl triethylene glycol ester and decanoyl tetraethylene glycol ester were synthesized and compared to their ether counterparts (C(10)E(4) and C(10)E(3)). Their physicochemical properties i.e. critical micelle concentrations (CMC), cloud points, and equilibrium surface tensions were determined. Binary water-surfactant phase behavior was also studied by polarized optical microscopy. The stability of the ester bond was determined by investigating alkaline hydrolysis of the compounds. It was found that CMC, cloud point and equilibrium surface tension are roughly the same for corresponding ethers and esters. In the binary diagram, the esters form only lamellar phases, the area of which is smaller than that of the ether counterparts. These different behaviors can be related to the modification of the molecular conformation induced by the replacement of the ether group by the ester group.

Viscous-shock-layer solutions with coupled radiation and ablation injection for earth entry

NASA Technical Reports Server (NTRS)

Gupta, Roop N.; Lee, Kam-Pui; Moos, James N.; Sutton, Kenneth

1990-01-01

Results are obtained for the forebody of a planetary exploration vehicle entering the earth's atmosphere. A viscous-shock-layer analysis is used assuming the flow to be laminar and in chemical equilibrium. Presented results include coupled radiation and ablation injection. This study further includes the effect of different transport and thermodynamic properties and radiation models. A Lewis number of 1.4 appears adequate for the radiation-dominated flows. Five velocities corresponding to different possible trajectory points at an altitude of 70 km have been further analyzed in detail. Sublimation and radiative equilibrium wall temperatures are employed for cases with and without coupled injection, respectively. For the cases analyzed here, the mass injection rates are small. However, the rates could become large if a lower altitude is used for aerobraking and/or the body size is increased. A comparison of the equilibrium results with finite-rate chemistry calculation shows the flowfield to be in chemical equilibrium.

Atmospheric aerosols: Their Optical Properties and Effects

NASA Technical Reports Server (NTRS)

1976-01-01

Measured properties of atmospheric aerosol particles are presented. These include aerosol size frequency distribution and complex retractive index. The optical properties of aerosols are computed based on the presuppositions of thermodynamic equilibrium and of Mie-theory.

Effect of synthesis parameters on polymethacrylic acid xerogel structures and equilibrium swelling

NASA Astrophysics Data System (ADS)

Panić, V.; Jovanović, J.; Adnadjević, B.; Velicković, S.

2009-09-01

Hydrogels based on crosslinked polymethacrylic acid were synthesized via free-radical polymerization in aqueous solution, using N,N'-methylene bisacrylamide as a crosslinking agent and 2,2'-azobis-[2-(2-imidazolin-2-yl)propane] dihydrochloride as an initiator. The influence of the reaction parameters (the neutralization degree of methacrylic acid and the initial monomer concentration) on the equilibrium swelling degree, the swelling kinetic parameters and the basic structural properties of xerogels was investigated. The change of synthesis parameters leads to the change of the basic structural parameters of xerogel, as well as the equilibrium swelling degree and the initial swelling rate of the hydrogels. It is found that there are power form relationships between the equilibrium swelling degree, the initial swelling rate and the structural xerogel’s properties and the change of the neutralization degree of monomer, i.e. the monomer concentration. The examined correlations proved that the crosslinking density is the crucial parameter which determines all the other investigated structural and swelling parameters.

Thermal characterization assessment of rigid and flexible water models in a nanogap using molecular dynamics

NASA Astrophysics Data System (ADS)

Akıner, Tolga; Mason, Jeremy; Ertürk, Hakan

2017-11-01

The thermal properties of the TIP3P and TIP5P water models are investigated using equilibrium and non-equilibrium molecular dynamics techniques in the presence of solid surfaces. The performance of the non-equilibrium technique for rigid molecules is found to depend significantly on the distribution of atomic degrees of freedom. An improved approach to distribute atomic degrees of freedom is proposed for which the thermal conductivity of the TIP5P model agrees more closely with equilibrium molecular dynamics and experimental results than the existing state of the art.

Local thermodynamic equilibrium for globally disequilibrium open systems under stress

NASA Astrophysics Data System (ADS)

Podladchikov, Yury

2016-04-01

Predictive modeling of far and near equilibrium processes is essential for understanding of patterns formation and for quantifying of natural processes that are never in global equilibrium. Methods of both equilibrium and non-equilibrium thermodynamics are needed and have to be combined. For example, predicting temperature evolution due to heat conduction requires simultaneous use of equilibrium relationship between internal energy and temperature via heat capacity (the caloric equation of state) and disequilibrium relationship between heat flux and temperature gradient. Similarly, modeling of rocks deforming under stress, reactions in system open for the porous fluid flow, or kinetic overstepping of the equilibrium reaction boundary necessarily needs both equilibrium and disequilibrium material properties measured under fundamentally different laboratory conditions. Classical irreversible thermodynamics (CIT) is the well-developed discipline providing the working recipes for the combined application of mutually exclusive experimental data such as density and chemical potential at rest under constant pressure and temperature and viscosity of the flow under stress. Several examples will be presented.

Table and charts of equilibrium normal shock and shock tube properties for pure argon with velocities to 18 km/sec

NASA Technical Reports Server (NTRS)

Miller, C. G., III; Wilder, S. E.

1976-01-01

Equilibrium thermodynamic and flow properties are presented in tabulated and graphical form for moving, standing, and reflected normal shock waves in pure argon. Properties include pressure, temperature, density, enthalpy, speed of sound, entropy, molecular-weight ratio, isentropic exponent, velocity, and species mole fractions. Incident (moving) shock velocities are varied from 2 to 18 km/sec for a range of initial pressure of 5 N/sq m to 500 kN/sq m. Working charts illustrating shock tube performance with argon test gas and heated helium and hydrogen driver gases are also presented.

Viscous real gas flowfields about three dimensional configurations

NASA Technical Reports Server (NTRS)

Balakrishnan, A.; Davy, W. C.

1983-01-01

Laminar, real gas hypersonic flowfields over a three dimensional configuration are computed using an unsteady, factored implicit scheme. Local chemical and thermodynamic properties are evaluated by an equilibrium composition method. Transport properties are obtained from individual species properties and application of a mixture rule. Numerical solutions are presented for an ideal gas and equilibrium air for free-stream Mach numbers of 13 and 15 and at various angles of attack. The effect of real gas is to decrease the shock-layer thickness resulting from decreased shock-layer temperatures and corresponding increased density. The combined effects of viscosity and real gas are to increase the subsonic layer near the wall.

Non-Equilibrium Properties from Equilibrium Free Energy Calculations

NASA Technical Reports Server (NTRS)

Pohorille, Andrew; Wilson, Michael A.

2012-01-01

Calculating free energy in computer simulations is of central importance in statistical mechanics of condensed media and its applications to chemistry and biology not only because it is the most comprehensive and informative quantity that characterizes the eqUilibrium state, but also because it often provides an efficient route to access dynamic and kinetic properties of a system. Most of applications of equilibrium free energy calculations to non-equilibrium processes rely on a description in which a molecule or an ion diffuses in the potential of mean force. In general case this description is a simplification, but it might be satisfactorily accurate in many instances of practical interest. This hypothesis has been tested in the example of the electrodiffusion equation . Conductance of model ion channels has been calculated directly through counting the number of ion crossing events observed during long molecular dynamics simulations and has been compared with the conductance obtained from solving the generalized Nernst-Plank equation. It has been shown that under relatively modest conditions the agreement between these two approaches is excellent, thus demonstrating the assumptions underlying the diffusion equation are fulfilled. Under these conditions the electrodiffusion equation provides an efficient approach to calculating the full voltage-current dependence routinely measured in electrophysiological experiments.

"Non-equilibrium" block copolymer micelles with glassy cores: a predictive approach based on theory of equilibrium micelles.

PubMed

Nagarajan, Ramanathan

2015-07-01

Micelles generated in water from most amphiphilic block copolymers are widely recognized to be non-equilibrium structures. Typically, the micelles are prepared by a kinetic process, first allowing molecular scale dissolution of the block copolymer in a common solvent that likes both the blocks and then gradually replacing the common solvent by water to promote the hydrophobic blocks to aggregate and create the micelles. The non-equilibrium nature of the micelle originates from the fact that dynamic exchange between the block copolymer molecules in the micelle and the singly dispersed block copolymer molecules in water is suppressed, because of the glassy nature of the core forming polymer block and/or its very large hydrophobicity. Although most amphiphilic block copolymers generate such non-equilibrium micelles, no theoretical approach to a priori predict the micelle characteristics currently exists. In this work, we propose a predictive approach for non-equilibrium micelles with glassy cores by applying the equilibrium theory of micelles in two steps. In the first, we calculate the properties of micelles formed in the mixed solvent while true equilibrium prevails, until the micelle core becomes glassy. In the second step, we freeze the micelle aggregation number at this glassy state and calculate the corona dimension from the equilibrium theory of micelles. The condition when the micelle core becomes glassy is independently determined from a statistical thermodynamic treatment of diluent effect on polymer glass transition temperature. The predictions based on this "non-equilibrium" model compare reasonably well with experimental data for polystyrene-polyethylene oxide diblock copolymer, which is the most extensively studied system in the literature. In contrast, the application of the equilibrium model to describe such a system significantly overpredicts the micelle core and corona dimensions and the aggregation number. The non-equilibrium model suggests ways to obtain different micelle sizes for the same block copolymer, by the choices we can make of the common solvent and the mode of solvent substitution. Published by Elsevier Inc.

Characterization of Low-Symmetry Structures from Phase Equilibrium of Fe-Al System-Microstructures and Mechanical Properties.

PubMed

Matysik, Piotr; Jóźwiak, Stanisław; Czujko, Tomasz

2015-03-04

Fe-Al intermetallic alloys with aluminum content over 60 at% are in the area of the phase equilibrium diagram that is considerably less investigated in comparison to the high-symmetry Fe₃Al and FeAl phases. Ambiguous crystallographic information and incoherent data referring to the phase equilibrium diagrams placed in a high-aluminum range have caused confusions and misinformation. Nowadays unequivocal material properties description of FeAl₂, Fe₂Al₅ and FeAl₃ intermetallic alloys is still incomplete. In this paper, the influence of aluminum content and processing parameters on phase composition is presented. The occurrence of low-symmetry FeAl₂, Fe₂Al₅ and FeAl₃ structures determined by chemical composition and phase transformations was defined by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) examinations. These results served to verify diffraction investigations (XRD) and to explain the mechanical properties of cast materials such as: hardness, Young's modulus and fracture toughness evaluated using the nano-indentation technique.

Pore Scale Dynamics of Microemulsion Formation.

PubMed

Unsal, Evren; Broens, Marc; Armstrong, Ryan T

2016-07-19

Experiments in various porous media have shown that multiple parameters come into play when an oleic phase is displaced by an aqueous solution of surfactant. In general, the displacement efficiency is improved when the fluids become quasi-miscible. Understanding the phase behavior oil/water/surfactant systems is important because microemulsion has the ability to generate ultralow interfacial tension (<10(-2) mN m(-1)) that is required for miscibility to occur. Many studies focus on microemulsion formation and the resulting properties under equilibrium conditions. However, the majority of applications where microemulsion is present also involve flow, which has received relatively less attention. It is commonly assumed that the characteristics of an oil/water/surfactant system under flowing conditions are identical to the one under equilibrium conditions. Here, we show that this is not necessarily the case. We studied the equilibrium phase behavior of a model system consisting of n-decane and an aqueous solution of olefin sulfonate surfactant, which has practical applications for enhanced oil recovery. The salt content of the aqueous solution was varied to provide a range of different microemulsion compositions and oil-water interfacial tensions. We then performed microfluidic flow experiments to study the dynamic in situ formation of microemulsion by coinjecting bulk fluids of n-decane and surfactant solution into a T-junction capillary geometry. A solvatochromatic fluorescent dye was used to obtain spatially resolved compositional information. In this way, we visualized the microemulsion formation and the flow of it along with the excess phases. A complex interaction between the flow patterns and the microemulsion properties was observed. The formation of microemulsion influenced the flow regimes, and the flow regimes affected the characteristics of the microemulsion formation. In particular, at low flow rates, slug flow was observed, which had profound consequences on the pore scale mixing behavior and resulting microemulsion properties.

Experimental and Ab-Initio Studies of High Temperature Reactions in Vapor above Sio2/Al2O3 and SiO2/CaO Melts

NASA Astrophysics Data System (ADS)

Cornelison, Dave; Bulak, Michal

2017-06-01

The study of solid-liquid equilibrium is well established for alloys likely to be found on hot, rocky extra-solar planets. However, in atmospheres established above these magmas, molecules released from the components of the melt can react to form adducts; new molecules containing fragments of these precursors. These adducts are not predicted from equilibrium modeling codes unless their thermodynamic properties are input prior to simulation. In addition, the spectroscopic properties and vapor pressures relative to their melt conditions may be poorly known. Using a Knudsen cell heated in a custom e-beam evaporator, the binary systems of SiO2/Al2O3 and SiO2/CaO were synthesized at temperatures above 2000 K. The molecules evaporated from the melts were deposited into an Argon matrix held at 15 K and studied using mass spectrometry and FTIR. The results were then compared to molecular stability calculations derived from ab-initio molecular dynamics simulations using VASP©, and to IR spectra obtained using Gaussian©. Based on this analysis, a set of molecular adducts was found for each of the two alloy systems. The thermodynamic properties of each adduct were then simulated and used as input parameters for equilibrium calculations of vapor pressures as a function of temperature. The applications of these results to exoplanet observations is also discussed. This work was supported by NASA EPSCoR (Experimental Program to Stimulate Competitive Research). NNX13AE52A , “Understanding the Atmospheres of Hot Earths and the Impact on Solar System Formation”with NASA Glenn Research Center, Missouri State University and Washington University, St. Louis

Unfolding single RNA molecules: bridging the gap between equilibrium and non-equilibrium statistical thermodynamics.

PubMed

Bustamante, Carlos

2005-11-01

During the last 15 years, scientists have developed methods that permit the direct mechanical manipulation of individual molecules. Using this approach, they have begun to investigate the effect of force and torque in chemical and biochemical reactions. These studies span from the study of the mechanical properties of macromolecules, to the characterization of molecular motors, to the mechanical unfolding of individual proteins and RNA. Here I present a review of some of our most recent results using mechanical force to unfold individual molecules of RNA. These studies make it possible to follow in real time the trajectory of each molecule as it unfolds and characterize the various intermediates of the reaction. Moreover, if the process takes place reversibly it is possible to extract both kinetic and thermodynamic information from these experiments at the same time that we characterize the forces that maintain the three-dimensional structure of the molecule in solution. These studies bring us closer to the biological unfolding processes in the cell as they simulate in vitro, the mechanical unfolding of RNAs carried out in the cell by helicases. If the unfolding process occurs irreversibly, I show here that single-molecule experiments can still provide equilibrium, thermodynamic information from non-equilibrium data by using recently discovered fluctuation theorems. Such theorems represent a bridge between equilibrium and non-equilibrium statistical mechanics. In fact, first derived in 1997, the first experimental demonstration of the validity of fluctuation theorems was obtained by unfolding mechanically a single molecule of RNA. It is perhaps a sign of the times that important physical results are these days used to extract information about biological systems and that biological systems are being used to test and confirm fundamental new laws in physics.

The influence of electric charge transferred during electro-mechanical reshaping on mechanical behavior of cartilage

NASA Astrophysics Data System (ADS)

Protsenko, Dimitry E.; Lim, Amanda; Wu, Edward C.; Manuel, Cyrus; Wong, Brian J. F.

2011-03-01

Electromechanical reshaping (EMR) of cartilage has been suggested as an alternative to the classical surgical techniques of modifying the shape of facial cartilages. The method is based on exposure of mechanically deformed cartilaginous tissue to a low level electric field. Electro-chemical reactions within the tissue lead to reduction of internal stress, and establishment of a new equilibrium shape. The same reactions offset the electric charge balance between collagen and proteoglycan matrix and interstitial fluid responsible for maintenance of cartilage mechanical properties. The objective of this study was to investigate correlation between the electric charge transferred during EMR and equilibrium elastic modulus. We used a finite element model based on the triphasic theory of cartilage mechanical properties to study how electric charges transferred in the electro-chemical reactions in cartilage can change its mechanical responses to step displacements in unconfined compression. The concentrations of the ions, the strain field and the fluid and ion velocities within the specimen subject to an applied mechanical deformation were estimated and apparent elastic modulus (the ratio of the equilibrium axial stress to the axial strain) was calculated as a function of transferred charge. The results from numerical calculations showed that the apparent elastic modulus decreases with increase in electric charge transfer. To compare numerical model with experimental observation we measured elastic modulus of cartilage as a function of electric charge transferred in electric circuit during EMR. Good correlation between experimental and theoretical data suggests that electric charge disbalance is responsible for alteration of cartilage mechanical properties.

A Numerical Characterization of the Gravito-Electrostatic Sheath Equilibrium Structure in Solar Plasma

NASA Astrophysics Data System (ADS)

Karmakar, Pralay Kumar

This article describes the equilibrium structure of the solar interior plasma (SIP) and solar wind plasma (SWP) in detail under the framework of the gravito-electrostatic sheath (GES) model. This model gives a precise definition of the solar surface boundary (SSB), surface origin mechanism of the subsonic SWP, and its supersonic acceleration. Equilibrium parameters like plasma potential, self-gravity, population density, flow, their gradients, and all the relevant inhomogeneity scale lengths are numerically calculated and analyzed as an initial value problem. Physical significance of the structure condition for the SSB is discussed. The plasma oscillation and Jeans time scales are also plotted and compared. In addition, different coupling parameters, and electric current profiles are also numerically studied. The current profiles exhibit an important behavior of directional reversibility, i.e., an electrodynamical transition from negative to positive value. It occurs beyond a few Jeans lengths away from the SSB. The virtual spherical surface lying at the current reversal point, where the net current becomes zero, has the property of a floating surface behavior of the real physical wall. Our investigation indicates that the SWP behaves as an ion current-carrying plasma system. The basic mechanism behind the GES formation and its distinctions from conventional plasma sheath are discussed. The electromagnetic properties of the Sun derived from our model with the most accurate available inputs are compared with those of others. These results are useful as an input element to study the properties of the linear and nonlinear dynamics of various solar plasma waves, oscillations and instabilities.

The Metallurgical Design of Steels for Optimum Mechanical Properties

DTIC Science & Technology

1945-10-22

to’casting and working), and to some extent, during deforma- tion. Th,. vwr{oua alloying elements have little effect upon the nature of the...procoed, tWho so-ca~lled "equilibrium~ states". This topic lies in thc fiold of thcr- modynrunics. When the equilibrium conditions are( understood, it...is ~o[ssi- ble to considnr thc rates Pand the moch~rmisms of the tra.-nsforr-Wtins: ton- ice in the field of reaction kinetics. Equilibrium Conditions

Nucleon matter equation of state, particle number fluctuations, and shear viscosity within UrQMD box calculations

NASA Astrophysics Data System (ADS)

Motornenko, A.; Bravina, L.; Gorenstein, M. I.; Magner, A. G.; Zabrodin, E.

2018-03-01

Properties of equilibrated nucleon system are studied within the ultra-relativistic quantum molecular dynamics (UrQMD) transport model. The UrQMD calculations are done within a finite box with periodic boundary conditions. The system achieves thermal equilibrium due to nucleon-nucleon elastic scattering. For the UrQMD-equilibrium state, nucleon energy spectra, equation of state, particle number fluctuations, and shear viscosity η are calculated. The UrQMD results are compared with both, statistical mechanics and Chapman-Enskog kinetic theory, for a classical system of nucleons with hard-core repulsion.

Analysis of non-equilibrium phenomena in inductively coupled plasma generators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, W.; Panesi, M., E-mail: mpanesi@illinois.edu; Lani, A.

This work addresses the modeling of non-equilibrium phenomena in inductively coupled plasma discharges. In the proposed computational model, the electromagnetic induction equation is solved together with the set of Navier-Stokes equations in order to compute the electromagnetic and flow fields, accounting for their mutual interaction. Semi-classical statistical thermodynamics is used to determine the plasma thermodynamic properties, while transport properties are obtained from kinetic principles, with the method of Chapman and Enskog. Particle ambipolar diffusive fluxes are found by solving the Stefan-Maxwell equations with a simple iterative method. Two physico-mathematical formulations are used to model the chemical reaction processes: (1) Amore » Local Thermodynamics Equilibrium (LTE) formulation and (2) a thermo-chemical non-equilibrium (TCNEQ) formulation. In the TCNEQ model, thermal non-equilibrium between the translational energy mode of the gas and the vibrational energy mode of individual molecules is accounted for. The electronic states of the chemical species are assumed in equilibrium with the vibrational temperature, whereas the rotational energy mode is assumed to be equilibrated with translation. Three different physical models are used to account for the coupling of chemistry and energy transfer processes. Numerical simulations obtained with the LTE and TCNEQ formulations are used to characterize the extent of non-equilibrium of the flow inside the Plasmatron facility at the von Karman Institute. Each model was tested using different kinetic mechanisms to assess the sensitivity of the results to variations in the reaction parameters. A comparison of temperatures and composition profiles at the outlet of the torch demonstrates that the flow is in non-equilibrium for operating conditions characterized by pressures below 30 000 Pa, frequency 0.37 MHz, input power 80 kW, and mass flow 8 g/s.« less

Analysis of non-equilibrium phenomena in inductively coupled plasma generators

NASA Astrophysics Data System (ADS)

Zhang, W.; Lani, A.; Panesi, M.

2016-07-01

This work addresses the modeling of non-equilibrium phenomena in inductively coupled plasma discharges. In the proposed computational model, the electromagnetic induction equation is solved together with the set of Navier-Stokes equations in order to compute the electromagnetic and flow fields, accounting for their mutual interaction. Semi-classical statistical thermodynamics is used to determine the plasma thermodynamic properties, while transport properties are obtained from kinetic principles, with the method of Chapman and Enskog. Particle ambipolar diffusive fluxes are found by solving the Stefan-Maxwell equations with a simple iterative method. Two physico-mathematical formulations are used to model the chemical reaction processes: (1) A Local Thermodynamics Equilibrium (LTE) formulation and (2) a thermo-chemical non-equilibrium (TCNEQ) formulation. In the TCNEQ model, thermal non-equilibrium between the translational energy mode of the gas and the vibrational energy mode of individual molecules is accounted for. The electronic states of the chemical species are assumed in equilibrium with the vibrational temperature, whereas the rotational energy mode is assumed to be equilibrated with translation. Three different physical models are used to account for the coupling of chemistry and energy transfer processes. Numerical simulations obtained with the LTE and TCNEQ formulations are used to characterize the extent of non-equilibrium of the flow inside the Plasmatron facility at the von Karman Institute. Each model was tested using different kinetic mechanisms to assess the sensitivity of the results to variations in the reaction parameters. A comparison of temperatures and composition profiles at the outlet of the torch demonstrates that the flow is in non-equilibrium for operating conditions characterized by pressures below 30 000 Pa, frequency 0.37 MHz, input power 80 kW, and mass flow 8 g/s.

Hyperdiffusive dynamics in Newtonian nanoparticle fluids [Hyperdiffusive dynamics in equilibrated nanoparticle fluids

DOE PAGES

Srivastava, Samanvaya; Agarwal, Praveen; Mangal, Rahul; ...

2015-09-24

Hyperdiffusive relaxations in soft glassy materials are typically associated with out-of-equilibrium states, and non-equilibrium physics and aging are often invoked in explaining their origins. Here, we report on hyperdiffusive motion in a model, equilibrium soft material comprised of single-component polymer-tethered-nanoparticles. In these materials, polymer mediated interactions lead to strong nanoparticle correlations, hyperdiffusive relaxations, and unusual variations of properties with temperature. Our experimental observations complement the current hypothesis that hyperdiffusive relaxations in soft materials require the material to exist in out–of–equilibrium states capable of driving structural rearrangements. Lastly, we propose alternatively that hyperdiffusive relaxations in our materials can arise naturally frommore » volume fluctuations brought about by equilibrium thermal forces.« less

The automated design of materials far from equilibrium

NASA Astrophysics Data System (ADS)

Miskin, Marc Z.

Automated design is emerging as a powerful concept in materials science. By combining computer algorithms, simulations, and experimental data, new techniques are being developed that start with high level functional requirements and identify the ideal materials that achieve them. This represents a radically different picture of how materials become functional in which technological demand drives material discovery, rather than the other way around. At the frontiers of this field, materials systems previously considered too complicated can start to be controlled and understood. Particularly promising are materials far from equilibrium. Material robustness, high strength, self-healing and memory are properties displayed by several materials systems that are intrinsically out of equilibrium. These and other properties could be revolutionary, provided they can first be controlled. This thesis conceptualizes and implements a framework for designing materials that are far from equilibrium. We show how, even in the absence of a complete physical theory, design from the top down is possible and lends itself to producing physical insight. As a prototype system, we work with granular materials: collections of athermal, macroscopic identical objects, since these materials function both as an essential component of industrial processes as well as a model system for many non-equilibrium states of matter. We show that by placing granular materials in the context of design, benefits emerge simultaneously for fundamental and applied interests. As first steps, we use our framework to design granular aggregates with extreme properties like high stiffness, and softness. We demonstrate control over nonlinear effects by producing exotic aggregates that stiffen under compression. Expanding on our framework, we conceptualize new ways of thinking about material design when automatic discovery is possible. We show how to build rules that link particle shapes to arbitrary granular packing density. We examine how the results of a design process are contingent upon operating conditions by studying which shapes dissipate energy fastest in a granular gas. We even move to create optimization algorithms for the expressed purpose of material design, by integrating them with statistical mechanics. In all of these cases, we show that turning to machines puts a fresh perspective on materials far from equilibrium. By matching forms to functions, complexities become possibilities, motifs emerge that describe new physics, and the door opens to rational design.

On the asymptotic stability of nonlinear mechanical switched systems

NASA Astrophysics Data System (ADS)

Platonov, A. V.

2018-05-01

Some classes of switched mechanical systems with dissipative and potential forces are considered. The case, where either dissipative or potential forces are essentially nonlinear, is studied. It is assumed that the zero equilibrium position of the system is asymptotically stable at least for one operating mode. We will look for sufficient conditions which guarantee the preservation of asymptotic stability of the equilibrium position under the switching of modes. The Lyapunov direct method is used. A Lyapunov function for considered system is constructed, which satisfies the differential inequality of special form for every operating mode. This inequality is nonlinear for the chosen mode with asymptotically stable equilibrium position, and it is linear for the rest modes. The correlations between the intervals of activity of the pointed mode and the intervals of activity of the rest modes are obtained which guarantee the required properties.

Molecular simulations of Crussard curves of detonation product mixtures at chemical equilibrium: Microscopic calculation of the Chapman-Jouguet state

NASA Astrophysics Data System (ADS)

Bourasseau, Emeric; Dubois, Vincent; Desbiens, Nicolas; Maillet, Jean-Bernard

2007-06-01

The simultaneous use of the Reaction Ensemble Monte Carlo (ReMC) method and the Adaptative Erpenbeck EOS (AE-EOS) method allows us to calculate direclty the thermodynamical and chemical equilibrium of a mixture on the hugoniot curve. The ReMC method allow to reach chemical equilibrium of detonation products and the AE-EOS method constraints ths system to satisfy the Hugoniot relation. Once the Crussard curve of detonation products has been established, CJ state properties may be calculated. An additional NPT simulation is performed at CJ conditions in order to compute derivative thermodynamic quantities like Cp, Cv, Gruneisen gama, sound velocity, and compressibility factor. Several explosives has been studied, of which PETN, nitromethane, tetranitromethane, and hexanitroethane. In these first simulations, solid carbon is eventually treated using an EOS.

Acid-Base Properties of Azo Dyes in Solution Studied Using Spectrophotometry and Colorimetry

NASA Astrophysics Data System (ADS)

Snigur, D. V.; Chebotarev, A. N.; Bevziuk, K. V.

2018-03-01

Colorimetry and spectrophotometry with chemometric data processing were used to study the acid-base properties of azo dyes in aqueous solution. The capabilities of both methods were compared. Ionization constants of all the functional groups of the azo compounds studied could be determined relative to the change in the specific color difference depending on the acidity of the medium. The colorimetric functions of ion-molecular forms of azo compounds used as an analytical signal allow us to obtain complete information on the acid-base equilibrium in a wide acidity range.

Computer program determines chemical composition of physical system at equilibrium

NASA Technical Reports Server (NTRS)

Kwong, S. S.

1966-01-01

FORTRAN 4 digital computer program calculates equilibrium composition of complex, multiphase chemical systems. This is a free energy minimization method with solution of the problem reduced to mathematical operations, without concern for the chemistry involved. Also certain thermodynamic properties are determined as byproducts of the main calculations.

A Novel Type of Chaotic Attractor for Quadratic Systems Without Equilibriums

NASA Astrophysics Data System (ADS)

Dantsev, Danylo

In this paper, a new chaotic dynamic system without equilibriums is presented. A conducted research of the qualitative properties of the discovered system reveals a noncompliance between the bifurcation behavior of the system and the Feigenbaum-Sharkovskii-Magnitsky theory. Additional research of known systems confirms the discrepancy.

Against the grain: The physical properties of anisotropic partially molten rocks

NASA Astrophysics Data System (ADS)

Ghanbarzadeh, S.; Hesse, M. A.; Prodanovic, M.

2014-12-01

Partially molten rocks commonly develop textures that appear close to textural equilibrium, where the melt network evolves to minimize the energy of the melt-solid interfaces, while maintaining the dihedral angle θ at solid-solid-melt contact lines. Textural equilibrium provides a powerful model for the melt distribution that controls the petro-physical properties of partially molten rocks, e.g., permeability, elastic moduli, and electrical resistivity. We present the first level-set computations of three-dimensional texturally equilibrated melt networks in rocks with an anisotropic fabric. Our results show that anisotropy induces wetting of smaller grain boundary faces for θ > 0 at realistic porosities ϕ < 3%. This was previously not thought to be possible at textural equilibrium and reconciles the theory with experimental observations. Wetting of the grain boundary faces leads to a dramatic redistribution of the melt from the edges to the faces that introduces strong anisotropy in the petro-physical properties such as permeability, effective electrical conductivity and mechanical properties. Figure, on left, shows that smaller grain boundaries become wetted at relatively low melt fractions of 3% in stretched polyhedral grains with elongation factor 1.5. Right plot represents the ratio of melt electrical conductivity to effective conductivity of medium (known as formation factor) as an example of anisotropy in physical properties. The plot shows that even slight anisotropy in grains induces considerable anisotropy in electrical properties.

Conformational equilibrium in supramolecular chemistry: Dibutyltriuret case.

PubMed

Mroczyńska, Karina; Kaczorowska, Małgorzata; Kolehmainen, Erkki; Grubecki, Ireneusz; Pietrzak, Marek; Ośmiałowski, Borys

2015-01-01

The association of substituted benzoates and naphthyridine dianions was used to study the complexation of dibutyltriuret. The title molecule is the simplest molecule able to form two intramolecular hydrogen bonds. The naphthyridine salt was used to break two intramolecular hydrogen bonds at a time while with the use of substituted benzoates the systematic approach to study association was achieved. Both, titrations and variable temperature measurements shed the light on the importance of conformational equilibrium and its influence on association in solution. Moreover, the associates were observed by mass spectrometry. The DFT-based computations for complexes and single bond rotational barriers supports experimental data and helps understanding the properties of multiply hydrogen bonded complexes.

Game dynamic model for yeast development.

PubMed

Huang, Yuanyuan; Wu, Zhijun

2012-07-01

Game theoretic models, along with replicator equations, have been applied successfully to the study of evolution of populations of competing species, including the growth of a population, the reaching of the population to an equilibrium state, and the evolutionary stability of the state. In this paper, we analyze a game model proposed by Gore et al. (Nature 456:253-256, 2009) in their recent study on the co-development of two mixed yeast strains. We examine the mathematical properties of this model with varying experimental parameters. We simulate the growths of the yeast strains and compare them with the experimental results. We also compute and analyze the equilibrium state of the system and prove that it is asymptotically and evolutionarily stable.

Near-equilibrium desorption of helium films

NASA Astrophysics Data System (ADS)

Weimer, M.; Housley, R. M.; Goodstein, D. L.

1987-10-01

The thermal desorption of helium films in the presence of their equilibrium vapor is studied experimentally for small but rapid departures from ambient temperature. The results are analyzed within the framework of a quasithermodynamic phenomenological model based on detailed balance. Under the usual experimental conditions, isothermal desorption at the temperature of the substrate is a general prediction of the model which seems to be substantiated. For realistic adsorption isotherms the time evolution of the net desorption flux nevertheless appears to be governed by a highly nonlinear equation. In such circumstances, a number of characteristic relaxation times may be identified. These time scales are distinct from, and in general unrelated to, the coverage-dependent mean lifetime of an atom on the surface. To characterize the overall nonlinear evolution towards steady state, a global time scale, defined in terms of both initial- and steady-state properties, is introduced to summarize the experimental data. Internal evidence suggests a criterion for judging when collisions among desorbed atoms are unimportant. When this condition is satisfied, data for near-equilibrium desorption agree well with the predictions of the model. Combining our results with earlier data at higher substrate temperatures and different ambient conditions, the overall picture is consistent with scaling properties implied by the theory. We show that the values of the parameters deduced from a Frenkel-Arrhenius parametrization of the global relaxation times, as well as a variety of other aspects of desorption kinetics, are actually consequences of the shape of the equilibrium adsorption isotherm.

Shape characteristics of equilibrium and non-equilibrium fractal clusters.

PubMed

Mansfield, Marc L; Douglas, Jack F

2013-07-28

It is often difficult in practice to discriminate between equilibrium and non-equilibrium nanoparticle or colloidal-particle clusters that form through aggregation in gas or solution phases. Scattering studies often permit the determination of an apparent fractal dimension, but both equilibrium and non-equilibrium clusters in three dimensions frequently have fractal dimensions near 2, so that it is often not possible to discriminate on the basis of this geometrical property. A survey of the anisotropy of a wide variety of polymeric structures (linear and ring random and self-avoiding random walks, percolation clusters, lattice animals, diffusion-limited aggregates, and Eden clusters) based on the principal components of both the radius of gyration and electric polarizability tensor indicates, perhaps counter-intuitively, that self-similar equilibrium clusters tend to be intrinsically anisotropic at all sizes, while non-equilibrium processes such as diffusion-limited aggregation or Eden growth tend to be isotropic in the large-mass limit, providing a potential means of discriminating these clusters experimentally if anisotropy could be determined along with the fractal dimension. Equilibrium polymer structures, such as flexible polymer chains, are normally self-similar due to the existence of only a single relevant length scale, and are thus anisotropic at all length scales, while non-equilibrium polymer structures that grow irreversibly in time eventually become isotropic if there is no difference in the average growth rates in different directions. There is apparently no proof of these general trends and little theoretical insight into what controls the universal anisotropy in equilibrium polymer structures of various kinds. This is an obvious topic of theoretical investigation, as well as a matter of practical interest. To address this general problem, we consider two experimentally accessible ratios, one between the hydrodynamic and gyration radii, the other between the viscosity and hydrodynamic radii, as potential measures of shape anisotropy. We also find a strong correlation between anisotropy and effective fractal dimension. These observations should provide new practical methods for quantifying the nature of particle clustering in diverse contexts.

Effect of Iron Redox Equilibrium on the Foaming Behavior of MgO-Saturated Slags

NASA Astrophysics Data System (ADS)

Park, Youngjoo; Min, Dong Joon

2018-04-01

In this study, the foaming index of CaO-SiO2-FetO and CaO-SiO2-FetO-Al2O3 slags saturated with MgO was measured to understand the relationship between their foaming behavior and physical properties. The foaming index of MgO-saturated slags increases with the FetO content due to the redox equilibrium of FetO. Experimental results indicated that MgO-saturated slag has relatively high ferric ion concentration, and the foaming index increases due to the effect of ferric ion. Therefore, the foaming behavior of MgO-saturated slag is more reasonably explained by considering the effect of ferric ion on the estimation of slag properties such as viscosity, surface tension, and density. Specifically, the estimation of slag viscosity was additionally verified by NBO/T, and this is experimentally obtained through Raman spectroscopy.

Induced Fit in Protein Multimerization: The HFBI Case

PubMed Central

Riccardi, Laura

2016-01-01

Hydrophobins, produced by filamentous fungi, are small amphipathic proteins whose biological functions rely on their unique surface-activity properties. Understanding the mechanistic details of the multimerization process is of primary importance to clarify the interfacial activity of hydrophobins. We used free energy calculations to study the role of a flexible β-hairpin in the multimerization process in hydrophobin II from Trichoderma reesei (HFBI). We characterized how the displacement of this β-hairpin controls the stability of the monomers/dimers/tetramers in solution. The regulation of the oligomerization equilibrium of HFBI will necessarily affect its interfacial properties, fundamental for its biological function and for technological applications. Moreover, we propose possible routes for the multimerization process of HFBI in solution. This is the first case where a mechanism by which a flexible loop flanking a rigid patch controls the protein-protein binding equilibrium, already known for proteins with charged binding hot-spots, is described within a hydrophobic patch. PMID:27832079

Influence of system size on the properties of a fluid adsorbed in a nanopore: Physical manifestations and methodological consequences

DOE Office of Scientific and Technical Information (OSTI.GOV)

Puibasset, Joël, E-mail: puibasset@cnrs-orleans.fr; Kierlik, Edouard, E-mail: edouard.kierlik@upmc.fr; Tarjus, Gilles, E-mail: tarjus@lptl.jussieu.fr

Hysteresis and discontinuities in the isotherms of a fluid adsorbed in a nanopore in general hamper the determination of equilibrium thermodynamic properties, even in computer simulations. A way around this has been to consider both a reservoir of small size and a pore of small extent in order to restrict the fluctuations of density and approach a classical van der Waals loop. We assess this suggestion by thoroughly studying through Monte Carlo simulations and density functional theory the influence of system size on the equilibrium configurations of the adsorbed fluid and on the resulting isotherms. We stress the importance ofmore » pore-symmetry-breaking states that even for modest pore sizes lead to discontinuous isotherms and we discuss the physical relevance of these states and the methodological consequences for computing thermodynamic quantities.« less

Non-equilibrium coherence dynamics in one-dimensional Bose gases.

PubMed

Hofferberth, S; Lesanovsky, I; Fischer, B; Schumm, T; Schmiedmayer, J

2007-09-20

Low-dimensional systems provide beautiful examples of many-body quantum physics. For one-dimensional (1D) systems, the Luttinger liquid approach provides insight into universal properties. Much is known of the equilibrium state, both in the weakly and strongly interacting regimes. However, it remains a challenge to probe the dynamics by which this equilibrium state is reached. Here we present a direct experimental study of the coherence dynamics in both isolated and coupled degenerate 1D Bose gases. Dynamic splitting is used to create two 1D systems in a phase coherent state. The time evolution of the coherence is revealed through local phase shifts of the subsequently observed interference patterns. Completely isolated 1D Bose gases are observed to exhibit universal sub-exponential coherence decay, in excellent agreement with recent predictions. For two coupled 1D Bose gases, the coherence factor is observed to approach a non-zero equilibrium value, as predicted by a Bogoliubov approach. This coupled-system decay to finite coherence is the matter wave equivalent of phase-locking two lasers by injection. The non-equilibrium dynamics of superfluids has an important role in a wide range of physical systems, such as superconductors, quantum Hall systems, superfluid helium and spin systems. Our experiments studying coherence dynamics show that 1D Bose gases are ideally suited for investigating this class of phenomena.

Boolean decision problems with competing interactions on scale-free networks: Equilibrium and nonequilibrium behavior in an external bias

NASA Astrophysics Data System (ADS)

Zhu, Zheng; Andresen, Juan Carlos; Moore, M. A.; Katzgraber, Helmut G.

2014-02-01

We study the equilibrium and nonequilibrium properties of Boolean decision problems with competing interactions on scale-free networks in an external bias (magnetic field). Previous studies at zero field have shown a remarkable equilibrium stability of Boolean variables (Ising spins) with competing interactions (spin glasses) on scale-free networks. When the exponent that describes the power-law decay of the connectivity of the network is strictly larger than 3, the system undergoes a spin-glass transition. However, when the exponent is equal to or less than 3, the glass phase is stable for all temperatures. First, we perform finite-temperature Monte Carlo simulations in a field to test the robustness of the spin-glass phase and show that the system has a spin-glass phase in a field, i.e., exhibits a de Almeida-Thouless line. Furthermore, we study avalanche distributions when the system is driven by a field at zero temperature to test if the system displays self-organized criticality. Numerical results suggest that avalanches (damage) can spread across the whole system with nonzero probability when the decay exponent of the interaction degree is less than or equal to 2, i.e., that Boolean decision problems on scale-free networks with competing interactions can be fragile when not in thermal equilibrium.

The removal of fluoride from aqueous solution by a lateritic soil adsorption: Kinetic and equilibrium studies.

PubMed

Iriel, Analia; Bruneel, Stijn P; Schenone, Nahuel; Cirelli, Alicia Fernández

2018-03-01

The use of natural sorbents to remove fluoride from drinking water is a promising alternative because of its low-cost and easy implementation. In this article, fluoride adsorption on a latosol soil from Misiones province (Argentina) was studied regarding kinetic and equilibrium aspects. Experiments were conducted in batch at room temperature under controlled conditions of pH 4-8) and ionic strength (1-10mM KNO 3 ). Experimental data indicated that adsorption processes followed a PSO kinetic where initial rates have showed to be influenced by pH solution. The necessary time to reach an equilibrium state had resulted approximately 30min. Equilibrium adsorption studies were performed at pH 8 which is similar to the natural groundwater. For that, fluoride adsorption data were successfully adjusted to Dubinin-Ataskhov model determining that the fluoride adsorption onto soil particles mainly followed a physical mechanism with a removal capacity of 0.48mgg -1 . Finally, a natural groundwater was tested with laterite obtaining a reduction close to 30% from initial concentration and without changing significantly the physicochemical properties of the natural water. Therefore, it was concluded that the use of lateritic soils for fluoride removal is very promising on a domestic scale. Copyright © 2017 Elsevier Inc. All rights reserved.

Near-equilibrium dumb-bell-shaped figures for cohesionless small bodies

NASA Astrophysics Data System (ADS)

Descamps, Pascal

2016-02-01

In a previous paper (Descamps, P. [2015]. Icarus 245, 64-79), we developed a specific method aimed to retrieve the main physical characteristics (shape, density, surface scattering properties) of highly elongated bodies from their rotational lightcurves through the use of dumb-bell-shaped equilibrium figures. The present work is a test of this method. For that purpose we introduce near-equilibrium dumb-bell-shaped figures which are base dumb-bell equilibrium shapes modulated by lognormal statistics. Such synthetic irregular models are used to generate lightcurves from which our method is successfully applied. Shape statistical parameters of such near-equilibrium dumb-bell-shaped objects are in good agreement with those calculated for example for the Asteroid (216) Kleopatra from its dog-bone radar model. It may suggest that such bilobed and elongated asteroids can be approached by equilibrium figures perturbed be the interplay with a substantial internal friction modeled by a Gaussian random sphere.

Electron density measurement of non-equilibrium atmospheric pressure plasma using dispersion interferometer

NASA Astrophysics Data System (ADS)

Yoshimura, Shinji; Kasahara, Hiroshi; Akiyama, Tsuyoshi

2017-10-01

Medical applications of non-equilibrium atmospheric plasmas have recently been attracting a great deal of attention, where many types of plasma sources have been developed to meet the purposes. For example, plasma-activated medium (PAM), which is now being studied for cancer treatment, has been produced by irradiating non-equilibrium atmospheric pressure plasma with ultrahigh electron density to a culture medium. Meanwhile, in order to measure electron density in magnetic confinement plasmas, a CO2 laser dispersion interferometer has been developed and installed on the Large Helical Device (LHD) at the National Institute for Fusion Science, Japan. The dispersion interferometer has advantages that the measurement is insensitive to mechanical vibrations and changes in neutral gas density. Taking advantage of these properties, we applied the dispersion interferometer to electron density diagnostics of atmospheric pressure plasmas produced by the NU-Global HUMAP-WSAP-50 device, which is used for producing PAM. This study was supported by the Grant of Joint Research by the National Institutes of Natural Sciences (NINS).

Inter-layer and intra-layer heat transfer in bilayer/monolayer graphene van der Waals heterostructure: Is there a Kapitza resistance analogous?

NASA Astrophysics Data System (ADS)

Rajabpour, Ali; Fan, Zheyong; Vaez Allaei, S. Mehdi

2018-06-01

Van der Waals heterostructures have exhibited interesting physical properties. In this paper, heat transfer in hybrid coplanar bilayer/monolayer (BL-ML) graphene, as a model layered van der Waals heterostructure, was studied using non-equilibrium molecular dynamics (MD) simulations. The temperature profile and inter- and intra-layer heat fluxes of the BL-ML graphene indicated that, there is no fully developed thermal equilibrium between layers and the drop in the average temperature profile at the step-like BL-ML interface is not attributable to the effect of Kapitza resistance. By increasing the length of the system up to 1 μm in the studied MD simulations, the thermally non-equilibrium region was reduced to a small area near the step-like interface. All MD results were compared to a continuum model and a good match was observed between the two approaches. Our results provide a useful understanding of heat transfer in nano- and micro-scale layered materials and van der Waals heterostructures.

Terahertz Spectroscopy of Low-Dimensional Nanomaterials: Nonlinear Emission and Ultrafast Electrodynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Liang; Wang, Jigang

Nonlinear and non-equilibrium properties of low-dimensional quantum materials are fundamental in nanoscale science yet transformative in nonlinear imaging/photonic technology today. These have been poorly addressed in many nano-materials despite of their well-established equilibrium optical and transport properties. The development of ultrafast terahertz (THz) sources and nonlinear spectroscopy tools facilitates understanding these issues and reveals a wide range of novel nonlinear and quantum phenomena that are not expected in bulk solids or atoms. In this paper, we discuss our recent discoveries in two model photonic and electronic nanostructures to solve two outstanding questions: (1) how to create nonlinear broadband terahertz emittersmore » using deeply subwavelength nanoscale meta-atom resonators? (2) How to access one-dimensional (1D) dark excitons and their non-equilibrium correlated states in single-walled carbon nanotubes (SWMTs)?« less

Terahertz Spectroscopy of Low-Dimensional Nanomaterials: Nonlinear Emission and Ultrafast Electrodynamics

DOE PAGES

Luo, Liang; Wang, Jigang

2016-01-01

Nonlinear and non-equilibrium properties of low-dimensional quantum materials are fundamental in nanoscale science yet transformative in nonlinear imaging/photonic technology today. These have been poorly addressed in many nano-materials despite of their well-established equilibrium optical and transport properties. The development of ultrafast terahertz (THz) sources and nonlinear spectroscopy tools facilitates understanding these issues and reveals a wide range of novel nonlinear and quantum phenomena that are not expected in bulk solids or atoms. In this paper, we discuss our recent discoveries in two model photonic and electronic nanostructures to solve two outstanding questions: (1) how to create nonlinear broadband terahertz emittersmore » using deeply subwavelength nanoscale meta-atom resonators? (2) How to access one-dimensional (1D) dark excitons and their non-equilibrium correlated states in single-walled carbon nanotubes (SWMTs)?« less

Magnetic property zonation in a thick lava flow

NASA Astrophysics Data System (ADS)

Audunsson, Haraldur; Levi, Shaul; Hodges, Floyd

1992-04-01

Intraflow structures and magmatic evolution in an extensive and thick (30-60 m) basaltic lava flow are examined on the basis of grain size and composition-dependent magnetic properties of titanomagnetite materials. Microprobe data indicate that the intraflow oxidation state Fe(3+)/Fe(2+) of the initially precipitated primary titanomagnetites increases with falling equilibrium temperature from the flow margins to a maximum near the center, the position of lowest equilibrium temperature. In contrast, Curie temperature measurements indicate that titanomagnetite oxidation increases with height in the flow. Modification of the initially symmetric equilibrium titanomagnetite compositions was caused by subsolidus high-temperature oxidation possibly due to hydrogen loss produced by dissociation of magmatic water, as well as unknown contributions of circulating air and percolating water from above. The titanomagnetites of the basal layer of the flow remain essentially unaltered.

Stability and bifurcation analysis on a ratio-dependent predator-prey model with time delay

NASA Astrophysics Data System (ADS)

Xu, Rui; Gan, Qintao; Ma, Zhien

2009-08-01

A ratio-dependent predator-prey model with time delay due to the gestation of the predator is investigated. By analyzing the corresponding characteristic equations, the local stability of a positive equilibrium and a semi-trivial boundary equilibrium is discussed, respectively. Further, it is proved that the system undergoes a Hopf bifurcation at the positive equilibrium. Using the normal form theory and the center manifold reduction, explicit formulae are derived to determine the direction of bifurcations and the stability and other properties of bifurcating periodic solutions. By means of an iteration technique, sufficient conditions are obtained for the global attractiveness of the positive equilibrium. By comparison arguments, the global stability of the semi-trivial equilibrium is also addressed. Numerical simulations are carried out to illustrate the main results.

Tables and charts of equilibrium thermodynamic properties of ammonia for temperatures from 500 to 50,000 K.

NASA Technical Reports Server (NTRS)

Simmonds, A. L.; Miller, C. G., III; Nealy, J. E.

1976-01-01

Equilibrium thermodynamic properties for pure ammonia were generated for a range of temperature from 500 to 50,000 K and pressure from 0.01 to 40 MN/sq m and are presented in tabulated and graphical form. Properties include pressure, temperature, density, enthalpy, speed of sound, entropy, molecular-weight ratio, specific heat at constant pressure, specific heat at constant volume, isentropic exponent, and species mole fractions. These properties were calculated by the method which is based on minimization of the Gibbs free energy. The data presented herein are for an 18-species ammonia model. Heats of formation and spectroscopic constants used as input data are presented. Comparison of several thermodynamic properties calculated with the present program and a second computer code is performed for a range of pressure and for temperatures up to 30,000 K.

The exploration of exoplanets: What can we learn from solar system synergies?

NASA Astrophysics Data System (ADS)

Encrenaz, Therese

2015-07-01

Most of the discovered exoplanets are "exotic" with regard to the Solar system, with characteristics that are very different from our own planets. Still, we can use the experience gained in the study of the solar system planets for trying to understand the physical nature of exoplanets. The properties of their atmospheres are, as in the case of the Solar system, constrained by a few parameters: their mass and radius, the stellar radiation flux (and thus the star's properties and its distance to the planet), the planet's ellipticity, its inclination, its rotation, the presence or absence of a magnetosphere... Under some simple hypotheses (thermochemical equilibrium and absence of migration), it is possible to make simple predictions about the nature of the exoplanet's atmospheric composition, on the basis of the planet's mass and its equilibrium temperature. The study of solar system planets also tells us which other mechanisms may lead to a departure from thermochemical equilibrium, in particular photochemistry and transport-induced quenching. The study of planetary spectra is a good starting point to try to understand the spectra of exoplanets that now become available through transit spectroscopy observations. From the spectral type of the hosting star and its distance to the exoplanet, one can estimate the spectral ranges where reflected/scattered stellar radiation and thermal emission dominate. In the thermal regime, the observation of a given molecule in different bands of different intensities may provide constraints on the vertical thermal profile and the vertical distribution of the molecule.

Meniscal material properties are minimally affected by matrix stabilization using glutaraldehyde and glycation with ribose.

PubMed

Hunter, Shawn A; Noyes, Frank R; Haridas, Balakrishna; Levy, Martin S; Butler, David L

2005-05-01

Knee meniscus replacement holds promise, but current allografts are susceptible to biodegradation. Matrix stabilization with glutaraldehyde, a crosslinking agent used clinically to fabricate cardiovascular bioprostheses, or with glycation, a process of crosslinking collagen with sugars such as ribose, is a potential means of rendering tissue resistant to such degradation. However, stabilization should not significantly alter meniscal material properties, which could disturb normal function in the knee. Our objective was to evaluate the effects of glutaraldehyde- and glycation-induced matrix stabilization on the material properties of porcine meniscus. Normal untreated meniscus specimens were tested in confined compression at one of three applied stresses (0.069, 0.208, 0.347 MPa), subjected to either a glutaraldehyde or glycation stabilization treatment, and then re-tested to measure changes in tissue aggregate modulus, permeability, and compressive strain at equilibrium. Changes in these properties significantly increased with glutaraldehyde concentration and exposure time to ribose. One glutaraldehyde and three glycation treatments did not alter aggregate modulus or compressive strain at equilibrium compared to controls (p > 0.10). However, all treatments increased permeability by at least 108% compared to controls (p < 0.001). This study reveals a dose-dependent relationship between meniscal material properties and certain stabilization conditions and identifies treatments that minimally affect these properties. Further research is necessary to determine whether these treatments prevent enzymatic degradation before and after surgical implantation in the knee.

Calculations of critical misfit and thickness: An overview

NASA Technical Reports Server (NTRS)

Vandermerwe, Jan H.; Jesser, W. A.

1988-01-01

This overview stresses the equilibrium/nonequilibrium nature of the physical properties, as well as the basic properties of the models, used to calculate critical misfit and critical thickness in epitaxy.

Flux Jacobian matrices and generaled Roe average for an equilibrium real gas

NASA Technical Reports Server (NTRS)

Vinokur, Marcel

1988-01-01

Inviscid flux Jacobian matrices and their properties used in numerical solutions of conservation laws are extended to general, equilibrium gas laws. Exact and approximate generalizations of the Roe average are presented. Results are given for one-dimensional flow, and then extended to three-dimensional flow with time-varying grids.

Thermodynamical Interactions: Subtleties of Heat and Work Concepts

ERIC Educational Resources Information Center

Anacleto, Joaquim; Anacleto, Joaquim Alberto C.

2008-01-01

This paper focuses on the determination of the final equilibrium state when two ideal gases, isolated from the exterior and starting from preset initial conditions, interact with each other through a piston. Depending on the piston properties, different processes take place and also different sets of equilibrium conditions must be satisfied. Three…

DNA-linked NanoParticle Lattices with Diamond Symmetry: Stability, Shape and Optical Properties

NASA Astrophysics Data System (ADS)

Emamy, Hamed; Tkachenko, Alexei; Gang, Oleg; Starr, Francis

The linking of nanoparticles (NP) by DNA has been proven to be an effective means to create NP lattices with specific order. Lattices with diamond symmetry are predicted to offer novel photonic properties, but self-assembly of such lattices has proven to be challenging due to the low packing fraction, sensitivity to bond orientation, and local heterogeneity. Recently, we reported an approach to create diamond NP lattices based on the association between anisotropic particles with well-defined tetravalent DNA binding topology and isotropically functionalized NP. Here, we use molecular dynamics simulations to evaluate the Gibbs free energy of these lattices, and thereby determine the stability of these lattices as a function of NP size and DNA stiffness. We also predict the equilibrium shape for the cubic diamond crystallite using the Wulff construction method. Specifically, we predict the equilibrium shape using the surface energy for different crystallographic planes. We evaluate surface energy directly form molecular dynamics simulation, which we correlate with theoretical estimates from the expected number of broken DNA bonds along a facet. Furthermore we study the optical properties of this structure, e.g optical bandgap.

Spatial and mesoscopic fluctuations in glassy dynamics

NASA Astrophysics Data System (ADS)

Chamon, Claudio C.; Cugliandolo, Leticia F.

2004-05-01

One of the striking properties of a glassy system is that many material properties depend on its age, i.e., the time since the system entered its glassy phase. In this this talk we shall review some recent progress (work in collaboration with H. E. Castillo, P. Charbonneau, J. L. Iguain, M. P. Kennett, D. R. Reichman and M. Sellitto) in understanding local aging, through the study of local observable quantities, which reveal that there are spatial heterogeneities and fluctuations in the aging process of macroscopic systems. We show that a number of universal properties are shared by many non-equilibrium systems, both with and without quenched disorder, such as the 3D Edwards-Anderson model and some kinetically constrained non-interacting 2D and 3D spin models, for example. Similar scaling relations are found for mesoscopic sample-to-sample fluctuations of global quantities in small size systems. We discuss how the emergence of a symmetry in aging systems, time-reparametrization invariance, could be responsible for the observed universal behavior of the local and mesoscopic non-equilibrium fluctuations.

On Nash-Equilibria of Approximation-Stable Games

NASA Astrophysics Data System (ADS)

Awasthi, Pranjal; Balcan, Maria-Florina; Blum, Avrim; Sheffet, Or; Vempala, Santosh

One reason for wanting to compute an (approximate) Nash equilibrium of a game is to predict how players will play. However, if the game has multiple equilibria that are far apart, or ɛ-equilibria that are far in variation distance from the true Nash equilibrium strategies, then this prediction may not be possible even in principle. Motivated by this consideration, in this paper we define the notion of games that are approximation stable, meaning that all ɛ-approximate equilibria are contained inside a small ball of radius Δ around a true equilibrium, and investigate a number of their properties. Many natural small games such as matching pennies and rock-paper-scissors are indeed approximation stable. We show furthermore there exist 2-player n-by-n approximation-stable games in which the Nash equilibrium and all approximate equilibria have support Ω(log n). On the other hand, we show all (ɛ,Δ) approximation-stable games must have an ɛ-equilibrium of support O(Δ^{2-o(1)}/ɛ2{log n}), yielding an immediate n^{O(Δ^{2-o(1)}/ɛ^2log n)}-time algorithm, improving over the bound of [11] for games satisfying this condition. We in addition give a polynomial-time algorithm for the case that Δ and ɛ are sufficiently close together. We also consider an inverse property, namely that all non-approximate equilibria are far from some true equilibrium, and give an efficient algorithm for games satisfying that condition.

Influence of metallic vapours on thermodynamic and transport properties of two-temperature air plasma

NASA Astrophysics Data System (ADS)

Zhong, Linlin; Wang, Xiaohua; Cressault, Yann; Teulet, Philippe; Rong, Mingzhe

2016-09-01

The metallic vapours (i.e., copper, iron, and silver in this paper) resulting from walls and/or electrode surfaces can significantly affect the characteristics of air plasma. Different from the previous works assuming local thermodynamic equilibrium, this paper investigates the influence of metallic vapours on two-temperature (2 T) air plasma. The 2 T compositions of air contaminated by Cu, Fe, and Ag are first determined based on Saha's and Guldberg-Waage's laws. The thermodynamic properties (including mass density, specific enthalpy, and specific heat) are then calculated according to their definitions. After determining the collision integrals for each pair of species in air-metal mixtures using the newly published methods and source data, the transport coefficients (including electrical conductivity, viscosity, and thermal conductivity) are calculated for air-Cu, air-Fe, and air-Ag plasmas with different non-equilibrium degree θ (Te/Th). The influences of metallic contamination as well as non-equilibrium degree are discussed. It is found that copper, iron, and silver exist mainly in the form of Cu2, FeO, and AgO at low temperatures. Generally, the metallic vapours increase mass density at most temperatures, reduce the specific enthalpy and specific heat in the whole temperature range, and affect the transport properties remarkably from 5000 K to 20 000 K. The effect arising from the type of metals is little except for silver at certain temperatures. Besides, the departure from thermal equilibrium results in the delay of dissociation and ionization reactions, leading to the shift of thermodynamic and transport properties towards a higher temperature.

A demonstration experiment for studying the properties of saturated vapor

NASA Astrophysics Data System (ADS)

Grebenev, Igor V.; Lebedeva, Olga V.; Polushkina, Svetlana V.

2017-11-01

The paper proposes an important demonstration experiment that can be used at secondary schools in physics. The described experiment helps students learn the main concepts of the topic ‘saturated vapor’, namely, evaporation, condensation, dynamic equilibrium, saturation vapor, partial pressure, and the dependence of saturated vapor pressure on temperature.

Use of a chemical equilibrium model to describe surface properties and uptake of cadmium, strontium, and lead by Chlorella (UTEX 252)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hassett, J.M.

1988-01-01

Metal-aquatic biota interactions are important in both natural and engineered systems. In this study, the uptake of cadmium, strontium and lead by the unicellular green alga Chlorella (UTEX 252) was investigated. Variables included metal concentration, pH, and ionic strength. Data gathered included dry weights (mg/l), cell counts (cells/ml), electrophoretic mobilities (EPMs, {mu}m/sec/V/cm) of metal-free and metal-exposed cells, and metal uptake - difference in concentration in filtrate of cell-metal and cell-free metal solutions. Derived data included cell volumes and surface area, uptake on a {mu}M/m{sup 2} basis, {zeta}-potentials, diffuse layer potentials and charge densities. Typical uptake values were 1.1, 5.2, andmore » 6 {mu}M/m{sup 2} for Cd, Pb, and Sr, respectively, from solutions of pH 6, ionic strength 0.02M, and metal concentration 10{sup {minus}4} M. Cell EPMs were insensitive to metal; under certain conditions, however, (pM > 4, pH > 8), cadmium exposed cells exhibited a reversal in surface charge from negative to positive. The chemical equilibrium model MINEQL1 + STANFORD was used to model algal surface properties and metal uptake. Input data included site pK, density, and {Delta}pK, estimated from EPM-pH data. The model described surface properties of Chlorella (UTEX 252) as judged by a close fit of {zeta}-potentials and model-derived diffuse layer potentials. Metal uptake was modelled by adjusting site density and/or metal-surface site equilibrium constants. Attempts to model surface properties and metal uptake simultaneously were not successful.« less

Direct comparison of the hygroscopic properties of ammonium sulfate and sodium chloride aerosol at relative humidities approaching saturation.

PubMed

Walker, Jim S; Wills, Jon B; Reid, Jonathan P; Wang, Liangyu; Topping, David O; Butler, Jason R; Zhang, Yun-Hong

2010-12-09

Holographic optical tweezers are used to make comparative measurements of the hygroscopic properties of single component aqueous aerosol containing sodium chloride and ammonium sulfate over a range of relative humidity from 84% to 96%. The change in RH over the course of the experiment is monitored precisely using a sodium chloride probe droplet with accuracy better than ±0.09%. The measurements are used to assess the accuracy of thermodynamic treatments of the relationship between water activity and solute mass fraction with particular attention focused on the dilute solute limit approaching saturation vapor pressure. The consistency of the frequently used Clegg-Brimblecombe-Wexler (CBW) treatment for predicting the hygroscopic properties of sodium chloride and ammonium sulfate aerosol is confirmed. Measurements of the equilibrium size of ammonium sulfate aerosol are found to agree with predictions to within an uncertainty of ±0.2%. Given the accuracy of treating equilibrium composition, the inconsistencies highlighted in recent calibration measurements of critical supersaturations of sodium chloride and ammonium sulfate aerosol cannot be attributed to uncertainties associated with the thermodynamic predictions and must have an alternative origin. It is concluded that the CBW treatment can allow the critical supersaturation to be estimated for sodium chloride and ammonium sulfate aerosol with an accuracy of better than ±0.002% in RH. This corresponds to an uncertainty of ≤1% in the critical supersaturation for typical supersaturations of 0.2% and above. This supports the view that these systems can be used to accurately calibrate instruments that measure cloud condensation nuclei concentrations at selected supersaturations. These measurements represent the first study in which the equilibrium properties of two particles of chemically distinct composition have been compared simultaneously and directly alongside each other in the same environment.

Flux line non-equilibrium relaxation kinetics following current quenches in disordered type-II superconductors

NASA Astrophysics Data System (ADS)

Chaturvedi, Harshwardhan; Assi, Hiba; Dobramysl, Ulrich; Pleimling, Michel; Täuber, Uwe

We investigate the relaxation dynamics of magnetic vortex lines in disordered type-II superconductors following rapid changes in the external driving current by means of Langevin molecular dynamics simulations for an elastic line model. A system of driven interacting flux lines in a sample with randomly distributed point pinning centers is initially relaxed to a moving non-equilibrium steady state. The current is then instantaneously decreased, such that the final stationary state resides either still in the moving regime, or in the pinned Bragg glass phase. The ensuing non-equilibrium relaxation kinetics of the vortices is studied in detail by measuring the mean flux line gyration radius and the two-time transverse height autocorrelation function. The latter allows us to investigate the physical aging properties for quenches from the moving into the glassy phase, and to compare with non-equilibrium relaxation features obtained with different initial configurations. Research supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award DE-FG02-09ER46613.

Non-equilibrium behaviour in coacervate-based protocells under electric-field-induced excitation

NASA Astrophysics Data System (ADS)

Yin, Yudan; Niu, Lin; Zhu, Xiaocui; Zhao, Meiping; Zhang, Zexin; Mann, Stephen; Liang, Dehai

2016-02-01

Although numerous strategies are now available to generate rudimentary forms of synthetic cell-like entities, minimal progress has been made in the sustained excitation of artificial protocells under non-equilibrium conditions. Here we demonstrate that the electric field energization of coacervate microdroplets comprising polylysine and short single strands of DNA generates membrane-free protocells with complex, dynamical behaviours. By confining the droplets within a microfluidic channel and applying a range of electric field strengths, we produce protocells that exhibit repetitive cycles of vacuolarization, dynamical fluctuations in size and shape, chaotic growth and fusion, spontaneous ejection and sequestration of matter, directional capture of solute molecules, and pulsed enhancement of enzyme cascade reactions. Our results highlight new opportunities for the study of non-equilibrium phenomena in synthetic protocells, provide a strategy for inducing complex behaviour in electrostatically assembled soft matter microsystems and illustrate how dynamical properties can be activated and sustained in microcompartmentalized media.

Non-equilibrium behaviour in coacervate-based protocells under electric-field-induced excitation

PubMed Central

Yin, Yudan; Niu, Lin; Zhu, Xiaocui; Zhao, Meiping; Zhang, Zexin; Mann, Stephen; Liang, Dehai

2016-01-01

Although numerous strategies are now available to generate rudimentary forms of synthetic cell-like entities, minimal progress has been made in the sustained excitation of artificial protocells under non-equilibrium conditions. Here we demonstrate that the electric field energization of coacervate microdroplets comprising polylysine and short single strands of DNA generates membrane-free protocells with complex, dynamical behaviours. By confining the droplets within a microfluidic channel and applying a range of electric field strengths, we produce protocells that exhibit repetitive cycles of vacuolarization, dynamical fluctuations in size and shape, chaotic growth and fusion, spontaneous ejection and sequestration of matter, directional capture of solute molecules, and pulsed enhancement of enzyme cascade reactions. Our results highlight new opportunities for the study of non-equilibrium phenomena in synthetic protocells, provide a strategy for inducing complex behaviour in electrostatically assembled soft matter microsystems and illustrate how dynamical properties can be activated and sustained in microcompartmentalized media. PMID:26876162

Communication: Influence of external static and alternating electric fields on water from long-time non-equilibrium ab initio molecular dynamics

NASA Astrophysics Data System (ADS)

Futera, Zdenek; English, Niall J.

2017-07-01

The response of water to externally applied electric fields is of central relevance in the modern world, where many extraneous electric fields are ubiquitous. Historically, the application of external fields in non-equilibrium molecular dynamics has been restricted, by and large, to relatively inexpensive, more or less sophisticated, empirical models. Here, we report long-time non-equilibrium ab initio molecular dynamics in both static and oscillating (time-dependent) external electric fields, therefore opening up a new vista in rigorous studies of electric-field effects on dynamical systems with the full arsenal of electronic-structure methods. In so doing, we apply this to liquid water with state-of-the-art non-local treatment of dispersion, and we compute a range of field effects on structural and dynamical properties, such as diffusivities and hydrogen-bond kinetics.

First principles calculations of thermal conductivity with out of equilibrium molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Puligheddu, Marcello; Gygi, Francois; Galli, Giulia

The prediction of the thermal properties of solids and liquids is central to numerous problems in condensed matter physics and materials science, including the study of thermal management of opto-electronic and energy conversion devices. We present a method to compute the thermal conductivity of solids by performing ab initio molecular dynamics at non equilibrium conditions. Our formulation is based on a generalization of the approach to equilibrium technique, using sinusoidal temperature gradients, and it only requires calculations of first principles trajectories and atomic forces. We discuss results and computational requirements for a representative, simple oxide, MgO, and compare with experiments and data obtained with classical potentials. This work was supported by MICCoM as part of the Computational Materials Science Program funded by the U.S. Department of Energy (DOE), Office of Science , Basic Energy Sciences (BES), Materials Sciences and Engineering Division under Grant DOE/BES 5J-30.

Characterization of Low-Symmetry Structures from Phase Equilibrium of Fe-Al System—Microstructures and Mechanical Properties

PubMed Central

Matysik, Piotr; Jóźwiak, Stanisław; Czujko, Tomasz

2015-01-01

Fe-Al intermetallic alloys with aluminum content over 60 at% are in the area of the phase equilibrium diagram that is considerably less investigated in comparison to the high-symmetry Fe3Al and FeAl phases. Ambiguous crystallographic information and incoherent data referring to the phase equilibrium diagrams placed in a high-aluminum range have caused confusions and misinformation. Nowadays unequivocal material properties description of FeAl2, Fe2Al5 and FeAl3 intermetallic alloys is still incomplete. In this paper, the influence of aluminum content and processing parameters on phase composition is presented. The occurrence of low-symmetry FeAl2, Fe2Al5 and FeAl3 structures determined by chemical composition and phase transformations was defined by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) examinations. These results served to verify diffraction investigations (XRD) and to explain the mechanical properties of cast materials such as: hardness, Young’s modulus and fracture toughness evaluated using the nano-indentation technique. PMID:28787979

Thermodynamic properties and transport coefficients of air thermal plasmas mixed with ablated vapors of Cu and polytetrafluoroethylene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, JunMin, E-mail: jmzhang@buaa.edu.cn, E-mail: guanyg@tsinghua.edu.cn; Lu, ChunRong; Guan, YongGang, E-mail: jmzhang@buaa.edu.cn, E-mail: guanyg@tsinghua.edu.cn

2015-10-15

Because the fault arc in aircraft electrical system often causes a fire, it is particularly important to analyze its energy and transfer for aircraft safety. The calculation of arc energy requires the basic parameters of the arc. This paper is mainly devoted to the calculations of equilibrium composition, thermodynamic properties (density, molar weight, enthalpy, and specific heat at constant pressure) and transport coefficients (thermal conductivity, electrical conductivity, and viscosity) of plasmas produced by a mixture of air, Cu, and polytetrafluoroethylene under the condition of local thermodynamic equilibrium. The equilibrium composition is determined by solving a system of equations around themore » number densities of each species. The thermodynamic properties are obtained according to the standard thermodynamic relationships. The transport coefficients are calculated using the Chapman-Enskog approximations. Results are presented in the temperature range from 3000 to 30 000 K for pressures of 0.08 and 0.1 MPa, respectively. The results are more accurate and are reliable reference data for theoretical analysis and computational simulation of the behavior of fault arc.« less

Dynamical quantum phase transitions: a review

NASA Astrophysics Data System (ADS)

Heyl, Markus

2018-05-01

Quantum theory provides an extensive framework for the description of the equilibrium properties of quantum matter. Yet experiments in quantum simulators have now opened up a route towards the generation of quantum states beyond this equilibrium paradigm. While these states promise to show properties not constrained by equilibrium principles, such as the equal a priori probability of the microcanonical ensemble, identifying the general properties of nonequilibrium quantum dynamics remains a major challenge, especially in view of the lack of conventional concepts such as free energies. The theory of dynamical quantum phase transitions attempts to identify such general principles by lifting the concept of phase transitions to coherent quantum real-time evolution. This review provides a pedagogical introduction to this field. Starting from the general setting of nonequilibrium dynamics in closed quantum many-body systems, we give the definition of dynamical quantum phase transitions as phase transitions in time with physical quantities becoming nonanalytic at critical times. We summarize the achieved theoretical advances as well as the first experimental observations, and furthermore provide an outlook to major open questions as well as future directions of research.

Dynamical quantum phase transitions: a review.

PubMed

Heyl, Markus

2018-05-01

Quantum theory provides an extensive framework for the description of the equilibrium properties of quantum matter. Yet experiments in quantum simulators have now opened up a route towards the generation of quantum states beyond this equilibrium paradigm. While these states promise to show properties not constrained by equilibrium principles, such as the equal a priori probability of the microcanonical ensemble, identifying the general properties of nonequilibrium quantum dynamics remains a major challenge, especially in view of the lack of conventional concepts such as free energies. The theory of dynamical quantum phase transitions attempts to identify such general principles by lifting the concept of phase transitions to coherent quantum real-time evolution. This review provides a pedagogical introduction to this field. Starting from the general setting of nonequilibrium dynamics in closed quantum many-body systems, we give the definition of dynamical quantum phase transitions as phase transitions in time with physical quantities becoming nonanalytic at critical times. We summarize the achieved theoretical advances as well as the first experimental observations, and furthermore provide an outlook to major open questions as well as future directions of research.

Building on the Legacy of Professor Keenan. Entropy An Intrinsic Property of Matter

NASA Astrophysics Data System (ADS)

Gyftopoulos, Elias P.

2008-08-01

In the scientific and engineering literature, entropy—the distinguishing feature of thermodynamics from other branches of physics—is viewed with skepticism, and thought to be not a physical property of matter—like mass or energy—but a measure either of disorder in a system, or of lack of information about the physics of a system in a thermodynamic equilibrium state, and a plethora of expressions are proposed for its analytical representation. In this article, I present briefly two revolutionary nonstatistical expositions of thermodynamics (revolutionary in the sense of Thomas Kuhn, The Structure of Scientific Revolutions, U. Chicago Press, 1970) that apply to all systems (both macroscopic and microscopic, including one spin or a single particle), to all states (thermodynamic equilibrium, and not thermodynamic equilibrium), and that disclose entropy as an intrinsic property of matter. The first theory is presented without reference to quantum mechanics even though quantum theoretic ideas are lurking behind the exposition. The second theory is a unified quantum theory of mechanics and thermodynamics without statistical probabilities, that is, I am not presenting another version of statistical quantum mechanics.

Disk in a groove with friction: An analysis of static equilibrium and indeterminacy

NASA Astrophysics Data System (ADS)

Donolato, Cesare

2018-05-01

This note studies the statics of a rigid disk placed in a V-shaped groove with frictional walls and subjected to gravity and a torque. The two-dimensional equilibrium problem is formulated in terms of the angles that contact forces form with the normal to the walls. This approach leads to a single trigonometric equation in two variables whose domain is determined by Coulomb's law of friction. The properties of solutions (existence, uniqueness, or indeterminacy) as functions of groove angle, friction coefficient and applied torque are derived by a simple geometric representation. The results modify some of the conclusions by other authors on the same problem.

Scattering-matrix approach to Casimir-Lifshitz force and heat transfer out of thermal equilibrium between arbitrary bodies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Messina, Riccardo; Antezza, Mauro; CNRS, Laboratoire Charles Coulomb UMR 5221, F-34095, Montpellier

2011-10-15

We study the radiative heat transfer and the Casimir-Lifshitz force occurring between two bodies in a system out of thermal equilibrium. We consider bodies of arbitrary shape and dielectric properties, held at two different temperatures and immersed in environmental radiation at a third different temperature. We derive explicit closed-form analytic expressions for the correlations of the electromagnetic field and for the heat transfer and Casimir-Lifshitz force in terms of the bodies' scattering matrices. We then consider some particular cases which we investigate in detail: the atom-surface and the slab-slab configurations.

The rock-paper-scissors game

NASA Astrophysics Data System (ADS)

Zhou, Hai-Jun

2016-04-01

Rock-Paper-Scissors (RPS), a game of cyclic dominance, is not merely a popular children's game but also a basic model system for studying decision-making in non-cooperative strategic interactions. Aimed at students of physics with no background in game theory, this paper introduces the concepts of Nash equilibrium and evolutionarily stable strategy, and reviews some recent theoretical and empirical efforts on the non-equilibrium properties of the iterated RPS, including collective cycling, conditional response patterns and microscopic mechanisms that facilitate cooperation. We also introduce several dynamical processes to illustrate the applications of RPS as a simplified model of species competition in ecological systems and price cycling in economic markets.

Small-molecule photostabilizing agents are modifiers of lipid bilayer properties.

PubMed

Alejo, Jose L; Blanchard, Scott C; Andersen, Olaf S

2013-06-04

Small-molecule photostabilizing or protective agents (PAs) provide essential support for the stability demands on fluorescent dyes in single-molecule spectroscopy and fluorescence microscopy. These agents are employed also in studies of cell membranes and model systems mimicking lipid bilayer environments, but there is little information about their possible effects on membrane structure and physical properties. Given the impact of amphipathic small molecules on bilayer properties such as elasticity and intrinsic curvature, we investigated the effects of six commonly used PAs--cyclooctatetraene (COT), para-nitrobenzyl alcohol (NBA), Trolox (TX), 1,4-diazabicyclo[2.2.2]octane (DABCO), para-nitrobenzoic acid (pNBA), and n-propyl gallate (nPG)--on bilayer properties using a gramicidin A (gA)-based fluorescence quench assay to probe for PA-induced changes in the gramicidin monomer↔dimer equilibrium. The experiments were done using fluorophore-loaded large unilamellar vesicles that had been doped with gA, and changes in the gA monomer↔dimer equilibrium were assayed using a gA channel-permeable fluorescence quencher (Tl⁺). Changes in bilayer properties caused by, e.g., PA adsorption at the bilayer/solution interface that alter the equilibrium constant for gA channel formation, and thus the number of conducting gA channels in the large unilamellar vesicle membrane, will be detectable as changes in the rate of Tl⁺ influx-the fluorescence quench rate. Over the experimentally relevant millimolar concentration range, TX, NBA, and pNBA, caused comparable increases in gA channel activity. COT, also in the millimolar range, caused a slight decrease in gA channel activity. nPG increased channel activity at submillimolar concentrations. DABCO did not alter gA activity. Five of the six tested PAs thus alter lipid bilayer properties at experimentally relevant concentrations, which becomes important for the design and analysis of fluorescence studies in cells and model membrane systems. We therefore tested combinations of COT, NBA, and TX; the combinations altered the fluorescence quench rate less than would be predicted assuming their effects on bilayer properties were additive. The combination of equimolar concentrations of COT and NBA caused minimal changes in the fluorescence quench rate. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Cooling of Accretion-Heated Neutron Stars

NASA Astrophysics Data System (ADS)

Wijnands, Rudy; Degenaar, Nathalie; Page, Dany

2017-09-01

We present a brief, observational review about the study of the cooling behaviour of accretion-heated neutron stars and the inferences about the neutron-star crust and core that have been obtained from these studies. Accretion of matter during outbursts can heat the crust out of thermal equilibrium with the core and after the accretion episodes are over, the crust will cool down until crust-core equilibrium is restored. We discuss the observed properties of the crust cooling sources and what has been learned about the physics of neutron-star crusts. We also briefly discuss those systems that have been observed long after their outbursts were over, i.e, during times when the crust and core are expected to be in thermal equilibrium. The surface temperature is then a direct probe for the core temperature. By comparing the expected temperatures based on estimates of the accretion history of the targets with the observed ones, the physics of neutron-star cores can be investigated. Finally, we discuss similar studies performed for strongly magnetized neutron stars in which the magnetic field might play an important role in the heating and cooling of the neutron stars.

Non-equilibrium Properties of a Pumped-Decaying Bose-Condensed Electron–Hole Gas in the BCS–BEC Crossover Region

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hanai, R.; Littlewood, P. B.; Ohashi, Y.

2016-03-01

We theoretically investigate a Bose-condensed exciton gas out of equilibrium. Within the framework of the combined BCS-Leggett strong-coupling theory with the non-equilibrium Keldysh formalism, we show how the Bose-Einstein condensation (BEC) of excitons is suppressed to eventually disappear, when the system is in the non-equilibrium steady state. The supply of electrons and holes from the bath is shown to induce quasi-particle excitations, leading to the partial occupation of the upper branch of Bogoliubov single-particle excitation spectrum. We also discuss how this quasi-particle induction is related to the suppression of exciton BEC, as well as the stability of the steady state.

A rapid method for the computation of equilibrium chemical composition of air to 15000 K

NASA Technical Reports Server (NTRS)

Prabhu, Ramadas K.; Erickson, Wayne D.

1988-01-01

A rapid computational method has been developed to determine the chemical composition of equilibrium air to 15000 K. Eleven chemically reacting species, i.e., O2, N2, O, NO, N, NO+, e-, N+, O+, Ar, and Ar+ are included. The method involves combining algebraically seven nonlinear equilibrium equations and four linear elemental mass balance and charge neutrality equations. Computational speeds for determining the equilibrium chemical composition are significantly faster than the often used free energy minimization procedure. Data are also included from which the thermodynamic properties of air can be computed. A listing of the computer program together with a set of sample results are included.

Dynamics of Equilibrium Points in a Uniformly Rotating Second-Order and Degree Gravitational Field

NASA Astrophysics Data System (ADS)

Feng, Jinglang; Hou, Xiyun

2017-07-01

Using tools such as periodic orbits and invariant manifolds, the global dynamics around equilibrium points (EPs) in a rotating second-order and degree gravitational field are studied. For EPs on the long axis, planar and vertical periodic families are computed, and their stability properties are investigated. Invariant manifolds are also computed, and their relation to the first-order resonances is briefly discussed. For EPs on the short axis, planar and vertical periodic families are studied, with special emphasis on the genealogy of the planar periodic families. Our studies show that the global dynamics around EPs are highly similar to those around libration points in the circular restricted three-body problem, such as spatial halo orbits, invariant manifolds, and the genealogy of planar periodic families.

Isotropy equilibrium of the double woven fabric with cotton face and wool reverse fibrous compositions

NASA Astrophysics Data System (ADS)

Rahnev, I.; Rimini, G.

2017-10-01

The equilibrium of the masses and the mechanical properties between the warp and the weft is a determining factor for the quality of the woven fabrics. When the fabric has a multi-layered structure and is designed for protective clothing, the uniform distribution of the elastical resistance acquires a paramount importance for the consumer properties. Isotropy in the sense of absolute equalising of the properties between the base and the weft evaluates the achieved optimum cohesion between the weaving threads and directs the weaving cycle settings. The possible variation of the ratio between the elastic modules of the warp and the weft, depending on the weft spacing and the warp tension, is the basic idea of this article.

Facile chemical synthesis and equilibrium unfolding properties of CopG

PubMed Central

Wales, Thomas E.; Richardson, Jane S.; Fitzgerald, Michael C.

2004-01-01

The 45-amino acid polypeptide chain of the homodimeric transcriptional repressor, CopG, was chemically synthesized by stepwise solid phase peptide synthesis (SPPS) using a protocol based on Boc-chemistry. The product obtained from the synthesis was readily purified by reversed-phase HPLC to give a good overall yield (21% by weight). Moreover, the synthetic CopG constructs prepared in this work folded into three-dimensional structures similar to the wild-type protein prepared using conventional recombinant methods as judged by far UV-CD spectroscopy. A fluorescent CopG analog, (Y39W)CopG, was also designed and chemically synthesized to facilitate biophysical studies of CopG’s protein folding and assembly reaction. The guanidinium chloride-induced equilibrium unfolding properties of the wild-type CopG and (Y39W)CopG constructs in this work were characterized and used to develop a model for CopG’s equilibrium unfolding reaction. Our results indicate that CopG’s folding and assembly reaction is well modeled by a two-state process involving folded dimer and unfolded monomer. Using this model, ΔGf and m-values of −13.42 ± 0.04 kcal/mole dimer and 1.92 ± 0.01 kcal/(mole M) were calculated for CopG. PMID:15169951

Controlling Non-Equilibrium Structure Formation on the Nanoscale.

PubMed

Buchmann, Benedikt; Hecht, Fabian Manfred; Pernpeintner, Carla; Lohmueller, Theobald; Bausch, Andreas R

2017-12-06

Controlling the structure formation of gold nanoparticle aggregates is a promising approach towards novel applications in many fields, ranging from (bio)sensing to (bio)imaging to medical diagnostics and therapeutics. To steer structure formation, the DNA-DNA interactions of DNA strands that are coated on the surface of the particles have become a valuable tool to achieve precise control over the interparticle potentials. In equilibrium approaches, this technique is commonly used to study particle crystallization and ligand binding. However, regulating the structural growth processes from the nano- to the micro- and mesoscale remains elusive. Here, we show that the non-equilibrium structure formation of gold nanoparticles can be stirred in a binary heterocoagulation process to generate nanoparticle clusters of different sizes. The gold nanoparticles are coated with sticky single stranded DNA and mixed at different stoichiometries and sizes. This not only allows for structural control but also yields access to the optical properties of the nanoparticle suspensions. As a result, we were able to reliably control the kinetic structure formation process to produce cluster sizes between tens of nanometers up to micrometers. Consequently, the intricate optical properties of the gold nanoparticles could be utilized to control the maximum of the nanoparticle suspension extinction spectra between 525 nm and 600 nm. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computational and theoretical modeling of pH and flow effects on the early-stage non-equilibrium self-assembly of optoelectronic peptides

NASA Astrophysics Data System (ADS)

Mansbach, Rachael; Ferguson, Andrew

Self-assembling π-conjugated peptides are attractive candidates for the fabrication of bioelectronic materials possessing optoelectronic properties due to electron delocalization over the conjugated peptide groups. We present a computational and theoretical study of an experimentally-realized optoelectronic peptide that displays triggerable assembly in low pH to resolve the microscopic effects of flow and pH on the non-equilibrium morphology and kinetics of assembly. Using a combination of molecular dynamics simulations and hydrodynamic modeling, we quantify the time and length scales at which convective flows employed in directed assembly compete with microscopic diffusion to influence assembly. We also show that there is a critical pH below which aggregation proceeds irreversibly, and quantify the relationship between pH, charge density, and aggregate size. Our work provides new fundamental understanding of pH and flow of non-equilibrium π-conjugated peptide assembly, and lays the groundwork for the rational manipulation of environmental conditions and peptide chemistry to control assembly and the attendant emergent optoelectronic properties. This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award # DE-SC0011847, and by the Computational Science and Engineering Fellowship from the University of Illinois at Urbana-Champaign.

The Nash Equilibrium Revisited: Chaos and Complexity Hidden in Simplicity

NASA Astrophysics Data System (ADS)

Fellman, Philip V.

The Nash Equilibrium is a much discussed, deceptively complex, method for the analysis of non-cooperative games (McLennan and Berg, 2005). If one reads many of the commonly available definitions the description of the Nash Equilibrium is deceptively simple in appearance. Modern research has discovered a number of new and important complex properties of the Nash Equilibrium, some of which remain as contemporary conundrums of extraordinary difficulty and complexity (Quint and Shubik, 1997). Among the recently discovered features which the Nash Equilibrium exhibits under various conditions are heteroclinic Hamiltonian dynamics, a very complex asymptotic structure in the context of two-player bi-matrix games and a number of computationally complex or computationally intractable features in other settings (Sato, Akiyama and Farmer, 2002). This paper reviews those findings and then suggests how they may inform various market prediction strategies.

Interaction of polyhedral oligomeric silsesquioxanes and dipalmitoylphosphatidylcholine at the air/water interface: Thermodynamic and rheological study.

PubMed

Skrzypiec, M; Georgiev, G As; Rojewska, M; Prochaska, K

2017-10-01

Polyhedral oligomeric silsesquioxanes (POSS) derivatives containing open silsesquioxane cage bear great potential for biomedical applications and therefore their lateral interactions with phospholipids, major biomembranes and drug vehicles constituent, should be studied in detail. That is why the properties of surface films by two POSS-derivatives, POSS-polyethylene glycol (POSS-PEG) and POSS-perfluoroalkyl (POSS-OFP), pure and in presence of 1,2-dipalmitoyl-sn-glycerol-3-phosphocholine (DPPC) were studied using Langmuir surface balance. Side chains of opposite nature (PEG is hydrophilic; OFP is hydrophobic) were selected, so that to evaluate their impact on polymers' surface properties. Two types of measurements were performed: (i) the miscibility of POSS-derivatives with DPPC was evaluated via thermodynamic analysis of the surface pressure (π)-area (A) isotherms and (ii) the dilatational rheology of selected POSS-polymer containing films was studied by the stress relaxation method. Fourier transformation analysis of the relaxation transients allows to access films' dynamic interfacial properties in broad frequency range (10 -5 -1Hz). Film morphology was monitored with Brewster Angle Microscopy. PEG moiety enabled POSS-PEG to stably incorporate in DPPC films, modifying their equilibrium and dynamic properties. In contrast OFP chains excluded from interactions with other molecules and diminished PEG-OFP amphiphilicity. Therefore at high packing densities (π≥25mN/m) PEG-OFP was expelled from the air/water interface in DPPC/PEG-OFP mixtures, and the binary films equilibrium and dynamic surface properties were determined primarily by DPPC. Thus the choice of POSS side chains can play key role in biomedical applications depending on whether strong or weak incorporation of POSS-polymers in lipid environment is aimed for. Copyright © 2017 Elsevier B.V. All rights reserved.

Multi-scale modelling of supercapacitors: From molecular simulations to a transmission line model

NASA Astrophysics Data System (ADS)

Pean, C.; Rotenberg, B.; Simon, P.; Salanne, M.

2016-09-01

We perform molecular dynamics simulations of a typical nanoporous-carbon based supercapacitor. The organic electrolyte consists in 1-ethyl-3-methylimidazolium and hexafluorophosphate ions dissolved in acetonitrile. We simulate systems at equilibrium, for various applied voltages. This allows us to determine the relevant thermodynamic (capacitance) and transport (in-pore resistivities) properties. These quantities are then injected in a transmission line model for testing its ability to predict the charging properties of the device. The results from this macroscopic model are in good agreement with non-equilibrium molecular dynamics simulations, which validates its use for interpreting electrochemical impedance experiments.

Fundamental Properties of Non-equilibrium Laser-Supported Detonation Wave

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shiraishi, Hiroyuki

For developing laser propulsion, it is very important to analyze the mechanism of Laser-Supported Detonation (LSD), because it can generate high pressure and high temperature to be used by laser propulsion can be categorized as one type of hypersonic reacting flows, where exothermicity is supplied not by chemical reaction but by radiation absorption. I have numerically simulated the 1-D and Quasi-1-D LSD waves propagating through an inert gas, which absorbs CO2 gasdynamic laser, using a 2-temperature model. Calculated results show the fundamental properties of the non-equilibrium LSD Waves.

Solution properties of almandine-pyrope garnet as determined by phase equilibrium experiments

USGS Publications Warehouse

Koziol, A.M.; Bohlen, S.R.

1992-01-01

The thermodynamic mixing properties of almandine-pyrope garnet were derived from phase equilibrium experiments at temperatures of 900 and 1000??C and pressures from 8 to 14 kbar. Almandine has essentially ideal behavior in almandine-pyrope garnet over the composition range Alm89-Alm61 at the above experimental conditions. In all experimental products a systematic partitioning of Fe and Mg between garnet and ilmenite was seen with ln Kd ??? 1.59 which was not temperature sensitive. The results support the use of garnet mixing models that incorporate ideal or nearly ideal Fe-Mg parameters. -from Authors

Coupling microscopic and mesoscopic scales to simulate chemical equilibrium between a nanometric carbon cluster and detonation products fluid.

PubMed

Bourasseau, Emeric; Maillet, Jean-Bernard

2011-04-21

This paper presents a new method to obtain chemical equilibrium properties of detonation products mixtures including a solid carbon phase. In this work, the solid phase is modelled through a mesoparticle immersed in the fluid, such that the heterogeneous character of the mixture is explicitly taken into account. Inner properties of the clusters are taken from an equation of state obtained in a previous work, and interaction potential between the nanocluster and the fluid particles is derived from all-atoms simulations using the LCBOPII potential (Long range Carbon Bond Order Potential II). It appears that differences in chemical equilibrium results obtained with this method and the "composite ensemble method" (A. Hervouet et al., J. Phys. Chem. B, 2008, 112.), where fluid and solid phases are considered as non-interacting, are not significant, underlining the fact that considering the inhomogeneity of such system is crucial.

Lagrangian formulation of irreversible thermodynamics and the second law of thermodynamics.

PubMed

Glavatskiy, K S

2015-05-28

We show that the equations which describe irreversible evolution of a system can be derived from a variational principle. We suggest a Lagrangian, which depends on the properties of the normal and the so-called "mirror-image" system. The Lagrangian is symmetric in time and therefore compatible with microscopic reversibility. The evolution equations in the normal and mirror-imaged systems are decoupled and describe therefore independent irreversible evolution of each of the systems. The second law of thermodynamics follows from a symmetry of the Lagrangian. Entropy increase in the normal system is balanced by the entropy decrease in the mirror-image system, such that there exists an "integral of evolution" which is a constant. The derivation relies on the property of local equilibrium, which states that the local relations between the thermodynamic quantities in non-equilibrium are the same as in equilibrium.

Lagrangian formulation of irreversible thermodynamics and the second law of thermodynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glavatskiy, K. S.

We show that the equations which describe irreversible evolution of a system can be derived from a variational principle. We suggest a Lagrangian, which depends on the properties of the normal and the so-called “mirror-image” system. The Lagrangian is symmetric in time and therefore compatible with microscopic reversibility. The evolution equations in the normal and mirror-imaged systems are decoupled and describe therefore independent irreversible evolution of each of the systems. The second law of thermodynamics follows from a symmetry of the Lagrangian. Entropy increase in the normal system is balanced by the entropy decrease in the mirror-image system, such thatmore » there exists an “integral of evolution” which is a constant. The derivation relies on the property of local equilibrium, which states that the local relations between the thermodynamic quantities in non-equilibrium are the same as in equilibrium.« less

A Counterintuitive Toy: The Bird That Never Falls Down.

ERIC Educational Resources Information Center

Fort, J.; Llebot, J. E.; Saurina, J.; Sunol, J. J.

1998-01-01

Describes a toy shaped like a bird that has an intuitively astonishing property: no matter how far away from equilibrium it is moved, it oscillates back to equilibrium. The behavior of this physical system is explained and is used to illustrate the concept of mechanical stability and the usefulness of making simple, idealized models for describing…

Multigrid method for the equilibrium equations of elasticity using a compact scheme

NASA Technical Reports Server (NTRS)

Taasan, S.

1986-01-01

A compact difference scheme is derived for treating the equilibrium equations of elasticity. The scheme is inconsistent and unstable. A multigrid method which takes into account these properties is described. The solution of the discrete equations, up to the level of discretization errors, is obtained by this method in just two multigrid cycles.

Generalized non-equilibrium vertex correction method in coherent medium theory for quantum transport simulation of disordered nanoelectronics

NASA Astrophysics Data System (ADS)

Yan, Jiawei; Ke, Youqi

In realistic nanoelectronics, disordered impurities/defects are inevitable and play important roles in electron transport. However, due to the lack of effective quantum transport method, the important effects of disorders remain poorly understood. Here, we report a generalized non-equilibrium vertex correction (NVC) method with coherent potential approximation to treat the disorder effects in quantum transport simulation. With this generalized NVC method, any averaged product of two single-particle Green's functions can be obtained by solving a set of simple linear equations. As a result, the averaged non-equilibrium density matrix and various important transport properties, including averaged current, disordered induced current fluctuation and the averaged shot noise, can all be efficiently computed in a unified scheme. Moreover, a generalized form of conditionally averaged non-equilibrium Green's function is derived to incorporate with density functional theory to enable first-principles simulation. We prove the non-equilibrium coherent potential equals the non-equilibrium vertex correction. Our approach provides a unified, efficient and self-consistent method for simulating non-equilibrium quantum transport through disorder nanoelectronics. Shanghaitech start-up fund.

Under What Conditions Can Equilibrium Gas-Particle Partitioning Be Expected to Hold in the Atmosphere?

PubMed

Mai, Huajun; Shiraiwa, Manabu; Flagan, Richard C; Seinfeld, John H

2015-10-06

The prevailing treatment of secondary organic aerosol formation in atmospheric models is based on the assumption of instantaneous gas-particle equilibrium for the condensing species, yet compelling experimental evidence indicates that organic aerosols can exhibit the properties of highly viscous, semisolid particles, for which gas-particle equilibrium may be achieved slowly. The approach to gas-particle equilibrium partitioning is controlled by gas-phase diffusion, interfacial transport, and particle-phase diffusion. Here we evaluate the controlling processes and the time scale to achieve gas-particle equilibrium as a function of the volatility of the condensing species, its surface accommodation coefficient, and its particle-phase diffusivity. For particles in the size range of typical atmospheric organic aerosols (∼50-500 nm), the time scale to establish gas-particle equilibrium is generally governed either by interfacial accommodation or particle-phase diffusion. The rate of approach to equilibrium varies, depending on whether the bulk vapor concentration is constant, typical of an open system, or decreasing as a result of condensation into the particles, typical of a closed system.

Thermal Non-Equilibrium Flows in Three Space Dimensions

NASA Astrophysics Data System (ADS)

Zeng, Yanni

2016-01-01

We study the equations describing the motion of a thermal non-equilibrium gas in three space dimensions. It is a hyperbolic system of six equations with a relaxation term. The dissipation mechanism induced by the relaxation is weak in the sense that the Shizuta-Kawashima criterion is violated. This implies that a perturbation of a constant equilibrium state consists of two parts: one decays in time while the other stays. In fact, the entropy wave grows weakly along the particle path as the process is irreversible. We study thermal properties related to the well-posedness of the nonlinear system. We also obtain a detailed pointwise estimate on the Green's function for the Cauchy problem when the system is linearized around an equilibrium constant state. The Green's function provides a complete picture of the wave pattern, with an exact and explicit leading term. Comparing with existing results for one dimensional flows, our results reveal a new feature of three dimensional flows: not only does the entropy wave not decay, but the velocity also contains a non-decaying part, strongly coupled with its decaying one. The new feature is supported by the second order approximation via the Chapman-Enskog expansions, which are the Navier-Stokes equations with vanished shear viscosity and heat conductivity.

Statistical investigation of simulated intestinal fluid composition on the equilibrium solubility of biopharmaceutics classification system class II drugs.

PubMed

Khadra, Ibrahim; Zhou, Zhou; Dunn, Claire; Wilson, Clive G; Halbert, Gavin

2015-01-25

A drug's solubility and dissolution behaviour within the gastrointestinal tract is a key property for successful administration by the oral route and one of the key factors in the biopharmaceutics classification system. This property can be determined by investigating drug solubility in human intestinal fluid (HIF) but this is difficult to obtain and highly variable, which has led to the development of multiple simulated intestinal fluid (SIF) recipes. Using a statistical design of experiment (DoE) technique this paper has investigated the effects and interactions on equilibrium drug solubility of seven typical SIF components (sodium taurocholate, lecithin, sodium phosphate, sodium chloride, pH, pancreatin and sodium oleate) within concentration ranges relevant to human intestinal fluid values. A range of poorly soluble drugs with acidic (naproxen, indomethacin, phenytoin, and piroxicam), basic (aprepitant, carvedilol, zafirlukast, tadalafil) or neutral (fenofibrate, griseofulvin, felodipine and probucol) properties have been investigated. The equilibrium solubility results determined are comparable with literature studies of the drugs in either HIF or SIF indicating that the DoE is operating in the correct space. With the exception of pancreatin, all of the factors individually had a statistically significant influence on equilibrium solubility with variations in magnitude of effect between the acidic and basic or neutral compounds and drug specific interactions were evident. Interestingly for the neutral compounds pH was the factor with the second largest solubility effect. Around one third of all the possible factor combinations showed a significant influence on equilibrium solubility with variations in interaction significance and magnitude of effect between the acidic and basic or neutral compounds. The least number of significant media component interactions were noted for the acidic compounds with three and the greatest for the neutral compounds at seven, with again drug specific effects evident. This indicates that a drug's equilibrium solubility in SIF is influenced depending upon drug type by between eight to fourteen individual or combinations of media components with some of these drug specific. This illustrates the complex nature of these fluids and provides for individual drugs a visualisation of the possible solubility envelope within the gastrointestinal tract, which may be of importance for modelling in vivo behaviour. In addition the results indicate that the design of experiment approach can be employed to provide greater detail of drug solubility behaviour, possible drug specific interactions and influence of variations in gastrointestinal media components due to disease. The approach is also feasible and amenable to adaptation for high throughput screening of drug candidates. Copyright © 2014 Elsevier B.V. All rights reserved.

Finding equilibrium in the spatiotemporal chaos of the complex Ginzburg-Landau equation

NASA Astrophysics Data System (ADS)

Ballard, Christopher C.; Esty, C. Clark; Egolf, David A.

2016-11-01

Equilibrium statistical mechanics allows the prediction of collective behaviors of large numbers of interacting objects from just a few system-wide properties; however, a similar theory does not exist for far-from-equilibrium systems exhibiting complex spatial and temporal behavior. We propose a method for predicting behaviors in a broad class of such systems and apply these ideas to an archetypal example, the spatiotemporal chaotic 1D complex Ginzburg-Landau equation in the defect chaos regime. Building on the ideas of Ruelle and of Cross and Hohenberg that a spatiotemporal chaotic system can be considered a collection of weakly interacting dynamical units of a characteristic size, the chaotic length scale, we identify underlying, mesoscale, chaotic units and effective interaction potentials between them. We find that the resulting equilibrium Takahashi model accurately predicts distributions of particle numbers. These results suggest the intriguing possibility that a class of far-from-equilibrium systems may be well described at coarse-grained scales by the well-established theory of equilibrium statistical mechanics.

Finding equilibrium in the spatiotemporal chaos of the complex Ginzburg-Landau equation.

PubMed

Ballard, Christopher C; Esty, C Clark; Egolf, David A

2016-11-01

Equilibrium statistical mechanics allows the prediction of collective behaviors of large numbers of interacting objects from just a few system-wide properties; however, a similar theory does not exist for far-from-equilibrium systems exhibiting complex spatial and temporal behavior. We propose a method for predicting behaviors in a broad class of such systems and apply these ideas to an archetypal example, the spatiotemporal chaotic 1D complex Ginzburg-Landau equation in the defect chaos regime. Building on the ideas of Ruelle and of Cross and Hohenberg that a spatiotemporal chaotic system can be considered a collection of weakly interacting dynamical units of a characteristic size, the chaotic length scale, we identify underlying, mesoscale, chaotic units and effective interaction potentials between them. We find that the resulting equilibrium Takahashi model accurately predicts distributions of particle numbers. These results suggest the intriguing possibility that a class of far-from-equilibrium systems may be well described at coarse-grained scales by the well-established theory of equilibrium statistical mechanics.

Direct measurement of the Einstein relation in a macroscopic, non-equilibrium system of chaotic surface waves

NASA Astrophysics Data System (ADS)

Welch, Kyle; Liebman-Pelaez, Alexander; Corwin, Eric

Equilibrium statistical mechanics is traditionally limited to thermal systems. Can it be applied to athermal, non-equilibrium systems that nonetheless satisfy the basic criteria of steady-state chaos and isotropy? We answer this question using a macroscopic system of chaotic surface waves which is, by all measures, non-equilibrium. The waves are generated in a dish of water that is vertically oscillated above a critical amplitude. We have constructed a rheometer that actively measures the drag imparted by the waves on a buoyant particle, a quantity entirely divorced in origin from the drag imparted by the fluid in which the particle floats. We also perform a separate, passive measurement, extracting a diffusion constant and effective temperature. Having directly measured all three properties (temperature, diffusion constant, and drag coefficient) we go on to show that our macroscopic, non-equilibrium case is wholly consistent with the Einstein relation, a classic result for equilibrium thermal systems.

A model of economic growth with physical and human capital: The role of time delays.

PubMed

Gori, Luca; Guerrini, Luca; Sodini, Mauro

2016-09-01

This article aims at analysing a two-sector economic growth model with discrete delays. The focus is on the dynamic properties of the emerging system. In particular, this study concentrates on the stability properties of the stationary solution, characterised by analytical results and geometrical techniques (stability crossing curves), and the conditions under which oscillatory dynamics emerge (through Hopf bifurcations). In addition, this article proposes some numerical simulations to illustrate the behaviour of the system when the stationary equilibrium is unstable.

Shuttle Tethered Aerothermodynamics Research Facility (STARFAC) Instrumentation Requirements

NASA Technical Reports Server (NTRS)

Wood, George M.; Siemers, Paul M.; Carlomagno, Giovanni M.; Hoffman, John

1986-01-01

The instrumentation requirements for the Shuttle Tethered Aerothermodynamic Research Facility (STARFAC) are presented. The typical physical properties of the terrestrial atmosphere are given along with representative atmospheric daytime ion concentrations and the equilibrium and nonequilibrium gas property comparison from a point away from a wall. STARFAC science and engineering measurements are given as are the TSS free stream gas analysis. The potential nonintrusive measurement techniques for hypersonic boundary layer research are outlined along with the quantitative physical measurement methods for aerothermodynamic studies.

Using Computer-Based "Experiments" in the Analysis of Chemical Reaction Equilibria

ERIC Educational Resources Information Center

Li, Zhao; Corti, David S.

2018-01-01

The application of the Reaction Monte Carlo (RxMC) algorithm to standard textbook problems in chemical reaction equilibria is discussed. The RxMC method is a molecular simulation algorithm for studying the equilibrium properties of reactive systems, and therefore provides the opportunity to develop computer-based "experiments" for the…

Impact of mutations on the allosteric conformational equilibrium

PubMed Central

Weinkam, Patrick; Chen, Yao Chi; Pons, Jaume; Sali, Andrej

2012-01-01

Allostery in a protein involves effector binding at an allosteric site that changes the structure and/or dynamics at a distant, functional site. In addition to the chemical equilibrium of ligand binding, allostery involves a conformational equilibrium between one protein substate that binds the effector and a second substate that less strongly binds the effector. We run molecular dynamics simulations using simple, smooth energy landscapes to sample specific ligand-induced conformational transitions, as defined by the effector-bound and unbound protein structures. These simulations can be performed using our web server: http://salilab.org/allosmod/. We then develop a set of features to analyze the simulations and capture the relevant thermodynamic properties of the allosteric conformational equilibrium. These features are based on molecular mechanics energy functions, stereochemical effects, and structural/dynamic coupling between sites. Using a machine-learning algorithm on a dataset of 10 proteins and 179 mutations, we predict both the magnitude and sign of the allosteric conformational equilibrium shift by the mutation; the impact of a large identifiable fraction of the mutations can be predicted with an average unsigned error of 1 kBT. With similar accuracy, we predict the mutation effects for an 11th protein that was omitted from the initial training and testing of the machine-learning algorithm. We also assess which calculated thermodynamic properties contribute most to the accuracy of the prediction. PMID:23228330

Direct Prediction of Cricondentherm and Cricondenbar Coordinates of Natural Gas Mixtures using Cubic Equation of State

NASA Astrophysics Data System (ADS)

Taraf, R.; Behbahani, R.; Moshfeghian, Mahmood

2008-12-01

A numerical algorithm is presented for direct calculation of the cricondenbar and cricondentherm coordinates of natural gas mixtures of known composition based on the Michelsen method. In the course of determination of these coordinates, the equilibrium mole fractions at these points are also calculated. In this algorithm, the property of the distance from the free energy surfaces to a tangent plane in equilibrium condition is added to saturation calculation as an additional criterion. An equation of state (EoS) was needed to calculate all required properties. Therefore, the algorithm was tested with Soave-Redlich-Kwong (SRK), Peng-Robinson (PR), and modified Nasrifar-Moshfeghian (MNM) equations of state. For different EoSs, the impact of the binary interaction coefficient ( k ij) was studied. The impact of initial guesses for temperature and pressure was also studied. The convergence speed and the accuracy of the results of this new algorithm were compared with experimental data and the results obtained from other methods and simulation softwares such as Hysys, Aspen Plus, and EzThermo.

Properties of model atomic free-standing thin films.

PubMed

Shi, Zane; Debenedetti, Pablo G; Stillinger, Frank H

2011-03-21

We present a computational study of the thermodynamic, dynamic, and structural properties of free-standing thin films, investigated via molecular dynamics simulation of a glass-forming binary Lennard-Jones mixture. An energy landscape analysis is also performed to study glassy states. At equilibrium, species segregation occurs, with the smaller minority component preferentially excluded from the surface. The film's interior density and interface width depend solely on temperature and not the initialization density. The atoms at the surface of the film have a higher lateral diffusivity when compared to the interior. The average difference between the equilibrium and inherent structure energies assigned to individual particles, as a function of the distance from the center of the film, increases near the surface. A minimum of this difference occurs in the region just under the liquid-vapor interface. This suggests that the surface atoms are able to sample the underlying energy landscape more effectively than those in the interior, and we suggest a possible relationship of this observation to the recently reported formation of stable glasses by vapor phase deposition.

Theoretical isotopic fractionation between structural boron in carbonates and aqueous boric acid and borate ion

NASA Astrophysics Data System (ADS)

Balan, Etienne; Noireaux, Johanna; Mavromatis, Vasileios; Saldi, Giuseppe D.; Montouillout, Valérie; Blanchard, Marc; Pietrucci, Fabio; Gervais, Christel; Rustad, James R.; Schott, Jacques; Gaillardet, Jérôme

2018-02-01

The 11B/10B ratio in calcite and aragonite is an important proxy of oceanic water pH. However, the physico-chemical mechanisms underpinning this approach are still poorly known. In the present study, we theoretically determine the equilibrium isotopic fractionation properties of structural boron species in calcium carbonates, BO33-, BO2(OH)2- and B(OH)4- anions substituted for carbonate groups, as well as those of B(OH)4- and B(OH)3 species in vacuum. Significant variability of equilibrium isotopic fractionation properties is observed among these structural species which is related to their contrasted coordination state, Bsbnd O bond lengths and atomic-scale environment. The isotopic composition of structural boron does not only depend on its coordination number but also on its medium range environment, i.e. farther than its first coordination shell. The isotopic fractionation between aqueous species and their counterparts in vacuum are assessed using previous investigations based on similar quantum-mechanical modeling approaches. At 300 K, the equilibrium isotope composition of structural trigonal species is 7-15‰ lighter than that of aqueous boric acid molecules, whereas substituted tetrahedral borate ions are heavier than their aqueous counterparts by 10-13‰. Although significant uncertainties are known to affect the theoretical prediction of fractionation factors between solids and solutions, the usually assumed lack of isotopic fractionation during borate incorporation in carbonates is challenged by these theoretical results. The present theoretical equilibrium fractionation factors between structural boron and aqueous species differ from those inferred from experiments which may indicate that isotopic equilibrium, unlike chemical equilibrium, was not reached in most experiments. Further research into the isotopic fractionation processes at the interface between calcium carbonates and aqueous solution as well as long duration experiments aimed at investigating the kinetics of equilibration of boron environment and isotopic composition are therefore required to refine our understanding of boron coprecipitation in carbonates and thus the theory behind the use of boron isotopes as an ocean pH proxy.

Effect of Sediment Availability in Bedload-Dominated Rivers on Fluvial Geomorphic Equilibrium

NASA Astrophysics Data System (ADS)

Marti, M.

2016-12-01

Channels are known to compensate for changes in sediment supply via covariate changes in channel properties, yet the timescale for adjustment remains poorly constrained. We propose that reductions in sediment flux inhibit equilibrium re-establishment and thus impact the timescale of system adjustment. Using run-of-river dams as natural experiments, this study quantifies the geomorphic response of channels to sediment supply reduction. Channel traits that facilitate increased sediment trapping behind the dam, such as large reservoir storage capacity relative to annual inflow and low slope, were expected to inhibit a channel's ability to re-establish equilibrium following impoundment, lengthening the equilibrium establishment timescale to tens or hundreds of years. Reaches associated with increased trapping were therefore anticipated to exhibit non-equilibrium forms. Channel equilibrium was evaluated downstream of 8 ROR dams in New England with varying degrees of sediment trapping. Sites cover a range of watershed sizes (3-155 km2), channel slopes (.05-5%), 2-year discharges (1.5-60 m3/s) and storage capacity volumes. Because equilibrium channel form is just sufficient to mobilize grains under bankfull conditions in bedload-dominated rivers, the Shields parameter was used to assess equilibrium form. Unregulated, upstream Shields values and regulated, downstream values were calculated at 14 total cross-sections extending 300-450 m upstream and downstream of each dam. Sediment trapping was estimated using Brune's curve (1953). On the Charles Brown Brook (VT), a marginally significant (p=0.08) increase in Shields values from a mean of 0.14 upstream to 0.41 downstream of a 100+ year old dam was observed. In contrast, reaches downstream of the 100+ year old Pelham dam (MA) exhibit significantly lower Shields values. This suggests that trapping behind the dam inhibits the downstream channel from reaching an equilibrium state, but not always in the same way. Better understanding of geomorphic response to reduced sediment flux as a control on equilibrium establishment will broaden the knowledge of geomorphic equilibrium and aid in management of regulated, bedload-dominated rivers.

Wall ablation of heated compound-materials into non-equilibrium discharge plasmas

NASA Astrophysics Data System (ADS)

Wang, Weizong; Kong, Linghan; Geng, Jinyue; Wei, Fuzhi; Xia, Guangqing

2017-02-01

The discharge properties of the plasma bulk flow near the surface of heated compound-materials strongly affects the kinetic layer parameters modeled and manifested in the Knudsen layer. This paper extends the widely used two-layer kinetic ablation model to the ablation controlled non-equilibrium discharge due to the fact that the local thermodynamic equilibrium (LTE) approximation is often violated as a result of the interaction between the plasma and solid walls. Modifications to the governing set of equations, to account for this effect, are derived and presented by assuming that the temperature of the electrons deviates from that of the heavy particles. The ablation characteristics of one typical material, polytetrafluoroethylene (PTFE) are calculated with this improved model. The internal degrees of freedom as well as the average particle mass and specific heat ratio of the polyatomic vapor, which strongly depends on the temperature, pressure and plasma non-equilibrium degree and plays a crucial role in the accurate determination of the ablation behavior by this model, are also taken into account. Our assessment showed the significance of including such modifications related to the non-equilibrium effect in the study of vaporization of heated compound materials in ablation controlled arcs. Additionally, a two-temperature magneto-hydrodynamic (MHD) model accounting for the thermal non-equilibrium occurring near the wall surface is developed and applied into an ablation-dominated discharge for an electro-thermal chemical launch device. Special attention is paid to the interaction between the non-equilibrium plasma and the solid propellant surface. Both the mass exchange process caused by the wall ablation and plasma species deposition as well as the associated momentum and energy exchange processes are taken into account. A detailed comparison of the results of the non-equilibrium model with those of an equilibrium model is presented. The non-equilibrium results show a non-equilibrium region near the plasma-wall interaction region and this indicates the need for the consideration of the influence of the possible departure from LTE in the plasma bulk on the determination of ablation rate.

Structural, electronic and thermal properties of super hard ternary boride, WAlB

NASA Astrophysics Data System (ADS)

Rajpoot, Priyanka; Rastogi, Anugya; Verma, U. P.

2018-04-01

A first principle study of the structural, electronic and thermal properties of Tungsten Aluminum Boride (WAlB) using full-potential linearized augmented plane wave (FP-LAPW) in the frame work of density function theory (DFT) have been calculated. The calculated equilibrium structural parameters are in excellent agreement with available experimental results. The calculated electronic band structure reveals that WAlB is metallic in nature. The quasi-harmonic Debye model is applied to study of the temperature and pressure effect on volume, Debye temperature, thermal expansion coefficient and specific heat at constant volume and constant pressure. To the best of our knowledge theoretical investigation of these properties of WAlB is reported for the first time.

Planetary geology: Impact processes on asteroids

NASA Technical Reports Server (NTRS)

Chapman, C. R.; Davis, D. R.; Greenberg, R.; Weidenschilling, S. J.

1982-01-01

The fundamental geological and geophysical properties of asteroids were studied by theoretical and simulation studies of their collisional evolution. Numerical simulations incorporating realistic physical models were developed to study the collisional evolution of hypothetical asteroid populations over the age of the solar system. Ideas and models are constrained by the observed distributions of sizes, shapes, and spin rates in the asteroid belt, by properties of Hirayama families, and by experimental studies of cratering and collisional phenomena. It is suggested that many asteroids are gravitationally-bound "rubble piles.' Those that rotate rapidly may have nonspherical quasi-equilibrium shapes, such as ellipsoids or binaries. Through comparison of models with astronomical data, physical properties of these asteroids (including bulk density) are determined, and physical processes that have operated in the solar system in primordial and subsequent epochs are studied.

A systematic and feasible method for computing nuclear contributions to electrical properties of polyatomic molecules

NASA Astrophysics Data System (ADS)

Luis, Josep M.; Duran, Miquel; Andrés, José L.

1997-08-01

An analytic method to evaluate nuclear contributions to electrical properties of polyatomic molecules is presented. Such contributions control changes induced by an electric field on equilibrium geometry (nuclear relaxation contribution) and vibrational motion (vibrational contribution) of a molecular system. Expressions to compute the nuclear contributions have been derived from a power series expansion of the potential energy. These contributions to the electrical properties are given in terms of energy derivatives with respect to normal coordinates, electric field intensity or both. Only one calculation of such derivatives at the field-free equilibrium geometry is required. To show the useful efficiency of the analytical evaluation of electrical properties (the so-called AEEP method), results for calculations on water and pyridine at the SCF/TZ2P and the MP2/TZ2P levels of theory are reported. The results obtained are compared with previous theoretical calculations and with experimental values.

Detecting temperature fluctuations at equilibrium.

PubMed

Dixit, Purushottam D

2015-05-21

The Gibbs and the Boltzmann definition of temperature agree only in the macroscopic limit. The ambiguity in identifying the equilibrium temperature of a finite-sized 'small' system exchanging energy with a bath is usually understood as a limitation of conventional statistical mechanics. We interpret this ambiguity as resulting from a stochastically fluctuating temperature coupled with the phase space variables giving rise to a broad temperature distribution. With this ansatz, we develop the equilibrium statistics and dynamics of small systems. Numerical evidence using an analytically tractable model shows that the effects of temperature fluctuations can be detected in the equilibrium and dynamical properties of the phase space of the small system. Our theory generalizes statistical mechanics to small systems relevant in biophysics and nanotechnology.

Stability and nonlinear adjustment of vortices in Keplerian flows

NASA Astrophysics Data System (ADS)

Bodo, G.; Tevzadze, A.; Chagelishvili, G.; Mignone, A.; Rossi, P.; Ferrari, A.

2007-11-01

Aims:We investigate the stability, nonlinear development and equilibrium structure of vortices in a background shearing Keplerian flow Methods: We make use of high-resolution global two-dimensional compressible hydrodynamic simulations. We introduce the concept of nonlinear adjustment to describe the transition of unbalanced vortical fields to a long-lived configuration. Results: We discuss the conditions under which vortical perturbations evolve into long-lived persistent structures and we describe the properties of these equilibrium vortices. The properties of equilibrium vortices appear to be independent from the initial conditions and depend only on the local disk parameters. In particular we find that the ratio of the vortex size to the local disk scale height increases with the decrease of the sound speed, reaching values well above the unity. The process of spiral density wave generation by the vortex, discussed in our previous work, appear to maintain its efficiency also at nonlinear amplitudes and we observe the formation of spiral shocks attached to the vortex. The shocks may have important consequences on the long term vortex evolution and possibly on the global disk dynamics. Conclusions: Our study strengthens the arguments in favor of anticyclonic vortices as the candidates for the promotion of planetary formation. Hydrodynamic shocks that are an intrinsic property of persistent vortices in compressible Keplerian flows are an important contributor to the overall balance. These shocks support vortices against viscous dissipation by generating local potential vorticity and should be responsible for the eventual fate of the persistent anticyclonic vortices. Numerical codes have be able to resolve shock waves to describe the vortex dynamics correctly.

High-temperature partition functions, specific heats and spectral radiative properties of diatomic molecules with an improved calculation of energy levels

NASA Astrophysics Data System (ADS)

Qin, Z.; Zhao, J. M.; Liu, L. H.

2018-05-01

The level energies of diatomic molecules calculated by the frequently used Dunham expansion will become less accurate for high-lying vibrational and rotational levels. In this paper, the potential curves for the lower-lying electronic states with accurate spectroscopic constants are reconstructed using the Rydberg-Klein-Rees (RKR) method, which are extrapolated to the dissociation limits by fitting of the theoretical potentials, and the rest of the potential curves are obtained from the ab-initio results in the literature. Solving the rotational dependence of the radial Schrödinger equation over the obtained potential curves, we determine the rovibrational level energies, which are then used to calculate the equilibrium and non-equilibrium thermodynamic properties of N2, N2+, NO, O2, CN, C2, CO and CO+. The partition functions and the specific heats are systematically validated by available data in the literature. Finally, we calculate the radiative source strengths of diatomic molecules in thermodynamic equilibrium, which agree well with the available values in the literature. The spectral radiative intensities for some diatomic molecules in thermodynamic non-equilibrium are calculated and validated by available experimental data.

Experimental verification of the thermodynamic properties for a jet-A fuel

NASA Technical Reports Server (NTRS)

Graciasalcedo, Carmen M.; Brabbs, Theodore A.; Mcbride, Bonnie J.

1988-01-01

Thermodynamic properties for a Jet-A fuel were determined by Shell Development Company in 1970 under a contract for NASA Lewis Research Center. The polynomial fit necessary to include Jet-A fuel (liquid and gaseous phases) in the library of thermodynamic properties of the NASA Lewis Chemical Equilibrium Program is calculated. To verify the thermodynamic data, the temperatures of mixtures of liquid Jet-A injected into a hot nitrogen stream were experimentally measured and compared to those calculated by the program. Iso-octane, a fuel for which the thermodynamic properties are well known, was used as a standard to calibrate the apparatus. The measured temperatures for the iso-octane/nitrogen mixtures reproduced the calculated temperatures except for a small loss due to the non-adiabatic behavior of the apparatus. The measurements for Jet-A were corrected for this heat loss and showed excellent agreement with the calculated temperatures. These experiments show that this process can be adequately described by the thermodynamic properties fitted for the Chemical Equilibrium Program.

Table and charts of equilibrium normal-shock and shock-tube properties for pure carbon dioxide with velocities from 1 to 16 km/sec

NASA Technical Reports Server (NTRS)

Miller, C. G., III; Wilder, S. E.

1976-01-01

Equilibrium thermodynamic and flow properties are presented in tabulated and graphical form for moving, standing, and reflected normal shock waves in pure CO2. Properties include pressure, temperature, density, enthalpy, speed of sound, entropy, molecular weight ratio, isentropic exponent, velocity, and species mole fractions. Incident (moving) shock velocities are varied from 1 to 16 km/sec for a range of initial pressure of 5 N/sq m to 500 kN/sq m. The present results are applicable to shock tube flows and to freeflight conditions for a blunt body at high velocities. Working charts illustrating idealized shock tube performance with CO2 test gas and heated helium and hydrogen driver gases are also presented.

Influence of atomic kinetics in the simulation of plasma microscopic properties and thermal instabilities for radiative bow shock experiments.

PubMed

Espinosa, G; Rodríguez, R; Gil, J M; Suzuki-Vidal, F; Lebedev, S V; Ciardi, A; Rubiano, J G; Martel, P

2017-03-01

Numerical simulations of laboratory astrophysics experiments on plasma flows require plasma microscopic properties that are obtained by means of an atomic kinetic model. This fact implies a careful choice of the most suitable model for the experiment under analysis. Otherwise, the calculations could lead to inaccurate results and inappropriate conclusions. First, a study of the validity of the local thermodynamic equilibrium in the calculation of the average ionization, mean radiative properties, and cooling times of argon plasmas in a range of plasma conditions of interest in laboratory astrophysics experiments on radiative shocks is performed in this work. In the second part, we have made an analysis of the influence of the atomic kinetic model used to calculate plasma microscopic properties of experiments carried out on magpie on radiative bow shocks propagating in argon. The models considered were developed assuming both local and nonlocal thermodynamic equilibrium and, for the latter situation, we have considered in the kinetic model different effects such as external radiation field and plasma mixture. The microscopic properties studied were the average ionization, the charge state distributions, the monochromatic opacities and emissivities, the Planck mean opacity, and the radiative power loss. The microscopic study was made as a postprocess of a radiative-hydrodynamic simulation of the experiment. We have also performed a theoretical analysis of the influence of these atomic kinetic models in the criteria for the onset possibility of thermal instabilities due to radiative cooling in those experiments in which small structures were experimentally observed in the bow shock that could be due to this kind of instability.

Influence of atomic kinetics in the simulation of plasma microscopic properties and thermal instabilities for radiative bow shock experiments

NASA Astrophysics Data System (ADS)

Espinosa, G.; Rodríguez, R.; Gil, J. M.; Suzuki-Vidal, F.; Lebedev, S. V.; Ciardi, A.; Rubiano, J. G.; Martel, P.

2017-03-01

Numerical simulations of laboratory astrophysics experiments on plasma flows require plasma microscopic properties that are obtained by means of an atomic kinetic model. This fact implies a careful choice of the most suitable model for the experiment under analysis. Otherwise, the calculations could lead to inaccurate results and inappropriate conclusions. First, a study of the validity of the local thermodynamic equilibrium in the calculation of the average ionization, mean radiative properties, and cooling times of argon plasmas in a range of plasma conditions of interest in laboratory astrophysics experiments on radiative shocks is performed in this work. In the second part, we have made an analysis of the influence of the atomic kinetic model used to calculate plasma microscopic properties of experiments carried out on magpie on radiative bow shocks propagating in argon. The models considered were developed assuming both local and nonlocal thermodynamic equilibrium and, for the latter situation, we have considered in the kinetic model different effects such as external radiation field and plasma mixture. The microscopic properties studied were the average ionization, the charge state distributions, the monochromatic opacities and emissivities, the Planck mean opacity, and the radiative power loss. The microscopic study was made as a postprocess of a radiative-hydrodynamic simulation of the experiment. We have also performed a theoretical analysis of the influence of these atomic kinetic models in the criteria for the onset possibility of thermal instabilities due to radiative cooling in those experiments in which small structures were experimentally observed in the bow shock that could be due to this kind of instability.

Physical principles of intracellular organization via active and passive phase transitions

NASA Astrophysics Data System (ADS)

Berry, Joel; Brangwynne, Clifford P.; Haataja, Mikko

2018-04-01

Exciting recent developments suggest that phase transitions represent an important and ubiquitous mechanism underlying intracellular organization. We describe key experimental findings in this area of study, as well as the application of classical theoretical approaches for quantitatively understanding these data. We also discuss the way in which equilibrium thermodynamic driving forces may interface with the fundamentally out-of-equilibrium nature of living cells. In particular, time and/or space-dependent concentration profiles may modulate the phase behavior of biomolecules in living cells. We suggest future directions for both theoretical and experimental work that will shed light on the way in which biological activity modulates the assembly, properties, and function of viscoelastic states of living matter.

Physical principles of intracellular organization via active and passive phase transitions.

PubMed

Berry, Joel; Brangwynne, Clifford P; Haataja, Mikko

2018-04-01

Exciting recent developments suggest that phase transitions represent an important and ubiquitous mechanism underlying intracellular organization. We describe key experimental findings in this area of study, as well as the application of classical theoretical approaches for quantitatively understanding these data. We also discuss the way in which equilibrium thermodynamic driving forces may interface with the fundamentally out-of-equilibrium nature of living cells. In particular, time and/or space-dependent concentration profiles may modulate the phase behavior of biomolecules in living cells. We suggest future directions for both theoretical and experimental work that will shed light on the way in which biological activity modulates the assembly, properties, and function of viscoelastic states of living matter.

Dynamics of Equilibrium Points in a Uniformly Rotating Second-Order and Degree Gravitational Field

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Jinglang; Hou, Xiyun, E-mail: jinglang@nju.edu.cn, E-mail: silence@nju.edu.cn

2017-07-01

Using tools such as periodic orbits and invariant manifolds, the global dynamics around equilibrium points (EPs) in a rotating second-order and degree gravitational field are studied. For EPs on the long axis, planar and vertical periodic families are computed, and their stability properties are investigated. Invariant manifolds are also computed, and their relation to the first-order resonances is briefly discussed. For EPs on the short axis, planar and vertical periodic families are studied, with special emphasis on the genealogy of the planar periodic families. Our studies show that the global dynamics around EPs are highly similar to those around libration points in the circularmore » restricted three-body problem, such as spatial halo orbits, invariant manifolds, and the genealogy of planar periodic families.« less

Dynamical properties of a family of collisionless models of elliptical galaxies

NASA Astrophysics Data System (ADS)

Bertin, G.; Trenti, M.

2004-04-01

N-body simulations of collisionless collapse have offered important clues to the construction of realistic stellar dynamical models of elliptical galaxies. Such simulations confirm and quantify the qualitative expectation that rapid collapse of a self-gravitating collisionless system, initially cool and significantly far from equilibrium, leads to incomplete relaxation, that is to a quasi-equilibrium configuration characterized by isotropic, quasi-Maxwellian distribution of stellar orbits in the inner regions and by radially biased anisotropic pressure in the outer parts. In earlier studies, as illustrated in a number of papers several years ago, the attention was largely focused on the successful comparison between the models (constructed under the qualitative clues offered by the N-body simulations mentioned above) and the observations. In this paper we revisit the problem of incomplete violent relaxation, by making a direct comparison between the detailed properties of a family of distribution functions and those of the products of collisionless collapse found in N-body simulations.

Study of clathrate hydrates via equilibrium molecular-dynamics simulation employing polarisable and non-polarisable, rigid and flexible water models

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burnham, Christian J., E-mail: christian.burnham@ucd.ie, E-mail: niall.english@ucd.ie; English, Niall J., E-mail: christian.burnham@ucd.ie, E-mail: niall.english@ucd.ie

Equilibrium molecular-dynamics (MD) simulations have been performed on metastable sI and sII polymorphs of empty hydrate lattices, in addition to liquid water and ice Ih. The non-polarisable TIP4P-2005, simple point charge model (SPC), and polarisable Thole-type models (TTM): TTM2, TTM3, and TTM4 water models were used in order to survey the differences between models and to see what differences can be expected when polarisability is incorporated. Rigid and flexible variants were used of each model to gauge the effects of flexibility. Power spectra are calculated and compared to density-of-states spectra inferred from inelastic neutron scattering (INS) measurements. Thermodynamic properties weremore » also calculated, as well as molecular-dipole distributions. It was concluded that TTM models offer optimal fidelity vis-à-vis INS spectra, together with thermodynamic properties, with the flexible TTM2 model offering optimal placement of vibrational modes.« less

Field determination and QSPR prediction of equilibrium-status soil/vegetation partition coefficient of PCDD/Fs.

PubMed

Li, Li; Wang, Qiang; Qiu, Xinghua; Dong, Yian; Jia, Shenglan; Hu, Jianxin

2014-07-15

Characterizing pseudo equilibrium-status soil/vegetation partition coefficient KSV, the quotient of respective concentrations in soil and vegetation of a certain substance at remote background areas, is essential in ecological risk assessment, however few previous attempts have been made for field determination and developing validated and reproducible structure-based estimates. In this study, KSV was calculated based on measurements of seventeen 2,3,7,8-substituted PCDD/F congeners in soil and moss (Dicranum angustum), and rouzi grass (Thylacospermum caespitosum) of two background sites, Ny-Ålesund of the Arctic and Zhangmu-Nyalam region of the Tibet Plateau, respectively. By both fugacity modeling and stepwise regression of field data, the air-water partition coefficient (KAW) and aqueous solubility (SW) were identified as the influential physicochemical properties. Furthermore, validated quantitative structure-property relationship (QSPR) model was developed to extrapolate the KSV prediction to all 210 PCDD/F congeners. Molecular polarizability, molecular size and molecular energy demonstrated leading effects on KSV. Copyright © 2014 Elsevier B.V. All rights reserved.

Influence of Molecular Shape on the Thermal Stability and Molecular Orientation of Vapor-Deposited Organic Semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walters, Diane M; Antony, Lucas; de Pablo, Juan

High thermal stability and anisotropic molecular orientation enhance the performance of vapor-deposited organic semiconductors, but controlling these properties is a challenge in amorphous materials. To understand the influence of molecular shape on these properties, vapor-deposited glasses of three disk-shaped molecules were prepared. For all three systems, enhanced thermal stability is observed for glasses prepared over a wide range of substrate temperatures and anisotropic molecular orientation is observed at lower substrate temperatures. For two of the disk-shaped molecules, atomistic simulations of thin films were also performed and anisotropic molecular orientation was observed at the equilibrium liquid surface. We find that themore » structure and thermal stability of these vapor-deposited glasses results from high surface mobility and partial equilibration toward the structure of the equilibrium liquid surface during the deposition process. For the three molecules studied, molecular shape is a dominant factor in determining the anisotropy of vapor-deposited glasses.« less

Electronic properties of solids excited with intermediate laser power densities

NASA Astrophysics Data System (ADS)

Sirotti, Fausto; Tempo Beamline Team

Intermediate laser power density up to about 100 GW/cm2 is below the surface damage threshold is currently used to induce modification in the physical properties on short time scales. The absorption of a short laser pulse induces non-equilibrium electronic distributions followed by lattice-mediated equilibrium taking place only in the picosecond range. The role of the hot electrons is particularly important in several domains as for example fast magnetization and demagnetization processes, laser induced phase transitions, charge density waves. Angular resolved photoelectron spectroscopy measuring directly energy and momentum of electrons is the most adapted tool to study the electronic excitations at short time scales during and after fast laser excitations. The main technical problem is the space charge created by the pumping laser pulse. I will present angular resolved multiphoton photoemission results obtained with 800 nm laser pulses showing how space charge electrons emitted during fast demagnetization processes can be measured. Unable enter Affiliation: CNRS-SOLEIL Synchrotron L'Orme des Merisiers , Saint Aubin 91192 Gif sur Yvette France.

Robustness analysis of uncertain dynamical neural networks with multiple time delays.

PubMed

Senan, Sibel

2015-10-01

This paper studies the problem of global robust asymptotic stability of the equilibrium point for the class of dynamical neural networks with multiple time delays with respect to the class of slope-bounded activation functions and in the presence of the uncertainties of system parameters of the considered neural network model. By using an appropriate Lyapunov functional and exploiting the properties of the homeomorphism mapping theorem, we derive a new sufficient condition for the existence, uniqueness and global robust asymptotic stability of the equilibrium point for the class of neural networks with multiple time delays. The obtained stability condition basically relies on testing some relationships imposed on the interconnection matrices of the neural system, which can be easily verified by using some certain properties of matrices. An instructive numerical example is also given to illustrate the applicability of our result and show the advantages of this new condition over the previously reported corresponding results. Copyright © 2015 Elsevier Ltd. All rights reserved.

Response surface methodology for cadmium biosorption on Pseudomonas aeruginosa.

PubMed

Ahmady-Asbchin, Salman

2016-01-01

In this research the effects of various physicochemical factors on Cd(2+) biosorption such as initial metal concentration, pH and contact exposure time were studied. This study has shown a Cd(2+) biosorption, equilibrium time of about 5 min for Pseudomonas aeruginosa and the adsorption equilibrium data were well described by Langmuir equation. The maximum capacity for biosorption has been extrapolated to 0.56 mmol.g(-1) for P. aeruginosa. The thermodynamic properties ΔG(0), ΔH(0), and ΔS(0) of Cd(2+) for biosorption were analyzed by the equilibrium constant value obtained from experimented data at different temperatures. The results show that biosorption of Cd(2+) by P. aeruginosa are endothermic and spontaneous with ΔH value of 36.35 J.mol(-1). By response surface methodology, the quadratic model has adequately described the experimental data based on the adjusted determination coefficient (R(2) = 0.98). The optimum conditions for maximum uptake onto the biosorbent were established at 0.5 g.l(-1) biosorbent concentration, pH 6 for the aqueous solution, and a temperature of 30 °C.

Thermodynamic analysis of fuels in gas phase: ethanol, gasoline and ethanol - gasoline predicted by DFT method.

PubMed

Neto, A F G; Lopes, F S; Carvalho, E V; Huda, M N; Neto, A M J C; Machado, N T

2015-10-01

This paper presents a theoretical study using density functional theory to calculate thermodynamics properties of major molecules compounds at gas phase of fuels like gasoline, ethanol, and gasoline-ethanol mixture in thermal equilibrium on temperature range up to 1500 K. We simulated a composition of gasoline mixture with ethanol for a thorough study of thermal energy, enthalpy, Gibbs free energy, entropy, heat capacity at constant pressure with respect to temperature in order to study the influence caused by ethanol as an additive to gasoline. We used semi-empirical computational methods as well in order to know the efficiency of other methods to simulate fuels through this methodology. In addition, the ethanol influence through the changes in percentage fractions of chemical energy released in combustion reaction and the variations on thermal properties for autoignition temperatures of fuels was analyzed. We verified how ethanol reduces the chemical energy released by gasoline combustion and how at low temperatures the gas phase fuels in thermal equilibrium have similar thermodynamic behavior. Theoretical results were compared with experimental data, when available, and showed agreement. Graphical Abstract Thermodynamic analysis of fuels in gas phase.

A Harris-Todaro Agent-Based Model to Rural-Urban Migration

NASA Astrophysics Data System (ADS)

Espíndola, Aquino L.; Silveira, Jaylson J.; Penna, T. J. P.

2006-09-01

The Harris-Todaro model of the rural-urban migration process is revisited under an agent-based approach. The migration of the workers is interpreted as a process of social learning by imitation, formalized by a computational model. By simulating this model, we observe a transitional dynamics with continuous growth of the urban fraction of overall population toward an equilibrium. Such an equilibrium is characterized by stabilization of rural-urban expected wages differential (generalized Harris-Todaro equilibrium condition), urban concentration and urban unemployment. These classic results obtained originally by Harris and Todaro are emergent properties of our model.

Insight into the SEA amide thioester equilibrium. Application to the synthesis of thioesters at neutral pH.

PubMed

Pira, S L; El Mahdi, O; Raibaut, L; Drobecq, H; Dheur, J; Boll, E; Melnyk, O

2016-07-26

The bis(2-sulfanylethyl)amide (SEA) N,S-acyl shift thioester surrogate has found a variety of useful applications in the field of protein total synthesis. Here we present novel insights into the SEA amide/thioester equilibrium in water which is an essential step in any reaction involving the thioester surrogate properties of the SEA group. We also show that the SEA amide thioester equilibrium can be efficiently displaced at neutral pH for accessing peptide alkylthioesters, i.e. the key components of the native chemical ligation (NCL) reaction.

Applications of the Soave-Redlich-Kwong Equations of State Using Mathematic

NASA Astrophysics Data System (ADS)

Sun, Lanyi; Zhai, Cheng; Zhang, Hui

The application of the Peng-Robinson equations of state (PR EOS) using Matlab and Mathematic has already been demonstrated. In this paper, using Mathematic to solve Soave-Redlich-Kwong (SRK) EOS, as well as the estimation of pure component properties, plotting of vapor-liquid equilibrium (VLE) diagram and calculation of chemical equilibrium, is presented. First the SRK EOS is used to predict several pure-component properties, such as liquid and gas molar volumes for isobutane. The vapor-liquid isobaric diagram is then plotted for a binary mixture composed of n-pentane and n-hexane under the pressures of 2*10^5 and 8*10^5 Pa respectively.

Machine learning predictions of molecular properties: Accurate many-body potentials and nonlocality in chemical space

DOE PAGES

Hansen, Katja; Biegler, Franziska; Ramakrishnan, Raghunathan; ...

2015-06-04

Simultaneously accurate and efficient prediction of molecular properties throughout chemical compound space is a critical ingredient toward rational compound design in chemical and pharmaceutical industries. Aiming toward this goal, we develop and apply a systematic hierarchy of efficient empirical methods to estimate atomization and total energies of molecules. These methods range from a simple sum over atoms, to addition of bond energies, to pairwise interatomic force fields, reaching to the more sophisticated machine learning approaches that are capable of describing collective interactions between many atoms or bonds. In the case of equilibrium molecular geometries, even simple pairwise force fields demonstratemore » prediction accuracy comparable to benchmark energies calculated using density functional theory with hybrid exchange-correlation functionals; however, accounting for the collective many-body interactions proves to be essential for approaching the “holy grail” of chemical accuracy of 1 kcal/mol for both equilibrium and out-of-equilibrium geometries. This remarkable accuracy is achieved by a vectorized representation of molecules (so-called Bag of Bonds model) that exhibits strong nonlocality in chemical space. The same representation allows us to predict accurate electronic properties of molecules, such as their polarizability and molecular frontier orbital energies.« less

Machine Learning Predictions of Molecular Properties: Accurate Many-Body Potentials and Nonlocality in Chemical Space

PubMed Central

2015-01-01

Simultaneously accurate and efficient prediction of molecular properties throughout chemical compound space is a critical ingredient toward rational compound design in chemical and pharmaceutical industries. Aiming toward this goal, we develop and apply a systematic hierarchy of efficient empirical methods to estimate atomization and total energies of molecules. These methods range from a simple sum over atoms, to addition of bond energies, to pairwise interatomic force fields, reaching to the more sophisticated machine learning approaches that are capable of describing collective interactions between many atoms or bonds. In the case of equilibrium molecular geometries, even simple pairwise force fields demonstrate prediction accuracy comparable to benchmark energies calculated using density functional theory with hybrid exchange-correlation functionals; however, accounting for the collective many-body interactions proves to be essential for approaching the “holy grail” of chemical accuracy of 1 kcal/mol for both equilibrium and out-of-equilibrium geometries. This remarkable accuracy is achieved by a vectorized representation of molecules (so-called Bag of Bonds model) that exhibits strong nonlocality in chemical space. In addition, the same representation allows us to predict accurate electronic properties of molecules, such as their polarizability and molecular frontier orbital energies. PMID:26113956

Stability analysis and nonstandard Grünwald-Letnikov scheme for a fractional order predator-prey model with ratio-dependent functional response

NASA Astrophysics Data System (ADS)

Suryanto, Agus; Darti, Isnani

2017-12-01

In this paper we discuss a fractional order predator-prey model with ratio-dependent functional response. The dynamical properties of this model is analyzed. Here we determine all equilibrium points of this model including their existence conditions and their stability properties. It is found that the model has two type of equilibria, namely the predator-free point and the co-existence point. If there is no co-existence equilibrium, i.e. when the coefficient of conversion from the functional response into the growth rate of predator is less than the death rate of predator, then the predator-free point is asymptotically stable. On the other hand, if the co-existence point exists then this equilibrium is conditionally stable. We also construct a nonstandard Grnwald-Letnikov (NSGL) numerical scheme for the propose model. This scheme is a combination of the Grnwald-Letnikov approximation and the nonstandard finite difference scheme. This scheme is implemented in MATLAB and used to perform some simulations. It is shown that our numerical solutions are consistent with the dynamical properties of our fractional predator-prey model.

Evaluating measurement uncertainty in fluid phase equilibrium calculations

NASA Astrophysics Data System (ADS)

van der Veen, Adriaan M. H.

2018-04-01

The evaluation of measurement uncertainty in accordance with the ‘Guide to the expression of uncertainty in measurement’ (GUM) has not yet become widespread in physical chemistry. With only the law of the propagation of uncertainty from the GUM, many of these uncertainty evaluations would be cumbersome, as models are often non-linear and require iterative calculations. The methods from GUM supplements 1 and 2 enable the propagation of uncertainties under most circumstances. Experimental data in physical chemistry are used, for example, to derive reference property data and support trade—all applications where measurement uncertainty plays an important role. This paper aims to outline how the methods for evaluating and propagating uncertainty can be applied to some specific cases with a wide impact: deriving reference data from vapour pressure data, a flash calculation, and the use of an equation-of-state to predict the properties of both phases in a vapour-liquid equilibrium. The three uncertainty evaluations demonstrate that the methods of GUM and its supplements are a versatile toolbox that enable us to evaluate the measurement uncertainty of physical chemical measurements, including the derivation of reference data, such as the equilibrium thermodynamical properties of fluids.

An ultrasonic measurement for in vitro depth-dependent equilibrium strains of articular cartilage in compression

NASA Astrophysics Data System (ADS)

Zheng, Y. P.; Mak, A. F. T.; Lau, K. P.; Qin, L.

2002-09-01

The equilibrium depth-dependent biomechanical properties of articular cartilage were measured using an ultrasound-compression method. Ten cylindrical bovine patella cartilage-bone specimens were tested in compression followed by a period of force-relaxation. A 50 MHz focused ultrasound beam was transmitted into the cartilage specimen through a remaining bone layer and a small hole at the centre of a specimen platform. The ultrasound echoes reflected or scattered within the articular cartilage were collected using the same transducer. The displacements of the tissues at different depths of the articular cartilage were derived from the ultrasound echo signals recorded during the compression and the subsequent force-relaxation. For two steps of 0.1 mm compression, the average strain at the superficial 0.2 mm thick layer (0.35 +/- 0.09) was significantly (p < 0.05) larger than that at the subsequent 0.2 mm thick layer (0.05 +/- 0.07) and that at deeper layers (0.01 +/- 0.02). It was demonstrated that the compressive biomechanical properties of cartilage were highly depth-dependent. The results suggested that the ultrasound-compression method could be a useful tool for the study of the depth-dependent biomechanical properties of articular cartilage.

Stochastic thermodynamics of quantum maps with and without equilibrium.

PubMed

Barra, Felipe; Lledó, Cristóbal

2017-11-01

We study stochastic thermodynamics for a quantum system of interest whose dynamics is described by a completely positive trace-preserving (CPTP) map as a result of its interaction with a thermal bath. We define CPTP maps with equilibrium as CPTP maps with an invariant state such that the entropy production due to the action of the map on the invariant state vanishes. Thermal maps are a subgroup of CPTP maps with equilibrium. In general, for CPTP maps, the thermodynamic quantities, such as the entropy production or work performed on the system, depend on the combined state of the system plus its environment. We show that these quantities can be written in terms of system properties for maps with equilibrium. The relations that we obtain are valid for arbitrary coupling strengths between the system and the thermal bath. The fluctuations of thermodynamic quantities are considered in the framework of a two-point measurement scheme. We derive the entropy production fluctuation theorem for general maps and a fluctuation relation for the stochastic work on a system that starts in the Gibbs state. Some simplifications for the probability distributions in the case of maps with equilibrium are presented. We illustrate our results by considering spin 1/2 systems under thermal maps, nonthermal maps with equilibrium, maps with nonequilibrium steady states, and concatenations of them. Finally, and as an important application, we consider a particular limit in which the concatenation of maps generates a continuous time evolution in Lindblad form for the system of interest, and we show that the concept of maps with and without equilibrium translates into Lindblad equations with and without quantum detailed balance, respectively. The consequences for the thermodynamic quantities in this limit are discussed.

Evidence for a Shared Mechanism in the Formation of Urea-Induced Kinetic and Equilibrium Intermediates of Horse Apomyoglobin from Ultrarapid Mixing Experiments.

PubMed

Mizukami, Takuya; Abe, Yukiko; Maki, Kosuke

2015-01-01

In this study, the equivalence of the kinetic mechanisms of the formation of urea-induced kinetic folding intermediates and non-native equilibrium states was investigated in apomyoglobin. Despite having similar structural properties, equilibrium and kinetic intermediates accumulate under different conditions and via different mechanisms, and it remains unknown whether their formation involves shared or distinct kinetic mechanisms. To investigate the potential mechanisms of formation, the refolding and unfolding kinetics of horse apomyoglobin were measured by continuous- and stopped-flow fluorescence over a time range from approximately 100 μs to 10 s, along with equilibrium unfolding transitions, as a function of urea concentration at pH 6.0 and 8°C. The formation of a kinetic intermediate was observed over a wider range of urea concentrations (0-2.2 M) than the formation of the native state (0-1.6 M). Additionally, the kinetic intermediate remained populated as the predominant equilibrium state under conditions where the native and unfolded states were unstable (at ~0.7-2 M urea). A continuous shift from the kinetic to the equilibrium intermediate was observed as urea concentrations increased from 0 M to ~2 M, which indicates that these states share a common kinetic folding mechanism. This finding supports the conclusion that these intermediates are equivalent. Our results in turn suggest that the regions of the protein that resist denaturant perturbations form during the earlier stages of folding, which further supports the structural equivalence of transient and equilibrium intermediates. An additional folding intermediate accumulated within ~140 μs of refolding and an unfolding intermediate accumulated in <1 ms of unfolding. Finally, by using quantitative modeling, we showed that a five-state sequential scheme appropriately describes the folding mechanism of horse apomyoglobin.

Stochastic thermodynamics of quantum maps with and without equilibrium

NASA Astrophysics Data System (ADS)

Barra, Felipe; Lledó, Cristóbal

2017-11-01

We study stochastic thermodynamics for a quantum system of interest whose dynamics is described by a completely positive trace-preserving (CPTP) map as a result of its interaction with a thermal bath. We define CPTP maps with equilibrium as CPTP maps with an invariant state such that the entropy production due to the action of the map on the invariant state vanishes. Thermal maps are a subgroup of CPTP maps with equilibrium. In general, for CPTP maps, the thermodynamic quantities, such as the entropy production or work performed on the system, depend on the combined state of the system plus its environment. We show that these quantities can be written in terms of system properties for maps with equilibrium. The relations that we obtain are valid for arbitrary coupling strengths between the system and the thermal bath. The fluctuations of thermodynamic quantities are considered in the framework of a two-point measurement scheme. We derive the entropy production fluctuation theorem for general maps and a fluctuation relation for the stochastic work on a system that starts in the Gibbs state. Some simplifications for the probability distributions in the case of maps with equilibrium are presented. We illustrate our results by considering spin 1/2 systems under thermal maps, nonthermal maps with equilibrium, maps with nonequilibrium steady states, and concatenations of them. Finally, and as an important application, we consider a particular limit in which the concatenation of maps generates a continuous time evolution in Lindblad form for the system of interest, and we show that the concept of maps with and without equilibrium translates into Lindblad equations with and without quantum detailed balance, respectively. The consequences for the thermodynamic quantities in this limit are discussed.

Isatinphenylsemicarbazones as efficient colorimetric sensors for fluoride and acetate anions - anions induce tautomerism.

PubMed

Jakusová, Klaudia; Donovalová, Jana; Cigáň, Marek; Gáplovský, Martin; Garaj, Vladimír; Gáplovský, Anton

2014-04-05

The anion induced tautomerism of isatin-3-4-phenyl(semicarbazone) derivatives is studied herein. The interaction of F(-), AcO(-), H2PO4(-), Br(-) or HSO4(-) anions with E and Z isomers of isatin-3-4-phenyl(semicarbazone) and N-methylisatin-3-4-phenyl(semicarbazone) as sensors influences the tautomeric equilibrium of these sensors in the liquid phase. This tautomeric equilibrium is affected by (1) the inter- and intra-molecular interactions' modulation of isatinphenylsemicarbazone molecules due to the anion induced change in the solvation shell of receptor molecules and (2) the sensor-anion interaction with the urea hydrogens. The acid-base properties of anions and the difference in sensor structure influence the equilibrium ratio of the individual tautomeric forms. Here, the tautomeric equilibrium changes were indicated by "naked-eye" experiment, UV-VIS spectral and (1)H NMR titration, resulting in confirmation that appropriate selection of experimental conditions leads to a high degree of sensor selectivity for some investigated anions. Sensors' E and Z isomers differ in sensitivity, selectivity and sensing mechanism. Detection of F(-) or CH3COO(-) anions at high weakly basic anions' excess is possible. Copyright © 2014 Elsevier B.V. All rights reserved.

Spectrin tetramer-dimer equilibrium and the stability of erythrocyte membrane skeletons

NASA Astrophysics Data System (ADS)

Liu, Shih-Chun; Palek, Jiri

1980-06-01

The inner side of the red-cell membrane is laminated by a two-dimensional network of membrane proteins which include spectrin, actin and some other components1-4. After extraction of lipids and integral proteins from the membrane, this membrane skeleton can be visualized as a ball-shaped network consisting of twisted fibres1-4 and globular protrusions4; however, the assembly of the individual proteins in the membrane skeleton is not well understood. Spectrin can be eluted from the membrane in the form of dimers and tetramers5-8. Electron microscopic study with low-angle shadowing technique shows that spectrin dimers are two parallel strands of twisted fibres presumably representing bands 1 and 2 of spectrin9. Spectrin tetramers presumably formed by head-to-head associations of two dimers are twice as long9. In solution, the spectrin dimer-tetramer equilibrium depends on temperature and salt concentration7,8; however, it is not known whether the same equilibrium exists in the membrane and whether it affects the physical properties of the membrane, such as its structural stability and deformability. We now demonstrate that spectrin dimers and tetramers are in a reversible equilibrium in the membrane and that in physiological conditions this equilibrium favours spectrin tetramers. Furthermore, we show that transformation of spectrin tetramers to dimers, as induced by ghost incubation in hypotonic conditions, diminishes the structural stability of the Triton-insoluble membrane skeletons.

Polymorphism in the two-locus Levene model with nonepistatic directional selection.

PubMed

Bürger, Reinhard

2009-11-01

For the Levene model with soft selection in two demes, the maintenance of polymorphism at two diallelic loci is studied. Selection is nonepistatic and dominance is intermediate. Thus, there is directional selection in every deme and at every locus. We assume that selection is in opposite directions in the two demes because otherwise no polymorphism is possible. If at one locus there is no dominance, then a complete analysis of the dynamical and equilibrium properties is performed. In particular, a simple necessary and sufficient condition for the existence of an internal equilibrium and sufficient conditions for global asymptotic stability are obtained. These results are extended to deme-independent degree of dominance at one locus. A perturbation analysis establishes structural stability within the full parameter space. In the absence of genotype-environment interaction, which requires deme-independent dominance at both loci, nongeneric equilibrium behavior occurs, and the introduction of arbitrarily small genotype-environment interaction changes the equilibrium structure and may destroy stable polymorphism. The volume of the parameter space for which a (stable) two-locus polymorphism is maintained is computed numerically. It is investigated how this volume depends on the strength of selection and on the dominance relations. If the favorable allele is (partially) dominant in its deme, more than 20% of all parameter combinations lead to a globally asymptotically stable, fully polymorphic equilibrium.

Self Assembled Particles

NASA Technical Reports Server (NTRS)

Palacci, Jeremie (Inventor); Pine, David J. (Inventor); Chaikin, Paul Michael (Inventor); Sacanna, Stefano (Inventor)

2017-01-01

A self-assembling structure using non-equilibrium driving forces leading to 'living crystals' and other maniputable particles with a complex dynamics. The dynamic self-assembly assembly results from a competition between self-propulsion of particles and an attractive interaction between the particles. As a result of non-equilibrium driving forces, the crystals form, grow, collide, anneal, repair themselves and spontaneously self-destruct, thereby enabling reconfiguration and assembly to achieve a desired property.

Bidding for Brains: Intellectual Property Rights and the International Migration of Knowledge Workers. NBER Working Paper No. 15486

ERIC Educational Resources Information Center

McAusland, Carol; Kuhn, Peter J.

2009-01-01

We introduce international mobility of knowledge workers into a model of Nash equilibrium IPR policy choice among countries. We show that governments have incentives to use IPRs in a bidding war for global talent, resulting in Nash equilibrium IPRs that can be too high, rather than too low, from a global welfare perspective. These incentives…

Shock-tube thermochemistry tables for high-temperature gases. Volume 5: Carbon dioxide

NASA Technical Reports Server (NTRS)

Menard, W. A.; Horton, T. E.

1971-01-01

Equilibrium thermodynamic properties and species concentrations for carbon dioxide are tabulated for moving, standing, and reflected shock waves. Initial pressures range from 6.665 to 6665 N/sq m (0.05 to 50.0 torr), and temperatures from 2,000 to over 80,000K. In this study, 20 molecular and atomic species were considered.

Program Gives Data On Physical Properties Of Hydrogen

NASA Technical Reports Server (NTRS)

Roder, H. M.; Mccarty, R. D.; Hall, W. J.

1994-01-01

TAB II computer program provides values of thermodynamic and transport properties of hydrogen in useful format. Also, provides values for equilibrium hydrogen and para-hydrogen. Program fast, moderately accurate, and operates over wide ranges of input variables. Written in FORTRAN 77.

Born energy, acid-base equilibrium, structure and interactions of end-grafted weak polyelectrolyte layers.

PubMed

Nap, R J; Tagliazucchi, M; Szleifer, I

2014-01-14

This work addresses the effect of the Born self-energy contribution in the modeling of the structural and thermodynamical properties of weak polyelectrolytes confined to planar and curved surfaces. The theoretical framework is based on a theory that explicitly includes the conformations, size, shape, and charge distribution of all molecular species and considers the acid-base equilibrium of the weak polyelectrolyte. Namely, the degree of charge in the polymers is not imposed but it is a local varying property that results from the minimization of the total free energy. Inclusion of the dielectric properties of the polyelectrolyte is important as the environment of a polymer layer is very different from that in the adjacent aqueous solution. The main effect of the Born energy contribution on the molecular organization of an end-grafted weak polyacid layer is uncharging the weak acid (or basic) groups and consequently decreasing the concentration of mobile ions within the layer. The magnitude of the effect increases with polymer density and, in the case of the average degree of charge, it is qualitatively equivalent to a small shift in the equilibrium constant for the acid-base equilibrium of the weak polyelectrolyte monomers. The degree of charge is established by the competition between electrostatic interactions, the polymer conformational entropy, the excluded volume interactions, the translational entropy of the counterions and the acid-base chemical equilibrium. Consideration of the Born energy introduces an additional energetic penalty to the presence of charged groups in the polyelectrolyte layer, whose effect is mitigated by down-regulating the amount of charge, i.e., by shifting the local-acid base equilibrium towards its uncharged state. Shifting of the local acid-base equilibrium and its effect on the properties of the polyelectrolyte layer, without considering the Born energy, have been theoretically predicted previously. Account of the Born energy leads to systematic, but in general small, corrections to earlier theoretical predictions describing the behavior of weak polyelectrolyte layers. However, polyelectrolyte uncharging results in a decrease in the concentration of counterions and inclusion of the Born Energy can result in a substantial decrease of the counterion concentration. The effect of considering the Born energy contribution is explored for end-grafted weak polyelectrolyte layers by calculating experimental observables which are known to depend on the presence of charges within the polyelectrolyte layer: inclusion of the Born energy contribution leads to a decrease in the capacitance of polyelectrolyte-modified electrodes, a decrease of conductivity of polyelectrolyte-modified nanopores and an increase in the repulsion exerted by a planar polyelectrolyte layer confined by an opposing wall.

Equilibrium and kinetic studies of copper biosorption by dead Ceriporia lacerata biomass isolated from the litter of an invasive plant in China.

PubMed

Li, Xiaona; Li, Airong; Long, Mingzhong; Tian, Xingjun

2015-01-01

Ceriporia lacerata, a strain of white-rot fungus isolated from the litter of an invasive plant (Solidago canadensis) in China, was little known about its properties and utilization. In this work, the copper(II) biosorption characteristics of formaldehyde inactivated C. lacerata biomass were examined as a function of initial pH, initial copper(II) concentration and contact time, and the adsorptive equilibrium and kinetics were simulated, too. The optimum pH was found to be 6.0 at experimental conditions of initial copper(II) concentration 100 mg/L, biomass dose 2 g/L, contact time 12 h, shaking rate 150 r/min and temperature 25°C. Biosorption equilibrium cost about 1 hour at experimental conditions of pH 6.0, initial copper(II) concentration 100 mg/L, C. lacerata dose 2 g/L, shaking rate 150 r/min and temperature 25°C. At optimum pH 6.0, highest copper(II) biosorption amounts were 6.79 and 7.76 mg/g for initial copper(II) concentration of 100 and 200 mg/L, respectively (with other experimental parameters of C. lacerata dose 2 g/L, shaking rate 150 r/min and temperature 25°C). The pseudo second-order adsorptive model gave the best adjustment for copper(II) biosorption kinetics. The equilibrium data fitted very well to both Langmuir and Freundlich adsorptive isotherm models. Without further acid or alkali treatment for improving adsorption properties, formaldehyde inactivated C. lacerata biomass possesses good biosorption characteristics on copper(II) removal from aqueous solutions.

Nuclear spin polarized H and D by means of spin-exchange optical pumping

NASA Astrophysics Data System (ADS)

Stenger, Jörn; Grosshauser, Carsten; Kilian, Wolfgang; Nagengast, Wolfgang; Ranzenberger, Bernd; Rith, Klaus; Schmidt, Frank

1998-01-01

Optically pumped spin-exchange sources for polarized hydrogen and deuterium atoms have been demonstrated to yield high atomic flow and high electron spin polarization. For maximum nuclear polarization the source has to be operated in spin temperature equilibrium, which has already been demonstrated for hydrogen. In spin temperature equilibrium the nuclear spin polarization PI equals the electron spin polarization PS for hydrogen and is even larger than PS for deuterium. We discuss the general properties of spin temperature equilibrium for a sample of deuterium atoms. One result are the equations PI=4PS/(3+PS2) and Pzz=PSṡPI, where Pzz is the nuclear tensor polarization. Furthermore we demonstrate that the deuterium atoms from our source are in spin temperature equilibrium within the experimental accuracy.

Linear and nonlinear stability criteria for compressible MHD flows in a gravitational field

NASA Astrophysics Data System (ADS)

Moawad, S. M.; Moawad

2013-10-01

The equilibrium and stability properties of ideal magnetohydrodynamics (MHD) of compressible flow in a gravitational field with a translational symmetry are investigated. Variational principles for the steady-state equations are formulated. The MHD equilibrium equations are obtained as critical points of a conserved Lyapunov functional. This functional consists of the sum of the total energy, the mass, the circulation along field lines (cross helicity), the momentum, and the magnetic helicity. In the unperturbed case, the equilibrium states satisfy a nonlinear second-order partial differential equation (PDE) associated with hydrodynamic Bernoulli law. The PDE can be an elliptic or a parabolic equation depending on increasing the poloidal flow speed. Linear and nonlinear Lyapunov stability conditions under translational symmetric perturbations are established for the equilibrium states.

Density functional theory study of structural, electronic, and thermal properties of Pt, Pd, Rh, Ir, Os and PtPd X (X = Ir, Os, and Rh) alloys

NASA Astrophysics Data System (ADS)

Shabbir, Ahmed; Muhammad, Zafar; M, Shakil; M, A. Choudhary

2016-03-01

The structural, electronic, mechanical, and thermal properties of Pt, Pd, Rh, Ir, Os metals and their alloys PtPdX (X = Ir, Os and Rh) are studied systematically using ab initio density functional theory. The groundstate properties such as lattice constant and bulk modulus are calculated to find the equilibrium atomic position for stable alloys. The electronic band structure and density of states are calculated to study the electronic behavior of metals on making their alloys. The electronic properties substantiate the metallic behavior for all studied materials. The firstprinciples density functional perturbation theory as implemented in quasi-harmonic approximation is used for the calculations of thermal properties. We have calculated the thermal properties such as the Debye temperature, vibrational energy, entropy and constant-volume specific heat. The calculated properties are compared with the previously reported experimental and theoretical data for metals and are found to be in good agreement. Calculated results for alloys could not be compared because there is no data available in the literature with such alloy composition.

Closed set of the uniqueness conditions and bifurcation criteria in generalized coupled thermoplasticity for small deformations

NASA Astrophysics Data System (ADS)

Śloderbach, Zdzisław

2016-05-01

This paper reports the results of a study into global and local conditions of uniqueness and the criteria excluding the possibility of bifurcation of the equilibrium state for small strains. The conditions and criteria are derived on the basis of an analysis of the problem of uniqueness of a solution involving the basic incremental boundary problem of coupled generalized thermo-elasto-plasticity. This work forms a follow-up of previous research (Śloderbach in Bifurcations criteria for equilibrium states in generalized thermoplasticity, IFTR Reports, 1980, Arch Mech 3(35):337-349, 351-367, 1983), but contains a new derivation of global and local criteria excluding a possibility of bifurcation of an equilibrium state regarding a comparison body dependent on the admissible fields of stress rate. The thermal elasto-plastic coupling effects, non-associated laws of plastic flow and influence of plastic strains on thermoplastic properties of a body were taken into account in this work. Thus, the mathematical problem considered here is not a self-conjugated problem.

Longitudinal magnetization dynamics in Heisenberg magnets: Spin Green functions approach (Review Article)

NASA Astrophysics Data System (ADS)

Krivoruchko, V. N.

2017-11-01

In spite of the fact that dynamical properties of magnets have been extensively studied over the past years, the longitudinal magnetization dynamics is still much less understood than transverse one even in the equilibrium state of a system. In this paper, we give a review of existing, based on quantum-mechanical approach, theoretical descriptions of the longitudinal magnetization dynamics for ferro-, ferri- and antiferromagnetic dielectrics. The aim is to reveal specific features of this type of magnetization vibrations under description a system within the framework of one of the basic model theory of magnetism—the Heisenberg model. Related experimental investigations as well as open questions are also briefly discussed. We hope that understanding of the longitudinal magnetization dynamics distinctive features in the equilibrium state have to be a reference point for a theory uncovering the physical mechanisms that govern ultrafast spin dynamics after femtosecond laser pulse demagnetization when a system is far beyond an equilibrium state.

Tidal Heating in Enceladus

NASA Astrophysics Data System (ADS)

Meyer, Jennifer; Wisdom, J.

2007-07-01

The heating in Enceladus in an equilibrium resonant configuration with other saturnian satellites can be estimated independently of the physical properties of Enceladus. Our results update the values obtained for the equilibrium tidal heating found by Lissauer et al. (1984) and Peale (2003). We find that equilibrium tidal heating cannot account for the heat that is observed to be coming from Enceladus, and current heating rates are even less for conventional estimates of the Love number for Enceladus. Even allowing for a much larger dynamic Love number, as can occur in viscoelastic models (Ross and Schubert, 1989), the equilibrium tidal heating is less than the heat observed to be coming from Enceladus. One resolution is that the tidal equilibrium is unstable and that the system oscillates about equilibrium. Yoder (1981) suggested that Enceladus might oscillate about equilibrium if the Q of Enceladus is stress dependent. An alternate suggestion was made by Ojakangas and Stevenson (1986), who emphasized the possible temperature dependence of Q. In these models Enceladus would now be releasing heat stored during a recent high eccentricity phase. However, we have shown that the Ojakangas and Stevenson model does not produce oscillations for parameters appropriate for Enceladus. Other low-order resonance configurations are possible for the saturnian satellites in the past. These include the 3:2 Mimas-Enceladus and the 3:4 Enceladus-Tethys resonances. The latter resonance has no equilibrium because the orbits are diverging, and the former has an equilibrium heating rate of only 0.48 GW. So equilibrium heating at past resonances is no more successful at explaining past resurfacing events than equilibrium heating is at explaining the present activity.

First-principles investigation on switching properties of spiropyran and merocyanine grafted graphyne nanotube device

NASA Astrophysics Data System (ADS)

Bhuvaneswari, R.; Nagarajan, V.; Chandiramouli, R.

2018-01-01

The density functional theory (DFT) method with non-equilibrium Green's function (NEGF) method is used to study the electronic properties of the graphyne nanotube device. The graphyne nanotube is used as a base material to graft photochromic spiropyran and merocyanine molecules. The current voltage characteristics clearly give the insights on the switching properties of spiropyran and merocyanine grafted graphyne device. The findings show that spiropyran grafted graphyne device as ON state and merocyanine grafted graphyne device as an OFF state device. Moreover, upon shining light of proper wavelength, the spiropyran/merocyanine grafted graphyne nanotube device can be used as a switch.

Potential-based dynamical reweighting for Markov state models of protein dynamics.

PubMed

Weber, Jeffrey K; Pande, Vijay S

2015-06-09

As simulators attempt to replicate the dynamics of large cellular components in silico, problems related to sampling slow, glassy degrees of freedom in molecular systems will be amplified manyfold. It is tempting to augment simulation techniques with external biases to overcome such barriers with ease; biased simulations, however, offer little utility unless equilibrium properties of interest (both kinetic and thermodynamic) can be recovered from the data generated. In this Article, we present a general scheme that harnesses the power of Markov state models (MSMs) to extract equilibrium kinetic properties from molecular dynamics trajectories collected on biased potential energy surfaces. We first validate our reweighting protocol on a simple two-well potential, and we proceed to test our method on potential-biased simulations of the Trp-cage miniprotein. In both cases, we find that equilibrium populations, time scales, and dynamical processes are reliably reproduced as compared to gold standard, unbiased data sets. We go on to discuss the limitations of our dynamical reweighting approach, and we suggest auspicious target systems for further application.

Preparation of Some Homologous TEMPO Nitroxides and Oxoammonium Salts; Notes on the NMR Spectroscopy of Nitroxide Free Radicals; Observed Radical Nature of Oxoammonium Salt Solutions Containing Trace Amounts of Corresponding Nitroxides in an Equilibrium Relationship.

PubMed

Bobbitt, James M; Eddy, Nicholas A; Cady, Clyde X; Jin, Jing; Gascon, Jose A; Gelpí-Dominguez, Svetlana; Zakrzewski, Jerzy; Morton, Martha D

2017-09-15

Three new homologous TEMPO oxoammonium salts and three homologous nitroxide radicals have been prepared and characterized. The oxidation properties of the salts have been explored. The direct 13 C NMR and EPR spectra of the nitroxide free radicals and the oxoammonium salts, along with TEMPO and its oxoammonium salt, have been successfully measured with little peak broadening of the NMR signals. In the spectra of all ten compounds (nitroxides and corresponding oxoammonium salts), the carbons in the 2,2,6,6-tetramethylpiperidine core do not appear, implying paramagnetic properties. This unpredicted overall paramagnetism in the oxoammonium salt solutions is explained by a redox equilibrium as shown between oxoammonium salts and trace amounts of corresponding nitroxide. This equilibrium is confirmed by electron interchange reactions between nitroxides with an N-acetyl substituent and oxoammonium salts with longer acyl side chains.

A Generalized Multi-Phase Framework for Modeling Cavitation in Cryogenic Fluids

NASA Technical Reports Server (NTRS)

Dorney, Dan (Technical Monitor); Hosangadi, Ashvin; Ahuja, Vineet

2003-01-01

A generalized multi-phase formulation for cavitation in fluids operating at temperatures elevated relative to their critical temperatures is presented. The thermal effects and the accompanying property variations due to phase change are modeled rigorously. Thermal equilibrium is assumed and fluid thermodynamic properties are specified along the saturation line using the NIST-12 databank. Fundamental changes in the physical characteristics of the cavity when thermal effects become pronounced are identified; the cavity becomes more porous, the interface less distinct, and has increased entrainment when temperature variations are present. Quantitative estimates of temperature and pressure depressions in both liquid nitrogen and liquid hydrogen were computed and compared with experimental data of Hord for hydrofoils. Excellent estimates of the leading edge temperature and pressure depression were obtained while the comparisons in the cavity closure region were reasonable. Liquid nitrogen cavities were consistently found to be in thermal equilibrium while liquid hydrogen cavities exhibited small, but distinct, non-equilibrium effects.

Nonequilibrium thermodynamics of dilute polymer solutions in flow.

PubMed

Latinwo, Folarin; Hsiao, Kai-Wen; Schroeder, Charles M

2014-11-07

Modern materials processing applications and technologies often occur far from equilibrium. To this end, the processing of complex materials such as polymer melts and nanocomposites generally occurs under strong deformations and flows, conditions under which equilibrium thermodynamics does not apply. As a result, the ability to determine the nonequilibrium thermodynamic properties of polymeric materials from measurable quantities such as heat and work is a major challenge in the field. Here, we use work relations to show that nonequilibrium thermodynamic quantities such as free energy and entropy can be determined for dilute polymer solutions in flow. In this way, we determine the thermodynamic properties of DNA molecules in strong flows using a combination of simulations, kinetic theory, and single molecule experiments. We show that it is possible to calculate polymer relaxation timescales purely from polymer stretching dynamics in flow. We further observe a thermodynamic equivalence between nonequilibrium and equilibrium steady-states for polymeric systems. In this way, our results provide an improved understanding of the energetics of flowing polymer solutions.

Thermal equilibrium concentrations and effects of negatively charged Ga vacancies in n-type GaAs

NASA Astrophysics Data System (ADS)

Tan, T. Y.; You, H.-M.; Gösele, U. M.

1993-03-01

We have calculated the thermal equilibrium concentrations of the various negatively charged Ga vacancy species in GaAs. The triply-negatively-charged Ga vacancy, V {Ga/3-}, has been emphasized, since it dominates Ga self-diffusion and Ga-Al interdiffusion under intrinsic and n-doping conditions, as well as the diffusion of Si donor atoms occupying Ga sites. Under strong n-doping conditions, the thermal equilibrium V {Ga/3-}concentration, C_{V_{_{Ga} }^{3 - } }^{eq} (n), has been found to exhibit a temperature independence or a negative temperature dependence, i.e., the C_{V_{_{Ga} }^{3 - } }^{eq} (n) value is either unchanged or increases as the temperature is lowered. This is quite contrary to the normal point defect behavior for which the point defect thermal equilibrium concentration decreases as the temperature is lowered. This C_{V_{_{Ga} }^{3 - } }^{eq} (n) property provides explanations to a number of outstanding experimental results, either requiring the interpretation that V {Ga/3-}has attained its thermal equilibrium concentration at the onset of each experiment, or requiring mechanisms involving point defect non-equilibrium phenomena.

Self-organization of grafted polyelectrolyte layers via the coupling of chemical equilibrium and physical interactions.

PubMed

Tagliazucchi, Mario; de la Cruz, Mónica Olvera; Szleifer, Igal

2010-03-23

The competition between chemical equilibrium, for example protonation, and physical interactions determines the molecular organization and functionality of biological and synthetic systems. Charge regulation by displacement of acid-base equilibrium induced by changes in the local environment provides a feedback mechanism that controls the balance between electrostatic, van der Waals, steric interactions and molecular organization. Which strategies do responsive systems follow to globally optimize chemical equilibrium and physical interactions? We address this question by theoretically studying model layers of end-grafted polyacids. These layers spontaneously form self-assembled aggregates, presenting domains of controlled local pH and whose morphologies can be manipulated by the composition of the solution in contact with the film. Charge regulation stabilizes micellar domains over a wide range of pH by reducing the local charge in the aggregate at the cost of chemical free energy and gaining in hydrophobic interactions. This balance determines the boundaries between different aggregate morphologies. We show that a qualitatively new form of organization arises from the coupling between physical interactions and protonation equilibrium. This optimization strategy presents itself with polyelectrolytes coexisting in two different and well-defined protonation states. Our results underline the need of considering the coupling between chemical equilibrium and physical interactions due to their highly nonadditive behavior. The predictions provide guidelines for the creation of responsive polymer layers presenting self-organized patterns with functional properties and they give insights for the understanding of competing interactions in highly inhomogeneous and constrained environments such as those relevant in nanotechnology and those responsible for biological cells function.

Mixing times towards demographic equilibrium in insect populations with temperature variable age structures.

PubMed

Damos, Petros

2015-08-01

In this study, we use entropy related mixing rate modules to measure the effects of temperature on insect population stability and demographic breakdown. The uncertainty in the age of the mother of a randomly chosen newborn, and how it is moved after a finite act of time steps, is modeled using a stochastic transformation of the Leslie matrix. Age classes are represented as a cycle graph and its transitions towards the stable age distribution are brought forth as an exact Markov chain. The dynamics of divergence, from a non equilibrium state towards equilibrium, are evaluated using the Kolmogorov-Sinai entropy. Moreover, Kullback-Leibler distance is applied as information-theoretic measure to estimate exact mixing times of age transitions probabilities towards equilibrium. Using empirically data, we show that on the initial conditions and simulated projection's trough time, that population entropy can effectively be applied to detect demographic variability towards equilibrium under different temperature conditions. Changes in entropy are correlated with the fluctuations of the insect population decay rates (i.e. demographic stability towards equilibrium). Moreover, shorter mixing times are directly linked to lower entropy rates and vice versa. This may be linked to the properties of the insect model system, which in contrast to warm blooded animals has the ability to greatly change its metabolic and demographic rates. Moreover, population entropy and the related distance measures that are applied, provide a means to measure these rates. The current results and model projections provide clear biological evidence why dynamic population entropy may be useful to measure population stability. Copyright © 2015 Elsevier Inc. All rights reserved.

Equilibrium and thermodynamic studies on biosorption of Pb(II) onto Candida albicans biomass.

PubMed

Baysal, Zübeyde; Cinar, Ercan; Bulut, Yasemin; Alkan, Hüseyin; Dogru, Mehmet

2009-01-15

Biosorption of Pb(II) ions from aqueous solutions was studied in a batch system by using Candida albicans. The optimum conditions of biosorption were determined by investigating the initial metal ion concentration, contact time, temperature, biosorbent dose and pH. The extent of metal ion removed increased with increasing contact time, initial metal ion concentration and temperature. Biosorption equilibrium time was observed in 30min. The Freundlich and Langmuir adsorption models were used for the mathematical description of biosorption equilibrium and isotherm constants were also evaluated. The maximum biosorption capacity of Pb(II) on C. albicans was determined as 828.50+/-1.05, 831.26+/-1.30 and 833.33+/-1.12mgg(-1), respectively, at different temperatures (25, 35 and 45 degrees C). Biosorption showed pseudo second-order rate kinetics at different initial concentration of Pb(II) and different temperatures. The activation energy of the biosorption (Ea) was estimated as 59.04kJmol(-1) from Arrhenius equation. Using the equilibrium constant value obtained at different temperatures, the thermodynamic properties of the biosorption (DeltaG degrees , DeltaH degrees and DeltaS degrees ) were also determined. The results showed that biosorption of Pb(II) ions on C. albicans were endothermic and spontaneous. The optimum initial pH for Pb(II) was determined as pH 5.0. FTIR spectral analysis of Pb(II) adsorbed and unadsorbed C. albicans biomass was also discussed.

First-principles study of structural stability, electronic, optical and elastic properties of binary intermetallic: PtZr

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pagare, Gitanjali, E-mail: gita-pagare@yahoo.co.in; Jain, Ekta, E-mail: jainekta05@gmail.com; Sanyal, S. P., E-mail: sps.physicsbu@gmail.com

2016-05-06

Structural, electronic, optical and elastic properties of PtZr have been studied using the full-potential linearized augmented plane wave (FP-LAPW) method within density functional theory (DFT). The energy against volume and enthalpy vs. pressure variation in three different structures i.e. B{sub 1}, B{sub 2} and B{sub 3} for PtZr has been presented. The equilibrium lattice parameter, bulk modulus and its pressure derivative have been obtained using optimization method for all the three phases. Furthermore, electronic structure was discussed to reveal the metallic character of the present compound. The linear optical properties are also studied under zero pressure for the first time.more » Results on elastic properties are obtained using generalized gradient approximation (GGA) for exchange correlation potentials. Ductile nature of PtZr compound is predicted in accordance with Pugh’s criteria.« less

Spreading of a pendant liquid drop underneath a textured substrate

NASA Astrophysics Data System (ADS)

Mistry, Aashutosh; Muralidhar, K.

2018-04-01

A pendant drop spreading underneath a partially wetting surface from an initial shape to its final equilibrium configuration and contact angle is studied. A mathematical formulation that quantifies spreading behavior of liquid drops over textured surfaces is discussed. The drop volume and the equilibrium contact angle are treated as parameters in the study. The unbalanced force at the three-phase contact line is modeled as being proportional to the degree of departure from the equilibrium state. Model predictions are verified against the available experimental data in the literature. Results show that the flow dynamics is strongly influenced by the fluid properties, drop volume, and contact angle of the liquid with the partially wetting surface. The drop exhibits rich dynamical behavior including inertial oscillations and gravitational instability, given that gravity tries to detach the drop against wetting contributions. Flow characteristics of drop motion, namely, the radius of the footprint, slip length, and dynamic contact angle in the pendant configuration are presented. Given the interplay among the competing time-dependent forces, a spreading drop can momentarily be destabilized and not achieve a stable equilibrium shape. Instability is then controlled by the initial drop shape as well. The spreading model is used to delineate stable and unstable regimes in the parameter space. Predictions of the drop volume based on the Young-Laplace equation are seen to be conservative relative to the estimates of the dynamical model discussed in the present study.

Atomic orbitals in molecules: general electronegativity and improvement of Mulliken population analysis.

PubMed

Lu, Haigang; Dai, Dadi; Yang, Pin; Li, Lemin

2006-01-21

An approach of atomic orbitals in molecules (AOIM) has been developed to study the atomic properties in molecules, in which the molecular orbitals are expressed in terms of the optimized minimal atomic orbitals. The atomic electronegativities are calculated using Pauling's electronegativity of free atom and are employed to find the electronegativity equilibrium in molecules and to describe the amphoteric properties of the transition metals from the groups 4 to 10. AOIM can also improve the numerical stability and accuracy of the original Mulliken population analysis.

Experimental Program to Stimulate Competitive Research (EPSCoR)

NASA Technical Reports Server (NTRS)

Dingerson, Michael R.

1997-01-01

Report includes: (1) CLUSTER: "Studies in Macromolecular Behavior in Microgravity Environment": The Role of Protein Oligomers in Protein Crystallization; Phase Separation Phenomena in Microgravity; Traveling Front Polymerizations; Investigating Mechanisms Affecting Phase Transition Response and Changes in Thermal Transport Properties in ER-Fluids under Normal and Microgravity Conditions. (2) CLUSTER: "Computational/Parallel Processing Studies": Flows in Local Chemical Equilibrium; A Computational Method for Solving Very Large Problems; Modeling of Cavitating Flows.

A 3-states magnetic model of binary decisions in sociophysics

NASA Astrophysics Data System (ADS)

Fernandez, Miguel A.; Korutcheva, Elka; de la Rubia, F. Javier

2016-11-01

We study a diluted Blume-Capel model of 3-states sites as an attempt to understand how some social processes as cooperation or organization happen. For this aim, we study the effect of the complex network topology on the equilibrium properties of the model, by focusing on three different substrates: random graph, Watts-Strogatz and Newman substrates. Our computer simulations are in good agreement with the corresponding analytical results.

Ab initio investigation of the thermodynamics of cation distribution and of the electronic and magnetic structures in the LiMn2O4 spinel

NASA Astrophysics Data System (ADS)

Santos-Carballal, David; Ngoepe, Phuti E.; de Leeuw, Nora H.

2018-02-01

The spinel-structured lithium manganese oxide (LiMn2O4 ) is a material currently used as cathode for secondary lithium-ion batteries, but whose properties are not yet fully understood. Here, we report a computational investigation of the inversion thermodynamics and electronic behavior of LiMn2O4 derived from spin-polarized density functional theory calculations with a Hubbard Hamiltonian and long-range dispersion corrections (DFT+U-D3). Based on the analysis of the configurational free energy, we have elucidated a partially inverse equilibrium cation distribution for the LiMn2O4 spinel. This equilibrium degree of inversion is rationalized in terms of the crystal field stabilization effects and the difference between the size of the cations. We compare the atomic charges with the oxidation numbers for each degree of inversion. We found segregation of the Mn charge once these ions occupy the tetrahedral and octahedral sites of the spinel. We have obtained the atomic projections of the electronic band structure and density of states, showing that the normal LiMn2O4 has half-metallic properties, while the fully inverse spinel is an insulator. This material is in the ferrimagnetic state for the inverse and partially inverse cation arrangement. The optimized lattice and oxygen parameters, as well as the equilibrium degree of inversion, are in agreement with the available experimental data. The partial equilibrium degree of inversion is important in the interpretation of the lithium ion migration and surface properties of the LiMn2O4 spinel.

Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)

NASA Astrophysics Data System (ADS)

Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)' providing data from direct measurement of pressure and mole fraction in vapor phase at variable mole fraction in liquid phase and constant temperature.

Cation disorder and gas phase equilibrium in an YBa 2Cu 3O 7- x superconducting thin film

NASA Astrophysics Data System (ADS)

Shin, Dong Chan; Ki Park, Yong; Park, Jong-Chul; Kang, Suk-Joong L.; Yong Yoon, Duk

1997-02-01

YBa 2Cu 3O 7- x superconducting thin films have been grown by in situ off-axis rf sputtering with varying oxygen pressure, Ba/Y ratio in a target, and deposition temperature. With decreasing oxygen pressure, increasing Ba/Y ratio, increasing deposition temperature, the critical temperature of the thin films decreased and the c-axis length increased. The property change of films with the variation of deposition variables has been explained by a gas phase equilibrium of the oxidation reaction of Ba and Y. Applying Le Chatelier's principle to the oxidation reaction, we were able to predict the relation of deposition variables and the resultant properties of thin films; the prediction was in good agreement with the experimental results. From the relation between the three deposition variables and gas phase equilibrium, a 3-dimensional processing diagram was introduced. This diagram has shown that the optimum deposition condition of YBa 2Cu 3O 7- x thin films is not a fixed point but can be varied. The gas phase equilibrium can also be applied to the explanation of previous results that good quality films were obtained at low deposition temperature using active species, such as O, O 3, and O 2+.

Self-assembled materials and supramolecular chemistry within microfluidic environments: from common thermodynamic states to non-equilibrium structures.

PubMed

Sevim, S; Sorrenti, A; Franco, C; Furukawa, S; Pané, S; deMello, A J; Puigmartí-Luis, J

2018-05-01

Self-assembly is a crucial component in the bottom-up fabrication of hierarchical supramolecular structures and advanced functional materials. Control has traditionally relied on the use of encoded building blocks bearing suitable moieties for recognition and interaction, with targeting of the thermodynamic equilibrium state. On the other hand, nature leverages the control of reaction-diffusion processes to create hierarchically organized materials with surprisingly complex biological functions. Indeed, under non-equilibrium conditions (kinetic control), the spatio-temporal command of chemical gradients and reactant mixing during self-assembly (the creation of non-uniform chemical environments for example) can strongly affect the outcome of the self-assembly process. This directly enables a precise control over material properties and functions. In this tutorial review, we show how the unique physical conditions offered by microfluidic technologies can be advantageously used to control the self-assembly of materials and of supramolecular aggregates in solution, making possible the isolation of intermediate states and unprecedented non-equilibrium structures, as well as the emergence of novel functions. Selected examples from the literature will be used to confirm that microfluidic devices are an invaluable toolbox technology for unveiling, understanding and steering self-assembly pathways to desired structures, properties and functions, as well as advanced processing tools for device fabrication and integration.

Energetics and magnetic properties of V-doped MgO bulk and (001) surface: A GGA, GGA+U , and hybrid density functional study

NASA Astrophysics Data System (ADS)

Århammar, C.; Moyses Araujo, C.; Rao, K. V.; Norgren, Susanne; Johansson, Börje; Ahuja, Rajeev

2010-10-01

In this work, a first-principles study of the energetic and magnetic properties of V-doped MgO is presented, where both the bulk and (001) surface were investigated. It is found that V assumes a high-spin state with a local moment of about 3μB . In the bulk, the interaction between these local moments is very short ranged and the antiferromagnetic (AFM) ordering is energetically more favorable. The formation of V-VMg-V defect clusters is found to weaken the antiferromagnetic coupling in bulk MgO, degenerating the AFM and ferromagnetic state. However, these clusters are high in energy and will not form at equilibrium conditions. By employing the GGA+U approach, with U=5eV , the V3d states on the (001) surface are shifted below the Fermi level, and a reasonable surface geometry was achieved. A calculation with the hybrid HSE03 functional, contradicts the GGA+U results, indicating that the V-MgO surface should be metallic at this concentration. From the energetics it is concluded that, at the modeled concentration, VxOy phases will limit the solubility of V in MgO at equilibrium conditions, which is in agreement with previous experimental findings. In order to achieve higher concentrations of V, an off-equilibrium synthesis method is needed. Finally, we find that the formation energy of V at the surface is considerably higher than in the bulk and V is thus expected to diffuse from the surface into the bulk of MgO.

Evaluating Status Change of Soil Potassium from Path Model

PubMed Central

He, Wenming; Chen, Fang

2013-01-01

The purpose of this study is to determine critical environmental parameters of soil K availability and to quantify those contributors by using a proposed path model. In this study, plot experiments were designed into different treatments, and soil samples were collected and further analyzed in laboratory to investigate soil properties influence on soil potassium forms (water soluble K, exchangeable K, non-exchangeable K). Furthermore, path analysis based on proposed path model was carried out to evaluate the relationship between potassium forms and soil properties. Research findings were achieved as followings. Firstly, key direct factors were soil S, ratio of sodium-potassium (Na/K), the chemical index of alteration (CIA), Soil Organic Matter in soil solution (SOM), Na and total nitrogen in soil solution (TN), and key indirect factors were Carbonate (CO3), Mg, pH, Na, S, and SOM. Secondly, path model can effectively determine direction and quantities of potassium status changes between Exchangeable potassium (eK), Non-exchangeable potassium (neK) and water-soluble potassium (wsK) under influences of specific environmental parameters. In reversible equilibrium state of , K balance state was inclined to be moved into β and χ directions in treatments of potassium shortage. However in reversible equilibrium of , K balance state was inclined to be moved into θ and λ directions in treatments of water shortage. Results showed that the proposed path model was able to quantitatively disclose moving direction of K status and quantify its equilibrium threshold. It provided a theoretical and practical basis for scientific and effective fertilization in agricultural plants growth. PMID:24204659

Understand rotating isothermal collapses yet

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tohline, J.E.

1985-01-01

A scalar virial equation is used to describe the dynamic properties of equilibrium gas clouds, taking into account the relative effects of surface pressure, rotation, self gravity and internal isothermal pressure. Details concerning the internal structure of the clouds are ignored in order to obtain a globalized analytical expression. The obtained solution to the equation is found to agree with the surface-pressure-dominated model of Stahler (1983), and the rotation-dominated model of Hayashi, Narita, and Miyama (1982). On the basis of the analytical expression of virial equilibrium in the clouds, some of the limiting properties of isothermal clouds are described, andmore » a realistic starting model for cloud collapse is proposed. 18 references.« less

Effective convergence of the two-particle irreducible 1/N expansion for nonequilibrium quantum fields

NASA Astrophysics Data System (ADS)

Aarts, Gert; Laurie, Nathan; Tranberg, Anders

2008-12-01

The 1/N expansion of the two-particle irreducible effective action offers a powerful approach to study quantum field dynamics far from equilibrium. We investigate the effective convergence of the 1/N expansion in the O(N) model by comparing results obtained numerically in 1+1 dimensions at leading, next-to-leading and next-to-next-to-leading order in 1/N as well as in the weak coupling limit. A comparison in classical statistical field theory, where exact numerical results are available, is made as well. We focus on early-time dynamics and quasiparticle properties far from equilibrium and observe rapid effective convergence already for moderate values of 1/N or the coupling.

Carbohydrate binding properties of the stinging nettle (Urtica dioica) rhizome lectin.

PubMed

Shibuya, N; Goldstein, I J; Shafer, J A; Peumans, W J; Broekaert, W F

1986-08-15

The interaction of the stinging nettle rhizome lectin (UDA) with carbohydrates was studied by using the techniques of quantitative precipitation, hapten inhibition, equilibrium dialysis, and uv difference spectroscopy. The Carbohydrate binding site of UDA was determined to be complementary to an N,N',N"-triacetylchitotriose unit and proposed to consist of three subsites, each of which has a slightly different binding specificity. UDA also has a hydrophobic interacting region adjacent to the carbohydrate binding site. Equilibrium dialysis and uv difference spectroscopy revealed that UDA has two carbohydrate binding sites per molecule consisting of a single polypeptide chain. These binding sites either have intrinsically different affinities for ligand molecules, or they may display negative cooperativity toward ligand binding.

A comparative study of the structures and electronic properties of graphene fragments: A DFT and MP2 survey

NASA Astrophysics Data System (ADS)

de Carvalho, E. F. V.; Lopez-Castillo, A.; Roberto-Neto, O.

2018-01-01

Graphene can be viewed as sheet of benzene rings fused together forming a variety of structures including the trioxotriangulenes (TOTs) which is a class of organic molecules with electro-active properties. In order to clarify such properties, structures and electronic properties of the graphene fragments phenalenyl, triangulene, 6-oxophenalenoxyl, and X3TOT (X = H, F, Cl) are computed. Validation of the methodologies are carried out using the density functionals B3LYP, M06-2X, B2PLYP-D, and the MP2 theory, giving equilibrium geometries of benzene, naphthalene, and anthracene with mean unsigned error (MUE) of only 0.003, 0.007, 0.004, and 0.007 Å, respectively in relation to experiment.

Biochemical thermodynamics: applications of Mathematica.

PubMed

Alberty, Robert A

2006-01-01

The most efficient way to store thermodynamic data on enzyme-catalyzed reactions is to use matrices of species properties. Since equilibrium in enzyme-catalyzed reactions is reached at specified pH values, the thermodynamics of the reactions is discussed in terms of transformed thermodynamic properties. These transformed thermodynamic properties are complicated functions of temperature, pH, and ionic strength that can be calculated from the matrices of species values. The most important of these transformed thermodynamic properties is the standard transformed Gibbs energy of formation of a reactant (sum of species). It is the most important because when this function of temperature, pH, and ionic strength is known, all the other standard transformed properties can be calculated by taking partial derivatives. The species database in this package contains data matrices for 199 reactants. For 94 of these reactants, standard enthalpies of formation of species are known, and so standard transformed Gibbs energies, standard transformed enthalpies, standard transformed entropies, and average numbers of hydrogen atoms can be calculated as functions of temperature, pH, and ionic strength. For reactions between these 94 reactants, the changes in these properties can be calculated over a range of temperatures, pHs, and ionic strengths, and so can apparent equilibrium constants. For the other 105 reactants, only standard transformed Gibbs energies of formation and average numbers of hydrogen atoms at 298.15 K can be calculated. The loading of this package provides functions of pH and ionic strength at 298.15 K for standard transformed Gibbs energies of formation and average numbers of hydrogen atoms for 199 reactants. It also provides functions of temperature, pH, and ionic strength for the standard transformed Gibbs energies of formation, standard transformed enthalpies of formation, standard transformed entropies of formation, and average numbers of hydrogen atoms for 94 reactants. Thus loading this package makes available 774 mathematical functions for these properties. These functions can be added and subtracted to obtain changes in these properties in biochemical reactions and apparent equilibrium constants.

Equilibrium-point control hypothesis examined by measured arm stiffness during multijoint movement.

PubMed

Gomi, H; Kawato

1996-04-05

For the last 20 years, it has been hypothesized that well-coordinated, multijoint movements are executed without complex computation by the brain, with the use of springlike muscle properties and peripheral neural feedback loops. However, it has been technically and conceptually difficult to examine this "equilibrium-point control" hypothesis directly in physiological or behavioral experiments. A high-performance manipulandum was developed and used here to measure human arm stiffness, the magnitude of which during multijoint movement is important for this hypothesis. Here, the equilibrium-point trajectory was estimated from the measured stiffness, the actual trajectory, and the generated torque. Its velocity profile differed from that of the actual trajectory. These results argue against the hypothesis that the brain sends as a motor command only an equilibrium-point trajectory similar to the actual trajectory.

Equilibrium properties of blackbody radiation with an ultraviolet energy cut-off

NASA Astrophysics Data System (ADS)

Mishra, Dheeraj Kumar; Chandra, Nitin; Vaibhav, Vinay

2017-10-01

We study various equilibrium thermodynamic properties of blackbody radiation (i.e. a photon gas) with an ultraviolet energy cut-off. We find that the energy density, specific heat etc. follow usual acoustic phonon dynamics as have been well studied by Debye. Other thermodynamic quantities like pressure, entropy etc. have also been calculated. The usual Stefan-Boltzmann law gets modified. We observe that the values of the thermodynamic quantities with the energy cut-off is lower than the corresponding values in the theory without any such scale. The phase-space measure is also expected to get modified for an exotic spacetime appearing at Planck scale, which in turn leads to the modification of Planck energy density distribution and the Wien's displacement law. We found that the non-perturbative nature of the thermodynamic quantities in the SR limit (for both unmodified and modified cases), due to nonanalyticity of the leading term, is a general feature of the theory accompanied with an ultraviolet energy cut-off. We have also discussed the possible modification in the case of Big Bang and the Stellar objects and have suggested a table top experiment for verification in effective low energy case.

Chemical Equilibrium And Transport (CET)

NASA Technical Reports Server (NTRS)

Mcbride, B. J.

1991-01-01

Powerful, machine-independent program calculates theoretical thermodynamic properties of chemical systems. Aids in design of compressors, turbines, engines, heat exchangers, and chemical processing equipment.

Relative properties of smooth terminating bands

NASA Astrophysics Data System (ADS)

Afanasjev, A. V.; Ragnarsson, I.

1998-01-01

The relative properties of smooth terminating bands observed in the A ∼ 110 mass region are studied within the effective alignment approach. Theoretical values of ietf are calculated using the configuration-dependent shell-correction model with the cranked Nilsson potential. Reasonable agreement with experiment shows that previous interpretations of these bands are consistent with the present study. Contrary to the case of superdeformed bands, the effective alignments of these bands deviate significantly from the pure single-particle alignments of the corresponding orbitals. This indicates that in the case of smooth terminating bands, the effects associated with changes in equilibrium deformations contribute significantly to the effective alignment.

On the dynamical basis of the classification of normal galaxies

PubMed Central

Haass, J.; Bertin, G.; Lin, C. C.

1982-01-01

Some realistic galaxy models have been found to support discrete unstable spiral modes. Here, through the study of the relevant physical mechanisms and an extensive numerical investigation of the properties of the dominant modes in a wide class of galactic equilibria, we show how spiral structures are excited with different morphological features, depending on the properties of the equilibrium model. We identify the basic dynamical parameters and mechanisms and compare the resulting morphology of spiral modes with the actual classification of galaxies. The present study suggests a dynamical basis for the transition among various types and subclasses of normal and barred spiral galaxies. Images PMID:16593200

Photons in dense nuclear matter: Random-phase approximation

NASA Astrophysics Data System (ADS)

Stetina, Stephan; Rrapaj, Ermal; Reddy, Sanjay

2018-04-01

We present a comprehensive and pedagogic discussion of the properties of photons in cold and dense nuclear matter based on the resummed one-loop photon self-energy. Correlations among electrons, muons, protons, and neutrons in β equilibrium that arise as a result of electromagnetic and strong interactions are consistently taken into account within the random phase approximation. Screening effects, damping, and collective excitations are systematically studied in a fully relativistic setup. Our study is relevant to the linear response theory of dense nuclear matter, calculations of transport properties of cold dense matter, and investigations of the production and propagation of hypothetical vector bosons such as the dark photons.

A Bayesian perspective on Markovian dynamics and the fluctuation theorem

NASA Astrophysics Data System (ADS)

Virgo, Nathaniel

2013-08-01

One of E. T. Jaynes' most important achievements was to derive statistical mechanics from the maximum entropy (MaxEnt) method. I re-examine a relatively new result in statistical mechanics, the Evans-Searles fluctuation theorem, from a MaxEnt perspective. This is done in the belief that interpreting such results in Bayesian terms will lead to new advances in statistical physics. The version of the fluctuation theorem that I will discuss applies to discrete, stochastic systems that begin in a non-equilibrium state and relax toward equilibrium. I will show that for such systems the fluctuation theorem can be seen as a consequence of the fact that the equilibrium distribution must obey the property of detailed balance. Although the principle of detailed balance applies only to equilibrium ensembles, it puts constraints on the form of non-equilibrium trajectories. This will be made clear by taking a novel kind of Bayesian perspective, in which the equilibrium distribution is seen as a prior over the system's set of possible trajectories. Non-equilibrium ensembles are calculated from this prior using Bayes' theorem, with the initial conditions playing the role of the data. I will also comment on the implications of this perspective for the question of how to derive the second law.

Estimating soil hydraulic parameters from transient flow experiments in a centrifuge using parameter optimization technique

USGS Publications Warehouse

Šimůnek, Jirka; Nimmo, John R.

2005-01-01

A modified version of the Hydrus software package that can directly or inversely simulate water flow in a transient centrifugal field is presented. The inverse solver for parameter estimation of the soil hydraulic parameters is then applied to multirotation transient flow experiments in a centrifuge. Using time‐variable water contents measured at a sequence of several rotation speeds, soil hydraulic properties were successfully estimated by numerical inversion of transient experiments. The inverse method was then evaluated by comparing estimated soil hydraulic properties with those determined independently using an equilibrium analysis. The optimized soil hydraulic properties compared well with those determined using equilibrium analysis and steady state experiment. Multirotation experiments in a centrifuge not only offer significant time savings by accelerating time but also provide significantly more information for the parameter estimation procedure compared to multistep outflow experiments in a gravitational field.

On the fundamental properties of dynamically hot galaxies

NASA Astrophysics Data System (ADS)

Kritsuk, Alexei G.

1997-01-01

A two-component isothermal equilibrium model is applied to reproduce basic structural properties of dynamically hot stellar systems immersed in their massive dark haloes. The origin of the fundamental plane relation for giant ellipticals is naturally explained as a consequence of dynamical equilibrium in the context of the model. The existence of two galactic families displaying different behaviour in the luminosity-surface-brightness diagram is shown to be a result of a smooth transition from dwarfs, dominated by dark matter near the centre, to giants dominated by the luminous stellar component. The comparison of empirical scaling relations with model predictions suggests that probably a unique dissipative process was operating during the violent stage of development of stellar systems in the dark haloes, and the depth of the potential well controlled the observed luminosity of the resulting galaxies. The interpretation also provides some restrictions on the properties of dark haloes implied by the fundamental scaling laws.

Analysis of user equilibrium for staggered shifts in a single-entry traffic corridor with no late arrivals

NASA Astrophysics Data System (ADS)

Li, Chuan-Yao; Huang, Hai-Jun; Tang, Tie-Qiao

2017-05-01

In this paper, we investigate the effects of staggered shifts on the user equilibrium (UE) state in a single-entry traffic corridor with no late arrivals from the analytical and numerical perspective. The LWR (Lighthill-Whitham-Richards) model and the Greenshields' velocity-density function are used to describe the dynamic properties of traffic flow. Propositions for the properties of flow patterns in UE, and the quasi-analytic solutions for three possible situations in UE are deduced. Numerical tests are carried out to testify the analytical results, where the three-dimensional evolution diagram of traffic flow illustrates that shock and rarefaction wave exist in UE and the space-time diagram indicates that UE solutions satisfy the propagation properties of traffic flow. In addition, the cost curves show that the UE solutions satisfy the UE trip-timing condition.

Non-Poisson Processes: Regression to Equilibrium Versus Equilibrium Correlation Functions

DTIC Science & Technology

2004-07-07

ARTICLE IN PRESSPhysica A 347 (2005) 268–2880378-4371/$ - doi:10.1016/j Correspo E-mail adwww.elsevier.com/locate/physaNon- Poisson processes : regression...05.40.a; 89.75.k; 02.50.Ey Keywords: Stochastic processes; Non- Poisson processes ; Liouville and Liouville-like equations; Correlation function...which is not legitimate with renewal non- Poisson processes , is a correct property if the deviation from the exponential relaxation is obtained by time

Nematic-like stable glasses without equilibrium liquid crystal phases

DOE Data Explorer

Gomez, Jaritza [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA; Gujral, Ankit [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA; Huang, Chengbin [School of Pharmacy, University of Wisconsin-Madison, 777 Highland Avenue, Madison, Wisconsin 53705-2222, USA; Bishop, Camille [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA; Yu, Lian [School of Pharmacy, University of Wisconsin-Madison, 777 Highland Avenue, Madison, Wisconsin 53705-2222, USA; Ediger, Mark [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA

2017-02-01

We report the thermal and structural properties of glasses of posaconazole, a rod-like molecule, prepared using physical vapor deposition (PVD). PVD glasses of posaconazole can show substantial molecular orientation depending upon the choice of substrate temperature, Tsubstrate, during deposition.Ellipsometry and IR measurements indicate that glasses prepared at Tsubstrate very near the glass transition temperature (Tg) are highly ordered. For these posaconazole glasses, the orientation order parameter is similar to that observed in macroscopically aligned nematic liquid crystals, indicating that the molecules are mostly parallel to one another and perpendicular to the interface. To our knowledge, these are the most anisotropic glasses ever prepared by PVD from a molecule that does not form equilibrium liquid crystal phases. These results are consistent with a previously proposed mechanism in which molecular orientation in PVD glasses is inherited from the orientation present at the free surface of the equilibrium liquid. This mechanism suggests that molecular orientation at the surface of the equilibrium liquid of posaconazole is nematic-like. Posaconazole glasses can show very high kinetic stability; the isothermal transformation of a 400 nm glass into the supercooled liquid occurs via a propagating front that originates at the free surface and requires ~105 times the structural relaxation time of the liquid (τα). We also studied the kinetic stability of PVD glasses of itraconazole, which is a structurally similar molecule with equilibrium liquid crystal phases. While itraconazole glasses can be even more anisotropic than posaconazole glasses, they exhibit lower kinetic stability.

Game Design and Analysis for Price-Based Demand Response: An Aggregate Game Approach.

PubMed

Ye, Maojiao; Hu, Guoqiang

2016-02-18

In this paper, an aggregate game is adopted for the modeling and analysis of energy consumption control in smart grid. Since the electricity users' cost functions depend on the aggregate energy consumption, which is unknown to the end users, an average consensus protocol is employed to estimate it. By neighboring communication among the users about their estimations on the aggregate energy consumption, Nash seeking strategies are developed. Convergence properties are explored for the proposed Nash seeking strategies. For energy consumption game that may have multiple isolated Nash equilibria, a local convergence result is derived. The convergence is established by utilizing singular perturbation analysis and Lyapunov stability analysis. Energy consumption control for a network of heating, ventilation, and air conditioning systems is investigated. Based on the uniqueness of the Nash equilibrium, it is shown that the players' actions converge to a neighborhood of the unique Nash equilibrium nonlocally. More specially, if the unique Nash equilibrium is an inner Nash equilibrium, an exponential convergence result is obtained. Energy consumption game with stubborn players is studied. In this case, the actions of the rational players can be driven to a neighborhood of their best response strategies by using the proposed method. Numerical examples are presented to verify the effectiveness of the proposed methods.

Rapid equilibrium sampling initiated from nonequilibrium data.

PubMed

Huang, Xuhui; Bowman, Gregory R; Bacallado, Sergio; Pande, Vijay S

2009-11-24

Simulating the conformational dynamics of biomolecules is extremely difficult due to the rugged nature of their free energy landscapes and multiple long-lived, or metastable, states. Generalized ensemble (GE) algorithms, which have become popular in recent years, attempt to facilitate crossing between states at low temperatures by inducing a random walk in temperature space. Enthalpic barriers may be crossed more easily at high temperatures; however, entropic barriers will become more significant. This poses a problem because the dominant barriers to conformational change are entropic for many biological systems, such as the short RNA hairpin studied here. We present a new efficient algorithm for conformational sampling, called the adaptive seeding method (ASM), which uses nonequilibrium GE simulations to identify the metastable states, and seeds short simulations at constant temperature from each of them to quantitatively determine their equilibrium populations. Thus, the ASM takes advantage of the broad sampling possible with GE algorithms but generally crosses entropic barriers more efficiently during the seeding simulations at low temperature. We show that only local equilibrium is necessary for ASM, so very short seeding simulations may be used. Moreover, the ASM may be used to recover equilibrium properties from existing datasets that failed to converge, and is well suited to running on modern computer clusters.

Wave packet dynamics, time scales and phase diagram in the IBM-Lipkin-Meshkov-Glick model

NASA Astrophysics Data System (ADS)

Castaños, Octavio; de los Santos, Francisco; Yáñez, Rafael; Romera, Elvira

2018-02-01

We derive the phase diagram of a scalar two-level boson model by studying the equilibrium and stability properties of its energy surface. The plane of control parameters is enlarged with respect to previous studies. We then analyze the time evolution of wave packets centered around the ground state at various quantum phase transition boundary lines. In particular, classical and revival times are computed numerically.

Kinetics of Cation and Oxyanion Adsorption and Desorption on Ferrihydrite: Roles of Ferrihydrite Binding Sites and a Unified Model.

PubMed

Tian, Lei; Shi, Zhenqing; Lu, Yang; Dohnalkova, Alice C; Lin, Zhang; Dang, Zhi

2017-09-19

Quantitative understanding the kinetics of toxic ion reactions with various heterogeneous ferrihydrite binding sites is crucial for accurately predicting the dynamic behavior of contaminants in environment. In this study, kinetics of As(V), Cr(VI), Cu(II), and Pb(II) adsorption and desorption on ferrihydrite was studied using a stirred-flow method, which showed that metal adsorption/desorption kinetics was highly dependent on the reaction conditions and varied significantly among four metals. High resolution scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy showed that all four metals were distributed within the ferrihydrite aggregates homogeneously after adsorption reactions. Based on the equilibrium model CD-MUSIC, we developed a novel unified kinetics model applicable for both cation and oxyanion adsorption and desorption on ferrihydrite, which is able to account for the heterogeneity of ferrihydrite binding sites, different binding properties of cations and oxyanions, and variations of solution chemistry. The model described the kinetic results well. We quantitatively elucidated how the equilibrium properties of the cation and oxyanion binding to various ferrihydrite sites and the formation of various surface complexes controlled the adsorption and desorption kinetics at different reaction conditions and time scales. Our study provided a unified modeling method for the kinetics of ion adsorption/desorption on ferrihydrite.

Review of current results in computational studies of hydrocarbon phase and transport properties in nanoporous structures

NASA Astrophysics Data System (ADS)

Stroev, N.; Myasnikov, A.

2017-12-01

This article provides a general overview of the main simulation results on the behavior of gas/liquids under confinement conditions, namely hydrocarbons in shale formations, and current understanding of such phenomena. In addition to the key effects, which different research groups obtained and which have to be taken into account during the creation of reservoir simulation software, a list of methods is briefly covered. Comprehensive understanding of both fluid phase equilibrium and transport properties in nanoscale structures is of great importance for many scientific and technical disciplines, especially for petroleum engineering considering the hydrocarbon behavior in complex shale formations, the development of which increases with time. Recent estimations show that a significant amount of resources are trapped inside organic matter and clays, which has extremely low permeability and yet great economic potential. The issue is not only of practical importance, as the existing conventional approaches by definition are unable to capture complicated physics phenomena for effective results, but it is also of fundamental value. The research of the processes connected with such deposits is necessary for both evaluations of petroleum reservoir deposits and hydrodynamic simulators. That is why the review is divided into two major parts—equilibrium states of hydrocarbons and their transport properties in highly confined conditions.

[Key physical parameters of hawthorn leaf granules by stepwise regression analysis method].

PubMed

Jiang, Qie-Ying; Zeng, Rong-Gui; Li, Zhe; Luo, Juan; Zhao, Guo-Wei; Lv, Dan; Liao, Zheng-Gen

2017-05-01

The purpose of this study was to investigate the effect of key physical properties of hawthorn leaf granule on its dissolution behavior. Hawthorn leaves extract was utilized as a model drug. The extract was mixed with microcrystalline cellulose or starch with the same ratio by using different methods. Appropriate amount of lubricant and disintegrating agent was added into part of the mixed powder, and then the granules were prepared by using extrusion granulation and high shear granulation. The granules dissolution behavior was evaluated by using equilibrium dissolution quantity and dissolution rate constant of the hypericin as the indicators. Then the effect of physical properties on dissolution behavior was analyzed through the stepwise regression analysis method. The equilibrium dissolution quantity of hypericin and adsorption heat constant in hawthorn leaves were positively correlated with the monolayer adsorption capacity and negatively correlated with the moisture absorption rate constant. The dissolution rate constants were decreased with the increase of Hausner rate, monolayer adsorption capacity and adsorption heat constant, and were increased with the increase of Carr index and specific surface area. Adsorption heat constant, monolayer adsorption capacity, moisture absorption rate constant, Carr index and specific surface area were the key physical properties of hawthorn leaf granule to affect its dissolution behavior. Copyright© by the Chinese Pharmaceutical Association.

Characterization of the low-temperature properties of a simplified protein model

NASA Astrophysics Data System (ADS)

Hagmann, Johannes-Geert; Nakagawa, Naoko; Peyrard, Michel

2014-01-01

Prompted by results that showed that a simple protein model, the frustrated Gō model, appears to exhibit a transition reminiscent of the protein dynamical transition, we examine the validity of this model to describe the low-temperature properties of proteins. First, we examine equilibrium fluctuations. We calculate its incoherent neutron-scattering structure factor and show that it can be well described by a theory using the one-phonon approximation. By performing an inherent structure analysis, we assess the transitions among energy states at low temperatures. Then, we examine nonequilibrium fluctuations after a sudden cooling of the protein. We investigate the violation of the fluctuation-dissipation theorem in order to analyze the protein glass transition. We find that the effective temperature of the quenched protein deviates from the temperature of the thermostat, however it relaxes towards the actual temperature with an Arrhenius behavior as the waiting time increases. These results of the equilibrium and nonequilibrium studies converge to the conclusion that the apparent dynamical transition of this coarse-grained model cannot be attributed to a glassy behavior.

Self-consistent calculation of the nuclear composition in hot and dense stellar matter

NASA Astrophysics Data System (ADS)

Furusawa, Shun; Mishustin, Igor

2017-03-01

We investigate the mass fractions and in-medium properties of heavy nuclei in stellar matter at characteristic densities and temperatures for supernova (SN) explosions. The individual nuclei are described within the compressible liquid-drop model taking into account modifications of bulk, surface, and Coulomb energies. The equilibrium properties of nuclei and the full ensemble of heavy nuclei are calculated self-consistently. It is found that heavy nuclei in the ensemble are either compressed or decompressed depending on the isospin asymmetry of the system. The compression or decompression has a little influence on the binding energies, total mass fractions, and average mass numbers of heavy nuclei, although the equilibrium densities of individual nuclei themselves are changed appreciably above one-hundredth of normal nuclear density. We find that nuclear structure in the single-nucleus approximation deviates from the actual one obtained in the multinucleus description, since the density of free nucleons is different between these two descriptions. This study indicates that a multinucleus description is required to realistically account for in-medium effects on the nuclear structure in supernova matter.

Geometric integrator for simulations in the canonical ensemble

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tapias, Diego, E-mail: diego.tapias@nucleares.unam.mx; Sanders, David P., E-mail: dpsanders@ciencias.unam.mx; Computer Science and Artificial Intelligence Laboratory, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139

2016-08-28

We introduce a geometric integrator for molecular dynamics simulations of physical systems in the canonical ensemble that preserves the invariant distribution in equations arising from the density dynamics algorithm, with any possible type of thermostat. Our integrator thus constitutes a unified framework that allows the study and comparison of different thermostats and of their influence on the equilibrium and non-equilibrium (thermo-)dynamic properties of a system. To show the validity and the generality of the integrator, we implement it with a second-order, time-reversible method and apply it to the simulation of a Lennard-Jones system with three different thermostats, obtaining good conservationmore » of the geometrical properties and recovering the expected thermodynamic results. Moreover, to show the advantage of our geometric integrator over a non-geometric one, we compare the results with those obtained by using the non-geometric Gear integrator, which is frequently used to perform simulations in the canonical ensemble. The non-geometric integrator induces a drift in the invariant quantity, while our integrator has no such drift, thus ensuring that the system is effectively sampling the correct ensemble.« less

The equilibrium point hypothesis and its application to speech motor control.

PubMed

Perrier, P; Ostry, D J; Laboissière, R

1996-04-01

In this paper, we address a number of issues in speech research in the context of the equilibrium point hypothesis of motor control. The hypothesis suggests that movements arise from shifts in the equilibrium position of the limb or the speech articulator. The equilibrium is a consequence of the interaction of central neural commands, reflex mechanisms, muscle properties, and external loads, but it is under the control of central neural commands. These commands act to shift the equilibrium via centrally specified signals acting at the level of the motoneurone (MN) pool. In the context of a model of sagittal plane jaw and hyoid motion based on the lambda version of the equilibrium point hypothesis, we consider the implications of this hypothesis for the notion of articulatory targets. We suggest that simple linear control signals may underlie smooth articulatory trajectories. We explore as well the phenomenon of intraarticulator coarticulation in jaw movement. We suggest that even when no account is taken of upcoming context, that apparent anticipatory changes in movement amplitude and duration may arise due to dynamics. We also present a number of simulations that show in different ways how variability in measured kinematics can arise in spite of constant magnitude speech control signals.

The Secondary Organic Aerosol Processor (SOAP v1.0) model: a unified model with different ranges of complexity based on the molecular surrogate approach

NASA Astrophysics Data System (ADS)

Couvidat, F.; Sartelet, K.

2014-01-01

The Secondary Organic Aerosol Processor (SOAP v1.0) model is presented. This model is designed to be modular with different user options depending on the computing time and the complexity required by the user. This model is based on the molecular surrogate approach, in which each surrogate compound is associated with a molecular structure to estimate some properties and parameters (hygroscopicity, absorption on the aqueous phase of particles, activity coefficients, phase separation). Each surrogate can be hydrophilic (condenses only on the aqueous phase of particles), hydrophobic (condenses only on the organic phase of particles) or both (condenses on both the aqueous and the organic phases of particles). Activity coefficients are computed with the UNIFAC thermodynamic model for short-range interactions and with the AIOMFAC parameterization for medium and long-range interactions between electrolytes and organic compounds. Phase separation is determined by Gibbs energy minimization. The user can choose between an equilibrium and a dynamic representation of the organic aerosol. In the equilibrium representation, compounds in the particle phase are assumed to be at equilibrium with the gas phase. However, recent studies show that the organic aerosol (OA) is not at equilibrium with the gas phase because the organic phase could be semi-solid (very viscous liquid phase). The condensation or evaporation of organic compounds could then be limited by the diffusion in the organic phase due to the high viscosity. A dynamic representation of secondary organic aerosols (SOA) is used with OA divided into layers, the first layer at the center of the particle (slowly reaches equilibrium) and the final layer near the interface with the gas phase (quickly reaches equilibrium).

Trapped nonneutral plasmas, liquids, and crystals (the thermal equilibrium states)

NASA Astrophysics Data System (ADS)

Dubin, Daniel H.; O'neil, T. M.

1999-01-01

Plasmas consisting exclusively of particles with a single sign of charge (e.g., pure electron plasmas and pure ion plasmas) can be confined by static electric and magnetic fields (in a Penning trap) and also be in a state of global thermal equilibrium. This important property distinguishes these totally unneutralized plasmas from neutral and quasineutral plasmas. This paper reviews the conditions for, and the structure of, the thermal equilibrium states. Both theory and experiment are discussed, but the emphasis is decidedly on theory. It is a huge advantage to be able to use thermal equilibrium statistical mechanics to describe the plasma state. Such a description is easily obtained and complete, including for example the details of the plasma shape and microscopic order. Pure electron and pure ion plasmas are routinely confined for hours and even days, and thermal equilibrium states are observed. These plasmas can be cooled to the cryogenic temperature range, where liquid and crystal-like states are realized. The authors discuss the structure of the correlated states separately for three plasma sizes: large plasmas, in which the free energy is dominated by the bulk plasma; mesoscale plasmas, in which the free energy is strongly influenced by the surface; and Coulomb clusters, in which the number of particles is so small that the canonical ensemble is not a good approximation for the microcanonical ensemble. All three cases have been studied through numerical simulations, analytic theory, and experiment. In addition to describing the structure of the thermal equilibrium states, the authors develop a thermodynamic theory of the trapped plasma system. Thermodynamic inequalities and Maxwell relations provide useful bounds on and general relationships between partial derivatives of the various thermodynamic variables.

Combustion Gas Properties I-ASTM Jet a Fuel and Dry Air

NASA Technical Reports Server (NTRS)

Jones, R. E.; Trout, A. M.; Wear, J. D.; Mcbride, B. J.

1984-01-01

A series of computations was made to produce the equilibrium temperature and gas composition for ASTM jet A fuel and dry air. The computed tables and figures provide combustion gas property data for pressures from 0.5 to 50 atmospheres and equivalence ratios from 0 to 2.0.

Systems biology and the origins of life? part II. Are biochemical networks possible ancestors of living systems? networks of catalysed chemical reactions: non-equilibrium, self-organization and evolution.

PubMed

Ricard, Jacques

2010-01-01

The present article discusses the possibility that catalysed chemical networks can evolve. Even simple enzyme-catalysed chemical reactions can display this property. The example studied is that of a two-substrate proteinoid, or enzyme, reaction displaying random binding of its substrates A and B. The fundamental property of such a system is to display either emergence or integration depending on the respective values of the probabilities that the enzyme has bound one of its substrate regardless it has bound the other substrate, or, specifically, after it has bound the other substrate. There is emergence of information if p(A)>p(AB) and p(B)>p(BA). Conversely, if p(A)

Determination of prestress and elastic properties of virus capsids

NASA Astrophysics Data System (ADS)

Aggarwal, Ankush

2018-03-01

Virus capsids are protein shells that protect the virus genome, and determination of their mechanical properties has been a topic of interest because of their potential use in nanotechnology and therapeutics. It has been demonstrated that stresses exist in virus capsids, even in their equilibrium state, due to their construction. These stresses, termed "prestresses" in this study, closely affect the capsid's mechanical behavior. Three methods—shape-based metric, atomic force microscope indentation, and molecular dynamics—have been proposed to determine the capsid elastic properties without fully accounting for prestresses. In this paper, we theoretically analyze the three methods used for mechanical characterization of virus capsids and numerically investigate how prestresses affect the capsid's mechanical properties. We consolidate all the results and propose that by using these techniques collectively, it is possible to accurately determine both the mechanical properties and prestresses in capsids.

Labor union members play an OLG repeated game

PubMed Central

Kandori, Michihiro; Obayashi, Shinya

2014-01-01

Humans are capable of cooperating with one another even when it is costly and a deviation provides an immediate gain. An important reason is that cooperation is reciprocated or rewarded and deviations are penalized in later stages. For cooperation to be sustainable, not only must rewards and penalties be strong enough but individuals should also have the right incentives to provide rewards and punishments. Codes of conduct with such properties have been studied extensively in game theory (as repeated game equilibria), and the literature on the evolution of cooperation shows how equilibrium behavior might emerge and proliferate in society. We found that community unions, a subclass of labor unions that admits individual affiliations, are ideal to corroborate these theories with reality, because (i) their activities are simple and (ii) they have a structure that closely resembles a theoretical model, the overlapping generations repeated game. A detailed case study of a community union revealed a possible equilibrium that can function under the very limited observability in the union. The equilibrium code of conduct appears to be a natural focal point based on simple heuristic reasoning. The union we studied was created out of necessity for cooperation, without knowing or anticipating how cooperation might be sustained. The union has successfully resolved about 3,000 labor disputes and created a number of offspring. PMID:25024211

An exact collisionless equilibrium for the Force-Free Harris Sheet with low plasma beta

DOE Office of Scientific and Technical Information (OSTI.GOV)

Allanson, O., E-mail: oliver.allanson@st-andrews.ac.uk; Neukirch, T., E-mail: tn3@st-andrews.ac.uk; Wilson, F., E-mail: fw237@st-andrews.ac.uk

We present a first discussion and analysis of the physical properties of a new exact collisionless equilibrium for a one-dimensional nonlinear force-free magnetic field, namely, the force-free Harris sheet. The solution allows any value of the plasma beta, and crucially below unity, which previous nonlinear force-free collisionless equilibria could not. The distribution function involves infinite series of Hermite polynomials in the canonical momenta, of which the important mathematical properties of convergence and non-negativity have recently been proven. Plots of the distribution function are presented for the plasma beta modestly below unity, and we compare the shape of the distribution functionmore » in two of the velocity directions to a Maxwellian distribution.« less

Thermodynamic properties of minerals

USGS Publications Warehouse

Robie, Richard A.

1962-01-01

In the ten years since the publication of the national Bureau of Standards comprehensive tables of thermochemical properties, by Rossini and other (1952), a very large body of modern calorimetric and equilibrium data has become available. Because of the complex interrelations among many thermochemical data and the necessity for internal consistency among these values, a complete revision of this standard reference is required. This is also true of the summaries of thermochemical data for the sulfides (Richardson and Jeffes 1952) and for the oxides (Coughlin 1954). The following tables present critically selected values for the heat and free energy of formation, the logarithm of the equilibrium constant of formation Log Kf, the entropy and the molar volume, at 298.15°K (25.0°C) and one atmosphere for minerals.

Interfaces at equilibrium: A guide to fundamentals.

PubMed

Marmur, Abraham

2017-06-01

The fundamentals of the thermodynamics of interfaces are reviewed and concisely presented. The discussion starts with a short review of the elements of bulk thermodynamics that are also relevant to interfaces. It continues with the interfacial thermodynamics of two-phase systems, including the definition of interfacial tension and adsorption. Finally, the interfacial thermodynamics of three-phase (wetting) systems is discussed, including the topic of non-wettable surfaces. A clear distinction is made between equilibrium conditions, in terms of minimizing energies (internal, Gibbs or Helmholtz), and equilibrium indicators, in terms of measurable, intrinsic properties (temperature, chemical potential, pressure). It is emphasized that the equilibrium indicators are the same whatever energy is minimized, if the boundary conditions are properly chosen. Also, to avoid a common confusion, a distinction is made between systems of constant volume and systems with drops of constant volume. Copyright © 2016 Elsevier B.V. All rights reserved.

N-Methyl Inversion and Accurate Equilibrium Structures in Alkaloids: Pseudopelletierine.

PubMed

Vallejo-López, Montserrat; Écija, Patricia; Vogt, Natalja; Demaison, Jean; Lesarri, Alberto; Basterretxea, Francisco J; Cocinero, Emilio J

2017-11-21

A rotational spectroscopy investigation has resolved the conformational equilibrium and structural properties of the alkaloid pseudopelletierine. Two different conformers, which originate from inversion of the N-methyl group from an axial to an equatorial position, have been unambiguously identified in the gas phase, and nine independent isotopologues have been recorded by Fourier-transform microwave spectroscopy in a jet expansion. Both conformers share a chair-chair configuration of the two bridged six-membered rings. The conformational equilibrium is displaced towards the axial form, with a relative population in the supersonic jet of N axial /N equatorial ≈2/1. An accurate equilibrium structure has been determined by using the semiexperimental mixed-estimation method and alternatively computed by quantum-chemical methods up to the coupled-cluster level of theory. A comparison with the N-methyl inversion equilibria in related tropanes is also presented. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mercury adsorption properties of sulfur-impregnated adsorbents

USGS Publications Warehouse

Hsi, N.-C.; Rood, M.J.; Rostam-Abadi, M.; Chen, S.; Chang, R.

2002-01-01

Carbonaceous and noncarbonaceous adsorbents were impregnated with elemental sulfur to evaluate the chemical and physical properties of the adsorbents and their equilibrium mercury adsorption capacities. Simulated coal combustion flue gas conditions were used to determine the equilibrium adsorption capacities for Hg0 and HgCl2 gases to better understand how to remove mercury from gas streams generated by coal-fired utility power plants. Sulfur was deposited onto the adsorbents by monolayer surface deposition or volume pore filling. Sulfur impregnation increased the total sulfur content and decreased the total and micropore surface areas and pore volumes for all of the adsorbents tested. Adsorbents with sufficient amounts of active adsorption sites and sufficient microporous structure had mercury adsorption capacities up to 4,509 ??g Hg/g adsorbent. Elemental sulfur, organic sulfur, and sulfate were formed on the adsorbents during sulfur impregnation. Correlations were established with R2>0.92 between the equilibrium Hg0/HgCl2 adsorption capacities and the mass concentrations of elemental and organic sulfur. This result indicates that elemental and organic sulfur are important active adsorption sites for Hg0 and HgCl2.

Functional organization of mitotic microtubules. Physical chemistry of the in vivo equilibrium system.

PubMed Central

Inoué, S; Fuseler, J; Salmon, E D; Ellis, G W

1975-01-01

Equilibrium between mitotic microtubules and tubulin is analyzed, using birefringence of mitotic spindle to measure microtubule concentration in vivo. A newly designed temperature-controlled slide and miniature, thermostated hydrostatic pressure chamber permit rapid alteration of temperature and of pressure. Stress birefringence of the windows is minimized, and a system for rapid recording of compensation is incorporated, so that birefringence can be measured to 0.1 nm retardation every few seconds. Both temperature and pressure data yield thermodynamic values (delta H similar to 35 kcal/mol, delta S similar to 120 entropy units [eu], delta V similar to 400 ml/mol of subunit polymerized) consistent with the explanation that polymerization of tubulin is entropy driven and mediated by hydrophobic interactions. Kinetic data suggest pseudo-zero-order polymerization and depolymerization following rapid temperature shifts, and a pseudo-first-order depolymerization during anaphase at constant temperature. The equilibrium properties of the in vivo mitotic microtubules are compared with properties of isolated brain tubules. Images FIGURE 1 FIGURE 2 FIGURE 5 FIGURE 12 FIGURE 13 FIGURE 14 FIGURE 19 PMID:1139037

Elasticity and Fluctuations of Frustrated Nanoribbons

NASA Astrophysics Data System (ADS)

Grossman, Doron; Sharon, Eran; Diamant, Haim

2016-06-01

We derive a reduced quasi-one-dimensional theory of geometrically frustrated elastic ribbons. Expressed in terms of geometric properties alone, it applies to ribbons over a wide range of scales, allowing the study of their elastic equilibrium, as well as thermal fluctuations. We use the theory to account for the twisted-to-helical transition of ribbons with spontaneous negative curvature and the effect of fluctuations on the corresponding critical exponents. The persistence length of such ribbons changes nonmonotonically with the ribbon's width, dropping to zero at the transition. This and other statistical properties qualitatively differ from those of nonfrustrated fluctuating filaments.

Rhenium-phthalocyanine molecular nanojunction with high magnetic anisotropy and high spin filtering efficiency

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, J.; Institute of Nanomaterial and Nanostructure, Changsha University of Science and Technology, Changsha 410114; Hu, J.

2015-07-20

Using the density functional and non-equilibrium Green's function approaches, we studied the magnetic anisotropy and spin-filtering properties of various transition metal-Phthalocyanine molecular junctions across two Au electrodes. Our important finding is that the Au-RePc-Au junction has both large spin filtering efficiency (>80%) and large magnetic anisotropy energy, which makes it suitable for device applications. To provide insights for the further experimental work, we discussed the correlation between the transport property, magnetic anisotropy, and wave function features of the RePc molecule, and we also illustrated the possibility of controlling its magnetic state.

Tunable terahertz optical properties of graphene in dc electric fields

NASA Astrophysics Data System (ADS)

Dong, H. M.; Huang, F.; Xu, W.

2018-03-01

We develop a simple theoretical approach to investigate terahertz (THz) optical properties of monolayer graphene in the presence of an external dc electric field. The analytical results for optical coefficients such as the absorptance and reflectivity are obtained self-consistently on the basis of a diagrammatic self-consistent field theory and a Boltzmann equilibrium equation. It is found that the optical refractive index, reflectivity and conductivity can be effectively tuned by not only a gate voltage but also a driving dc electric field. This study is relevant to the applications of graphene as advanced THz optoelectronic devices.

Evidence for a Shared Mechanism in the Formation of Urea-Induced Kinetic and Equilibrium Intermediates of Horse Apomyoglobin from Ultrarapid Mixing Experiments

PubMed Central

Mizukami, Takuya; Abe, Yukiko; Maki, Kosuke

2015-01-01

In this study, the equivalence of the kinetic mechanisms of the formation of urea-induced kinetic folding intermediates and non-native equilibrium states was investigated in apomyoglobin. Despite having similar structural properties, equilibrium and kinetic intermediates accumulate under different conditions and via different mechanisms, and it remains unknown whether their formation involves shared or distinct kinetic mechanisms. To investigate the potential mechanisms of formation, the refolding and unfolding kinetics of horse apomyoglobin were measured by continuous- and stopped-flow fluorescence over a time range from approximately 100 μs to 10 s, along with equilibrium unfolding transitions, as a function of urea concentration at pH 6.0 and 8°C. The formation of a kinetic intermediate was observed over a wider range of urea concentrations (0–2.2 M) than the formation of the native state (0–1.6 M). Additionally, the kinetic intermediate remained populated as the predominant equilibrium state under conditions where the native and unfolded states were unstable (at ~0.7–2 M urea). A continuous shift from the kinetic to the equilibrium intermediate was observed as urea concentrations increased from 0 M to ~2 M, which indicates that these states share a common kinetic folding mechanism. This finding supports the conclusion that these intermediates are equivalent. Our results in turn suggest that the regions of the protein that resist denaturant perturbations form during the earlier stages of folding, which further supports the structural equivalence of transient and equilibrium intermediates. An additional folding intermediate accumulated within ~140 μs of refolding and an unfolding intermediate accumulated in <1 ms of unfolding. Finally, by using quantitative modeling, we showed that a five-state sequential scheme appropriately describes the folding mechanism of horse apomyoglobin. PMID:26244984

A Novel Method for Dynamic Short-Beam Shear Testing of 3D Woven Composites

DTIC Science & Technology

2011-08-11

specimen was homogenized as an orthotropic elastic material with properties given in Table 1 [38]. The use of fully elastic model removes any material...impact event however after approximately 0.5 mm of deflection, equilibrium is reached. It is observed from Fig. 4(d) that equilibrium is never fully ...The public reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing

User's guide for vectorized code EQUIL for calculating equilibrium chemistry on Control Data STAR-100 computer

NASA Technical Reports Server (NTRS)

Kumar, A.; Graves, R. A., Jr.; Weilmuenster, K. J.

1980-01-01

A vectorized code, EQUIL, was developed for calculating the equilibrium chemistry of a reacting gas mixture on the Control Data STAR-100 computer. The code provides species mole fractions, mass fractions, and thermodynamic and transport properties of the mixture for given temperature, pressure, and elemental mass fractions. The code is set up for the electrons H, He, C, O, N system of elements. In all, 24 chemical species are included.

Fugacity of H2O from 0° to 350°C at the liquid-vapor equilibrium and at 1 atmosphere

USGS Publications Warehouse

Hass, John L.

1970-01-01

The fugacity and fugacity coefficient of H2O at the liquid-vapor equilibrium, the fugacity and the Gibbs free energy of formation of H2O at 1 atm (1.01325 bars) total pressure have been calculated from published data on the physical and thermodynamic properties of H2O and are presented at ten-degree intervals from 0° to 350°C.

Non-equilibrium character of resistive switching and negative differential resistance in Ga-doped Cr2O3 system

NASA Astrophysics Data System (ADS)

Bhowmik, R. N.; Siva, K. Venkata

2018-07-01

The samples of Ga-doped Cr2O3 system in rhombohedral crystal structure with space group R 3 bar C were prepared by chemical co-precipitation route and annealing at 800 °C. The current-voltage (I-V) curves exhibited many unique non-linear properties, e.g., hysteresis loop, resistive switching, and negative differential resistance (NDR). In this work, we report non-equilibrium properties of resistive switching and NDR phenomena. The non-equilibrium I-V characteristics were confirmed by repetiting measurement and time relaxation of current. The charge conduction process was understood by analysing the I-V curves using electrode-limited and bulk-limited charge conduction mechanisms, which were proposed for metal electrode/metal oxide/metal electrode structure. The I-V curves in the NDR regime and at higher bias voltage regime in our samples did not obey Fowler-Nordheim equation, which was proposed for charge tunneling mechanism in many thin film junctions. The non-equilibrium I-V phenomena were explained by considering the competitions between the injection of charge carriers from metal electrode to metal oxide, the charge flow through bulk material mediated by trapping/de-trapping and recombination of charge carriers at the defect sites of ions, the space charge effects at the junctions of electrodes and metal oxides, and finally, the out flow of electrons from metal oxide to metal electrode.

A Theoretically Informed Model for the Rheology of Entangled Block Copolymer Nanocomposites

NASA Astrophysics Data System (ADS)

Su, Yongrui; Ramirez-Hernandez, Abelardo; Peters, Brandon; de Pablo, Juan J.

2014-03-01

The addition of nanoparticles to block copolymer systems has been shown to have important effects on their equilibrium structure and properties. Less is known about the non-equilibrium behavior of block polymer nanocomposites. A new particle-based, theoretically informed coarse-grained model for multicomponent nanocomposites is proposed to examine the effects of nanoparticles on the rheology of entangled block copolymer melts. Entanglements are treated at the two-molecule level, through slip-springs that couple the dynamics of neighboring pairs of chains. The inclusion of slip-springs changes the polymer dynamics from unentangled to entangled. The nanoparticles are functionalized with short polymer chains that can entangle with the copolymers. We study the nonlinear rheology of the resulting nanocomposites under shear flow with a dissipative particle dynamics (DPD) thermostat.

Significance of vapor phase chemical reactions on CVD rates predicted by chemically frozen and local thermochemical equilibrium boundary layer theories

NASA Technical Reports Server (NTRS)

Gokoglu, Suleyman A.

1988-01-01

This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.

Equilibrium structures of carbon diamond-like clusters and their elastic properties

NASA Astrophysics Data System (ADS)

Lisovenko, D. S.; Baimova, Yu. A.; Rysaeva, L. Kh.; Gorodtsov, V. A.; Dmitriev, S. V.

2017-04-01

Three-dimensional carbon diamond-like phases consisting of sp 3-hybridized atoms, obtained by linking of carcasses of fullerene-like molecules, are studied by methods of molecular dynamics modeling. For eight cubic and one hexagonal diamond-like phases on the basis of four types of fullerene-like molecules, equilibrium configurations are found and the elastic constants are calculated. The results obtained by the method of molecular dynamics are used for analytical calculations of the elastic characteristics of the diamond- like phases with the cubic and hexagonal anisotropy. It is found that, for a certain choice of the dilatation axis, three of these phases have negative Poisson's ratio, i.e., are partial auxetics. The variability of the engineering elasticity coefficients (Young's modulus, Poisson's ratio, shear modulus, and bulk modulus) is analyzed.

Kinetic and equilibrium studies of acrylonitrile binding to cytochrome c peroxidase and oxidation of acrylonitrile by cytochrome c peroxidase compound I.

PubMed

Chinchilla, Diana; Kilheeney, Heather; Vitello, Lidia B; Erman, James E

2014-01-03

Ferric heme proteins bind weakly basic ligands and the binding affinity is often pH dependent due to protonation of the ligand as well as the protein. In an effort to find a small, neutral ligand without significant acid/base properties to probe ligand binding reactions in ferric heme proteins we were led to consider the organonitriles. Although organonitriles are known to bind to transition metals, we have been unable to find any prior studies of nitrile binding to heme proteins. In this communication we report on the equilibrium and kinetic properties of acrylonitrile binding to cytochrome c peroxidase (CcP) as well as the oxidation of acrylonitrile by CcP compound I. Acrylonitrile binding to CcP is independent of pH between pH 4 and 8. The association and dissociation rate constants are 0.32±0.16 M(-1) s(-1) and 0.34±0.15 s(-1), respectively, and the independently measured equilibrium dissociation constant for the complex is 1.1±0.2 M. We have demonstrated for the first time that acrylonitrile can bind to a ferric heme protein. The binding mechanism appears to be a simple, one-step association of the ligand with the heme iron. We have also demonstrated that CcP can catalyze the oxidation of acrylonitrile, most likely to 2-cyanoethylene oxide in a "peroxygenase"-type reaction, with rates that are similar to rat liver microsomal cytochrome P450-catalyzed oxidation of acrylonitrile in the monooxygenase reaction. CcP compound I oxidizes acrylonitrile with a maximum turnover number of 0.61 min(-1) at pH 6.0. Copyright © 2013 Elsevier Inc. All rights reserved.

Synthesis, structure and study of azo-hydrazone tautomeric equilibrium of 1,3-dimethyl-5-(arylazo)-6-amino-uracil derivatives.

PubMed

Debnath, Diptanu; Roy, Subhadip; Li, Bing-Han; Lin, Chia-Her; Misra, Tarun Kumar

2015-04-05

Azo dyes, 1,3-dimethyl-5-(arylazo)-6-aminouracil (aryl=-C6H5 (1), -p-CH3C6H4 (2), -p-ClC6H4 (3), -p-NO2C6H4 (4)) were prepared and characterized by UV-vis, FT-IR, 1H NMR, 13C NMR spectroscopic techniques and single crystal X-ray crystallographic analysis. In the light of spectroscopic analysis it evidences that of the tautomeric forms, the azo-enamine-keto (A) form is the predominant form in the solid state whereas in different solvents it is the hydrazone-imine-keto (B) form. The study also reveals that the hydrazone-imine-keto (B) form exists in an equilibrium mixture with its anionic form in various organic solvents. The solvatochromic and photophysical properties of the dyes in various solvents with different hydrogen bonding parameter were investigated. The dyes exhibit positive solvatochromic property on moving from polar protic to polar aprotic solvents. They are fluorescent active molecules and exhibit high intense fluorescent peak in some solvents like DMSO and DMF. It has been demonstrated that the anionic form of the hydrazone-imine form is responsible for the high intense fluorescent peak. In addition, the acid-base equilibrium in between neutral and anionic form of hydrazone-imine form in buffer solution of varying pH was investigated and evaluated the pKa values of the dyes by making the use of UV-vis spectroscopic methods. The determined acid dissociation constant (pKa) values increase according to the sequence of 2>1>3>4. Copyright © 2014 Elsevier B.V. All rights reserved.

Kinetic and equilibrium studies of acrylonitrile binding to cytochrome c peroxidase and oxidation of acrylonitrile by cytochrome c peroxidase compound I

PubMed Central

Chinchilla, Diana; Kilheeney, Heather; Vitello, Lidia B.; Erman, James E.

2013-01-01

Ferric heme proteins bind weakly basic ligands and the binding affinity is often pH dependent due to protonation of the ligand as well as the protein. In an effort to find a small, neutral ligand without significant acid/base properties to probe ligand binding reactions in ferric heme proteins we were led to consider the organonitriles. Although organonitriles are known to bind to transition metals, we have been unable to find any prior studies of nitrile binding to heme proteins. In this communication we report on the equilibrium and kinetic properties of acrylonitrile binding to cytochrome c peroxidase (CcP) as well as the oxidation of acrylonitrile by CcP compound I. Acrylonitrile binding to CcP is independent of pH between pH 4 and 8. The association and dissociation rate constants are 0.32 ± 0.16 M−1s−1 and 0.34 ± 0.15 s−1, respectively, and the independently measured equilibrium dissociation constant for the complex is 1.1 ± 0.2 M. We have demonstrated for the first time that acrylonitrile can bind to a ferric heme protein. The binding mechanism appears to be a simple, one-step association of the ligand with the heme iron. We have also demonstrated that CcP can catalyze the oxidation of acrylonitrile, most likely to 2-cyanoethylene oxide in a “peroxygenase”-type reaction, with rates that are similar to rat liver microsomal cytochrome P450-catalyzed oxidation of acrylonitrile in the monooxygenase reaction. CcP compound I oxidizes acrylonitrile with a maximum turnover number of 0.61 min−1 at pH 6.0. PMID:24291498

Effects of initial saturation on properties modification and displacement of tetrachloroethene with aqueous isobutanol.

PubMed

Boyd, Glen R; Ocampo-Gómez, Ana M; Li, Minghua; Husserl, Johana

2006-11-20

Packed column experiments were conducted to study effects of initial saturation of tetrachloroethene (PCE) in the range of 1.0-14% pore volume (PV) on mobilization and downward migration of the non-aqueous phase liquid (NAPL) product upon contact with aqueous isobutanol ( approximately 10 vol.%). This study focused on the consequences of swelling beyond residual saturation. Columns were packed with mixtures of neat PCE, water and glass beads and waterflooded to establish a desired homogeneous residual saturation, and then flooded with aqueous isobutanol under controlled hydraulic conditions. Results showed a critical saturation of approximately 8% PV for these packed column experimental conditions. At low initial PCE saturations (<8% PV), experimental results showed reduced risk of NAPL-product migration upon contact with aqueous isobutanol. At higher initial PCE saturations (>8% PV), results showed NAPL-product mobilization and downward migration which was attributed to interfacial tension (IFT) reduction, swelling of the NAPL-product, and reduced density modification. Packed column results were compared with good agreement to theoretical predictions of NAPL-product mobilization using the total trapping number, N(T). In addition to the packed column study, preliminary batch experiments were conducted to study the effects of PCE volumetric fraction in the range of 0.5-20% on density, viscosity, and IFT modification as a function of time following contact with aqueous isobutanol ( approximately 10 vol.%). Modified NAPL-product fluid properties approached equilibrium within approximately 2 h of contact for density and viscosity. IFT reduction occurred immediately as expected. Measured fluid properties were compared with good agreement to theoretical equilibrium predictions based on UNIQUAC. Overall, this study demonstrates the importance of initial DNAPL saturation, and the associated risk of downward NAPL-product migration, in applying alcohol flooding for remediation of DNAPL contaminated ground water sites.

The Precise Measurement of Vapor-Liquid Equilibrium Properties of the CO2/Isopentane Binary Mixture, and Fitted Parameters for a Helmholtz Energy Mixture Model

NASA Astrophysics Data System (ADS)

Miyamoto, H.; Shoji, Y.; Akasaka, R.; Lemmon, E. W.

2017-10-01

Natural working fluid mixtures, including combinations of CO2, hydrocarbons, water, and ammonia, are expected to have applications in energy conversion processes such as heat pumps and organic Rankine cycles. However, the available literature data, much of which were published between 1975 and 1992, do not incorporate the recommendations of the Guide to the Expression of Uncertainty in Measurement. Therefore, new and more reliable thermodynamic property measurements obtained with state-of-the-art technology are required. The goal of the present study was to obtain accurate vapor-liquid equilibrium (VLE) properties for complex mixtures based on two different gases with significant variations in their boiling points. Precise VLE data were measured with a recirculation-type apparatus with a 380 cm3 equilibration cell and two windows allowing observation of the phase behavior. This cell was equipped with recirculating and expansion loops that were immersed in temperature-controlled liquid and air baths, respectively. Following equilibration, the composition of the sample in each loop was ascertained by gas chromatography. VLE data were acquired for CO2/ethanol and CO2/isopentane binary mixtures within the temperature range from 300 K to 330 K and at pressures up to 7 MPa. These data were used to fit interaction parameters in a Helmholtz energy mixture model. Comparisons were made with the available literature data and values calculated by thermodynamic property models.

First-principles study of structural and electronic properties of Be0.25Zn0.75S mixed compound

NASA Astrophysics Data System (ADS)

Paliwal, U.; Joshi, K. B.

2018-05-01

In this work the first-principles study of structural and electronic properties of Be0.25Zn0.75S mixed compound is presented. The calculations are performed applying the QUANTUM ESPRESSO code utilizing the Perdew, Becke, Ernzerhof generalized gradient approximation in the framework of density functional theory. Adopting standard optimization strategy, the ground state equilibrium lattice constant and bulk modulus are calculated. After settling the structure the electronic band structure, bandgap and static dielectric constant are evaluated. In absence of any experimental work on this system our findings are compared with the available theoretical calculations which are found to follow well anticipated general trends.

Photo-crosslinked alginate hydrogels support enhanced matrix accumulation by nucleus pulposus cells in vivo.

PubMed

Chou, A I; Akintoye, S O; Nicoll, S B

2009-10-01

Intervertebral disc (IVD) degeneration is a major health concern in the United States. Replacement of the nucleus pulposus (NP) with injectable biomaterials represents a potential treatment strategy for IVD degeneration. The objective of this study was to characterize the extracellular matrix (ECM) assembly and functional properties of NP cell-encapsulated, photo-crosslinked alginate hydrogels in comparison to ionically crosslinked alginate constructs. Methacrylated alginate was synthesized by esterification of hydroxyl groups with methacrylic anhydride. Bovine NP cells were encapsulated in alginate hydrogels by ionic crosslinking using CaCl(2) or through photo-crosslinking upon exposure to long-wave UV light in the presence of a photoinitiator. The hydrogels were evaluated in vitro by gross and histological analysis and in vivo using a murine subcutaneous pouch model. In vivo samples were analyzed for gene expression, ECM localization and accumulation, and equilibrium mechanical properties. Ionically crosslinked hydrogels exhibited inferior proteoglycan accumulation in vitro and were unable to maintain structural integrity in vivo. In further studies, photo-crosslinked alginate hydrogels were implanted for up to 8 weeks to examine NP tissue formation. Photo-crosslinked hydrogels displayed temporal increases in gene expression and assembly of type II collagen and proteoglycans. Additionally, hydrogels remained intact over the duration of the study and the equilibrium Young's modulus increased from 1.24+/-0.09 kPa to 4.31+/-1.39 kPa, indicating the formation of functional matrix with properties comparable to those of the native NP. These findings support the use of photo-crosslinked alginate hydrogels as biomaterial scaffolds for NP replacement.

Molecular-dynamics simulations of crosslinking and confinement effects on structure, segmental mobility and mechanics of filled elastomers

NASA Astrophysics Data System (ADS)

Davris, Theodoros; Lyulin, Alexey V.

2016-05-01

The significant drop of the storage modulus under uniaxial deformation (Payne effect) restrains the performance of the elastomer-based composites and the development of possible new applications. In this paper molecular-dynamics (MD) computer simulations using LAMMPS MD package have been performed to study the mechanical properties of a coarse-grained model of this family of nanocomposite materials. Our goal is to provide simulational insights into the viscoelastic properties of filled elastomers, and try to connect the macroscopic mechanics with composite microstructure, the strength of the polymer-filler interactions and the polymer mobility at different scales. To this end we simulate random copolymer films capped between two infinite solid (filler aggregate) walls. We systematically vary the strength of the polymer-substrate adhesion interactions, degree of polymer confinement (film thickness), polymer crosslinking density, and study their influence on the equilibrium and non-equilibrium structure, segmental dynamics, and the mechanical properties of the simulated systems. The glass-transition temperature increases once the mesh size became smaller than the chain radius of gyration; otherwise it remained invariant to mesh-size variations. This increase in the glass-transition temperature was accompanied by a monotonic slowing-down of segmental dynamics on all studied length scales. This observation is attributed to the correspondingly decreased width of the bulk density layer that was obtained in films whose thickness was larger than the end-to-end distance of the bulk polymer chains. To test this hypothesis additional simulations were performed in which the crystalline walls were replaced with amorphous or rough walls.

Statics and dynamics of DNA knotting

NASA Astrophysics Data System (ADS)

Orlandini, Enzo

2018-02-01

Knots and entanglement in polymers and biopolymers such as DNA and proteins constitute a timely topic that spans various scientific disciplines ranging from physics to chemistry, biology and mathematics. Although in the past many advancements have been made in understanding the equilibrium knotting probability and knot complexity of long polymer chains in solutions, many questions have been addressed in recent years by both experimental and theoretical means—for instance, how the knotting probability depends on the quality of the solvent, the elastic properties of the molecule and its degree of confinement. How knots form, evolve and eventually disappear in a fluctuating chain. Are the equilibrium and non-equilibrium properties of knotted molecules affected by the knot swelling/shrinking dynamics? Moreover, thanks to the great advance in nanotechnology and micromanipulation techniques, nowadays knots can be ‘manually’ tied in a single DNA molecule, followed during their motion along the chains, forced to pass through nanopores, or stretched by external forces or elongational flows. All these experimental approaches allow access to new information on the interplay of topology and polymer physics, and this has opened new perspectives in the field. Here, we provide an overview of the current knowledge of this topic, stressing the main results obtained, including the recent developments in experimental and computational approaches. Since almost all experiments on knotting involve DNA, the review will be mainly focused on the topological properties of this fascinating and biologically relevant molecule.

Strong DNA deformation required for extremely slow DNA threading intercalation by a binuclear ruthenium complex

PubMed Central

Almaqwashi, Ali A.; Paramanathan, Thayaparan; Lincoln, Per; Rouzina, Ioulia; Westerlund, Fredrik; Williams, Mark C.

2014-01-01

DNA intercalation by threading is expected to yield high affinity and slow dissociation, properties desirable for DNA-targeted therapeutics. To measure these properties, we utilize single molecule DNA stretching to quantify both the binding affinity and the force-dependent threading intercalation kinetics of the binuclear ruthenium complex Δ,Δ-[μ‐bidppz‐(phen)4Ru2]4+ (Δ,Δ-P). We measure the DNA elongation at a range of constant stretching forces using optical tweezers, allowing direct characterization of the intercalation kinetics as well as the amount intercalated at equilibrium. Higher forces exponentially facilitate the intercalative binding, leading to a profound decrease in the binding site size that results in one ligand intercalated at almost every DNA base stack. The zero force Δ,Δ-P intercalation Kd is 44 nM, 25-fold stronger than the analogous mono-nuclear ligand (Δ-P). The force-dependent kinetics analysis reveals a mechanism that requires DNA elongation of 0.33 nm for association, relaxation to an equilibrium elongation of 0.19 nm, and an additional elongation of 0.14 nm from the equilibrium state for dissociation. In cells, a molecule with binding properties similar to Δ,Δ-P may rapidly bind DNA destabilized by enzymes during replication or transcription, but upon enzyme dissociation it is predicted to remain intercalated for several hours, thereby interfering with essential biological processes. PMID:25245944

Implementation of equilibrium aqueous speciation and solubility (EQ3 type) calculations into Cantera for electrolyte solutions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moffat, Harry K.; Jove-Colon, Carlos F.

2009-06-01

In this report, we summarize our work on developing a production level capability for modeling brine thermodynamic properties using the open-source code Cantera. This implementation into Cantera allows for the application of chemical thermodynamics to describe the interactions between a solid and an electrolyte solution at chemical equilibrium. The formulations to evaluate the thermodynamic properties of electrolytes are based on Pitzer's model to calculate molality-based activity coefficients using a real equation-of-state (EoS) for water. In addition, the thermodynamic properties of solutes at elevated temperature and pressures are computed using the revised Helgeson-Kirkham-Flowers (HKF) EoS for ionic and neutral aqueous species.more » The thermodynamic data parameters for the Pitzer formulation and HKF EoS are from the thermodynamic database compilation developed for the Yucca Mountain Project (YMP) used with the computer code EQ3/6. We describe the adopted equations and their implementation within Cantera and also provide several validated examples relevant to the calculations of extensive properties of electrolyte solutions.« less

Effect of Dermatan Sulfate on the Indentation and Tensile Properties of Articular Cartilage

PubMed Central

Hall, Melanie L.; Krawczak, David A.; Simha, Narendra K.; Lewis, Jack L.

2009-01-01

Objective This paper examines the hypothesis that the dermatan sulfate (DS) chain on decorin is a load carrying element in cartilage and that its damage or removal will alter the material properties. Methods To test this hypothesis, indentation and tensile testing of cartilage from bovine patella was performed before and after digestion with chondroitinase B (cB). Removal of significant amounts of DS by cB digestion was verified by Western blot analysis of proteoglycans extracted from whole and sectioned specimens. Specimens (control and treated) were subjected to a series of step-hold displacements. Elastic modulus during the step rise (rapid modulus) and at equilibrium (equilibrium modulus), and the relaxation function during each step were measured for test (cB and buffer) and control (buffer alone) conditions. Results cB had no effect on any of the viscoelastic mechanical properties measured, either in indentation or tension Conclusion Removing or damaging approximately 50% of the dermatan sulfate had no effect on the mechanical properties, strongly suggesting that dermatan sulfate either carries very low load or no load. PMID:19036614

Thermodynamics and kinetics of vesicles formation processes.

PubMed

Guida, Vincenzo

2010-12-15

Vesicles are hollow aggregates, composed of bilayers of amphiphilic molecules, dispersed into and filled with a liquid solvent. These aggregates can be formed either as equilibrium or as out of equilibrium meta-stable structures and they exhibit a rich variety of different morphologies. The surprising richness of structures, the vast range of industrial applications and the presence of vesicles in a number of biological systems have attracted the interest of numerous researchers and scientists. In this article, we review both the thermodynamics and the kinetics aspects of the phenomena of formation of vesicles. We start presenting the thermodynamics of bilayer membranes formation and deformation, with the aim of deriving the conditions for the existence of equilibrium vesicles. Specifically, we use the results from continuum thermodynamics to discuss the possibility of formation of stable equilibrium vesicles, from both mixed amphiphiles and single component systems. We also link the bilayer membrane properties to the molecular structure of the starting amphiphiles. In the second part of this article, we focus on the dynamics and kinetics of vesiculation. We review the process of vesicles formation both from planar lamellar phase under shear and from isotropic micelles. In order to clarify the physical mechanisms of vesicles formation, we continuously draw a parallel between emulsification and vesiculation processes. Specifically, we compare the experimental results, the driving forces and the relative scaling laws identified for the two processes. Describing the dynamics of vesicles formation, we also discuss why non equilibrium vesicles can be formed by kinetics control and why they are meta-stable. Understanding how to control the properties, the stability and the formation process of vesicles is of fundamental importance for a vast number of industrial applications. Copyright © 2009. Published by Elsevier B.V.

Effect of Annealing Treatment on Mechanical Properties of Nanocrystalline α-iron: an Atomistic Study

PubMed Central

Tong, Xuhang; Zhang, Hao; Li, D. Y.

2015-01-01

Claims are often found in the literature that metallic materials can be nanocrystallized by severe plastic deformation (SPD). However, SPD does not generate a well-defined nanocrystalline (NC) material, which can be achieved by subsequent annealing/recovery treatment. In this study, molecular dynamics (MD) simulation is employed to study the effect of annealing on structure and mechanical properties of cyclic deformed NC α-iron, which simulates SPD-processed α-iron. It is demonstrated that grain boundaries in the deformed NC α-iron evolve to a more equilibrium state during annealing, eliminating or minimizing the residual stress. The annealing treatment increases the system's strength by reducing dislocation emission sources, and improves material ductility through strengthening grain boundaries' resistance to intergranular cracks. The results indicate that the annealing treatment is an essential process for obtaining a well-defined NC structure with superior mechanical properties. PMID:25675978

Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles

NASA Technical Reports Server (NTRS)

Liechty, Derek S.; Lewis, Mark J.

2010-01-01

Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

Liquid-glass transition in equilibrium

NASA Astrophysics Data System (ADS)

Parisi, G.; Seoane, B.

2014-02-01

We show in numerical simulations that a system of two coupled replicas of a binary mixture of hard spheres undergoes a phase transition in equilibrium at a density slightly smaller than the glass transition density for an unreplicated system. This result is in agreement with the theories that predict that such a transition is a precursor of the standard ideal glass transition. The critical properties are compatible with those of an Ising system. The relations of this approach to the conventional approach based on configurational entropy are briefly discussed.

Some properties of correlations of quantum lattice systems in thermal equilibrium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fröhlich, Jürg, E-mail: juerg@phys.ethz.ch; Ueltschi, Daniel, E-mail: daniel@ueltschi.org

Simple proofs of uniqueness of the thermodynamic limit of KMS states and of the decay of equilibrium correlations are presented for a large class of quantum lattice systems at high temperatures. New quantum correlation inequalities for general Heisenberg models are described. Finally, a simplified derivation of a general result on power-law decay of correlations in 2D quantum lattice systems with continuous symmetries is given, extending results of McBryan and Spencer for the 2D classical XY model.

Real gas flow fields about three dimensional configurations

NASA Technical Reports Server (NTRS)

Balakrishnan, A.; Lombard, C. K.; Davy, W. C.

1983-01-01

Real gas, inviscid supersonic flow fields over a three-dimensional configuration are determined using a factored implicit algorithm. Air in chemical equilibrium is considered and its local thermodynamic properties are computed by an equilibrium composition method. Numerical solutions are presented for both real and ideal gases at three different Mach numbers and at two different altitudes. Selected results are illustrated by contour plots and are also tabulated for future reference. Results obtained compare well with existing tabulated numerical solutions and hence validate the solution technique.

Equilibrium fractionation of H and O isotopes in water from path integral molecular dynamics

NASA Astrophysics Data System (ADS)

Pinilla, Carlos; Blanchard, Marc; Balan, Etienne; Ferlat, Guillaume; Vuilleumier, Rodolphe; Mauri, Francesco

2014-06-01

The equilibrium fractionation factor between two phases is of importance for the understanding of many planetary and environmental processes. Although thermodynamic equilibrium can be achieved between minerals at high temperature, many natural processes involve reactions between liquids or aqueous solutions and solids. For crystals, the fractionation factor α can be theoretically determined using a statistical thermodynamic approach based on the vibrational properties of the phases. These calculations are mostly performed in the harmonic approximation, using empirical or ab-initio force fields. In the case of aperiodic and dynamic systems such as liquids or solutions, similar calculations can be done using finite-size molecular clusters or snapshots obtained from molecular dynamics (MD) runs. It is however difficult to assess the effect of these approximate models on the isotopic fractionation properties. In this work we present a systematic study of the calculation of the D/H and 18O/16O equilibrium fractionation factors in water for the liquid/vapour and ice/vapour phases using several levels of theory within the simulations. Namely, we use a thermodynamic integration approach based on Path Integral MD calculations (PIMD) and an empirical potential model of water. Compared with standard MD, PIMD takes into account quantum effects in the thermodynamic modeling of systems and the exact fractionation factor for a given potential can be obtained. We compare these exact results with those of modeling strategies usually used, which involve the mapping of the quantum system on its harmonic counterpart. The results show the importance of including configurational disorder for the estimation of isotope fractionation in liquid phases. In addition, the convergence of the fractionation factor as a function of parameters such as the size of the simulated system and multiple isotope substitution is analyzed, showing that isotope fractionation is essentially a local effect in the investigated system.

First-principles study of elastic and thermodynamic properties of orthorhombic OsB4 under high pressure

NASA Astrophysics Data System (ADS)

Yan, Hai-Yan; Zhang, Mei-Guang; Huang, Duo-Hui; Wei, Qun

2013-04-01

The first-principles study on the elastic properties, elastic anisotropy and thermodynamic properties of the orthorhombic OsB4 is reported using density functional theory method with the ultrasoft pseudopotential scheme in the frame of the generalized gradient approximation. The calculated equilibrium parameters are in good agreement with the available theoretical data. A complete elastic tensor and crystal anisotropies of the ultra-incompressible OsB4 are determined in the pressure range of 0-50 GPa. By the elastic stability criteria, it is predicted that the orthorhombic OsB4 is stable below 50 GPa. By using the quasi-harmonic Debye model, the heat capacity, the coefficient of thermal expansion, and the Grüneisen parameter of OsB4 are also successfully obtained in the present work.

Computer program for calculation of complex chemical equilibrium compositions and applications. Supplement 1: Transport properties

NASA Technical Reports Server (NTRS)

Gordon, S.; Mcbride, B.; Zeleznik, F. J.

1984-01-01

An addition to the computer program of NASA SP-273 is given that permits transport property calculations for the gaseous phase. Approximate mixture formulas are used to obtain viscosity and frozen thermal conductivity. Reaction thermal conductivity is obtained by the same method as in NASA TN D-7056. Transport properties for 154 gaseous species were selected for use with the program.

Predictions for partial and monolayer coverages of O2 on graphite

NASA Technical Reports Server (NTRS)

Pan, R. P.; Etters, R. D.; Kobashi, K.; Chandrasekharan, V.

1982-01-01

Monolayer properties of O2 on graphite are calculated using a pattern recognition, optimization scheme. Equilibrium monolayers are predicted at two different densities with properties in agreement with recent X-ray diffraction, specific heat, and neutron scattering data. Properties of the extremely low density regime are calculated using a model based upon a distribution of two-dimensional O2 clusters. The results are consistent with experimental evidence.

Electronic structure of alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ehrenreich, H.; Schwartz, L.M.

1976-01-01

The description of electronic properties of binary substitutional alloys within the single particle approximation is reviewed. Emphasis is placed on a didactic exposition of the equilibrium properties of the transport and magnetic properties of such alloys. Topics covered include: multiple scattering theory; the single band alloy; formal extensions of the theory; the alloy potential; realistic model state densities; the s-d model; and the muffin tin model. 43 figures, 3 tables, 151 references. (GHT)

Kinetic equation and nonequilibrium entropy for a quasi-two-dimensional gas.

PubMed

Brey, J Javier; Maynar, Pablo; García de Soria, M I

2016-10-01

A kinetic equation for a dilute gas of hard spheres confined between two parallel plates separated a distance smaller than two particle diameters is derived. It is a Boltzmann-like equation, which incorporates the effect of the confinement on the particle collisions. A function S(t) is constructed by adding to the Boltzmann expression a confinement contribution. Then it is shown that for the solutions of the kinetic equation, S(t) increases monotonically in time, until the system reaches a stationary inhomogeneous state, when S becomes the equilibrium entropy of the confined system as derived from equilibrium statistical mechanics. From the entropy, other equilibrium properties are obtained, and molecular dynamics simulations are used to verify some of the theoretical predictions.

Temperature-Dependent Estimation of Gibbs Energies Using an Updated Group-Contribution Method.

PubMed

Du, Bin; Zhang, Zhen; Grubner, Sharon; Yurkovich, James T; Palsson, Bernhard O; Zielinski, Daniel C

2018-06-05

Reaction-equilibrium constants determine the metabolite concentrations necessary to drive flux through metabolic pathways. Group-contribution methods offer a way to estimate reaction-equilibrium constants at wide coverage across the metabolic network. Here, we present an updated group-contribution method with 1) additional curated thermodynamic data used in fitting and 2) capabilities to calculate equilibrium constants as a function of temperature. We first collected and curated aqueous thermodynamic data, including reaction-equilibrium constants, enthalpies of reaction, Gibbs free energies of formation, enthalpies of formation, entropy changes of formation of compounds, and proton- and metal-ion-binding constants. Next, we formulated the calculation of equilibrium constants as a function of temperature and calculated the standard entropy change of formation (Δ f S ∘ ) using a model based on molecular properties. The median absolute error in estimating Δ f S ∘ was 0.013 kJ/K/mol. We also estimated magnesium binding constants for 618 compounds using a linear regression model validated against measured data. We demonstrate the improved performance of the current method (8.17 kJ/mol in median absolute residual) over the current state-of-the-art method (11.47 kJ/mol) in estimating the 185 new reactions added in this work. The efforts here fill in gaps for thermodynamic calculations under various conditions, specifically different temperatures and metal-ion concentrations. These, to our knowledge, new capabilities empower the study of thermodynamic driving forces underlying the metabolic function of organisms living under diverse conditions. Copyright © 2018 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Making fired bricks with spent equilibrium catalyst-a technical feasibility study

USGS Publications Warehouse

Chou, M.-L.; Chen, L.-M.; Lai, Y.-C.; Chou, S.-F.

2009-01-01

Fluid catalytic cracking in an oil refinery uses a catalyst, such as an alumino-silicate zeolite, in the conversion of heavy hydrocarbons to light hydrocarbons. A small fraction of the catalyst is continually replaced with fresh catalyst to maintain activity. In North America, more than 400 tons of spent alumino-silicate equilibrium catalyst (spent e-cat), and worldwide, more than 1,100 tons, are generated daily, most of which is disposed of in landfills (municipal and on-site facilities). In this study, three spent e-cat samples were tested in a value-added application that would utilize this waste in the manufacturing of fired bricks. The results of this study indicate that spent e-cat is a technically feasible raw material substitute for the clay and shale commonly used in fired brick production. Fired bricks produced with up to 30 wt% of spent e-cat showed good physical appearance and their water absorption properties met the ASTM C 62 specifications for building bricks of either the moderate-or severe-weathering grade.

Transport Coefficients for the NASA Lewis Chemical Equilibrium Program

NASA Technical Reports Server (NTRS)

Svehla, Roger A.

1995-01-01

The new transport property data that will be used in the NASA Lewis Research Center's Chemical Equilibrium and Applications Program (CEA) is presented. It complements a previous publication that documented the thermodynamic and transport property data then in use. Sources of the data and a brief description of the method by which the data were obtained are given. Coefficients to calculate the viscosity, thermal conductivity, and binary interactions are given for either one, or usually, two temperature intervals, typically 300 to 1000 K and 1000 to 5000 K. The form of the transport equation is the same as used previously. The number of species was reduced from the previous database. Many species for which the data were estimated were eliminated from the database. Some ionneutral interactions were added.

The elevation, slope, and curvature spectra of a wind roughened sea surface

NASA Technical Reports Server (NTRS)

Pierson, W. J., Jr.; Stacy, R. A.

1973-01-01

The elevation, slope and curvature spectra are defined as a function of wave number and depend on the friction velocity. There are five wave number ranges of definition called the gravity wave-gravity equilibrium range, the isotropic turbulence range, the connecting range due to Leykin Rosenberg, the capillary range, and the viscous cutoff range. The higher wave number ranges are strongly wind speed dependent, and there is no equilibrium (or saturated) capillary range, at least for winds up to 30 meters/sec. Some properties of the angular variation of the spectra are also found. For high wave numbers, especially in the capillary range, the results are shown to be consistent with the Rayleigh-Rice backscattering theory (Bragg scattering), and certain properties of the angular variation are deduced from backscatter measurements.

Soil-Moisture Retention Curves, Capillary Pressure Curves, and Mercury Porosimetry: A Theoretical and Computational Investigation of the Determination of the Geometric Properties of the Pore Space

NASA Astrophysics Data System (ADS)

Strand, T. E.; Wang, H. F.

2003-12-01

Immiscible displacement protocols have long been used to infer the geometric properties of the void space in granular porous media. The three most commonly used experimental techniques are the measurement of soil-moisture retention curves and relative permeability-capillary pressure-saturation relations, as well as mercury intrusion porosimetry experiments. A coupled theoretical and computational investigation was performed that provides insight into the limitations associated with each technique and quantifies the relationship between experimental observations and the geometric properties of the void space. It is demonstrated that the inference of the pore space geometry from both mercury porosimetry experiments and measurements of capillary pressure curves is influenced by trapping/mobilization phenomena and subject to scaling behavior. In addition, both techniques also assume that the capillary pressure at a location on the meniscus can be approximated by a pressure difference across a region or sample. For example, when performing capillary pressure measurements, the capillary pressure, taken to be the difference between the injected fluid pressure at the inlet and the defending fluid pressure at the outlet, is increased in a series of small steps and the fluid saturation is measured each time the system reaches steady. Regions of defending fluid that become entrapped by the invading fluid can be subsequently mobilized at higher flow rates (capillary pressures), contributing to a scale-dependence of the capillary pressure-saturation curve that complicates the determination of the properties of the pore space. This scale-dependence is particularly problematic for measurements performed at the core scale. Mercury porosimetry experiments are subject to similar limitations. Trapped regions of defending fluid are also present during the measurement of soil-moisture retention curves, but the effects of scaling behavior on the evaluation of the pore space properties from the immiscible displacement structure are much simpler to account for due to the control of mobilization phenomena. Some mobilization may occur due to film flow, but this can be limited by keeping time scales relatively small or exploited at longer time scales in order to quantify the rate of film flow. Computer simulations of gradient-stabilized drainage and imbibition to the (respective) equilibrium positions were performed using a pore-scale modified invasion percolation (MIP) model in order to quantify the relationship between the saturation profile and the geometric properties of the void space. These simulations are similar to the experimental measurement of soil-moisture retention curves. Results show that the equilibrium height and the width of the equilibrium fringe depend on two length scale distributions, one controlling the imbibition equilibrium structure and the other controlling the drainage structure. The equilibrium height is related to the mean value of the appropriate distribution as described by Jurin's law, and the width of the equilibrium fringe scales as a function of a combined parameter, the Bond number, Bo, divided by the coefficient of variation (cov). Simulations also demonstrate that the apparent radius distribution obtained from saturation profiles using direct inversion by Jurin's law is a subset of the actual distribution in the porous medium. The relationship between the apparent and actual radius distributions is quantified in terms of the combined parameter, Bo/cov, and the mean coordination number of the porous medium.

Inactivation of tumor suppressor genes and cancer therapy: An evolutionary game theory approach.

PubMed

Khadem, Heydar; Kebriaei, Hamed; Veisi, Zahra

2017-06-01

Inactivation of alleles in tumor suppressor genes (TSG) is one of the important issues resulting in evolution of cancerous cells. In this paper, the evolution of healthy, one and two missed allele cells is modeled using the concept of evolutionary game theory and replicator dynamics. The proposed model also takes into account the interaction rates of the cells as designing parameters of the system. Different combinations of the equilibrium points of the parameterized nonlinear system is studied and categorized into some cases. In each case, the interaction rates' values are suggested in a way that the equilibrium points of the replicator dynamics are located on an appropriate region of the state space. Based on the suggested interaction rates, it is proved that the system doesn't have any undesirable interior equilibrium point as well. Therefore, the system will converge to the desirable region, where there is a scanty level of cancerous cells. In addition, the proposed conditions for interaction rates guarantee that, when a trajectory of the system reaches the boundaries, then it will stay there forever which is a desirable property since the equilibrium points have been already located on the boundaries, appropriately. The simulation results show the effectiveness of the suggestions in the elimination of the cancerous cells in different scenarios. Copyright © 2017 Elsevier Inc. All rights reserved.

A Review of the Thermodynamic, Transport, and Chemical Reaction Rate Properties of High-temperature Air

NASA Technical Reports Server (NTRS)

Hansen, C Frederick; Heims, Steve P

1958-01-01

Thermodynamic and transport properties of high temperature air, and the reaction rates for the important chemical processes which occur in air, are reviewed. Semiempirical, analytic expressions are presented for thermodynamic and transport properties of air. Examples are given illustrating the use of these properties to evaluate (1) equilibrium conditions following shock waves, (2) stagnation region heat flux to a blunt high-speed body, and (3) some chemical relaxation lengths in stagnation region flow.

Spectral and Fluorescent Studies of the Interaction of an Anionic Oxacarbocyanine Dye with Bovine Serum Albumin

NASA Astrophysics Data System (ADS)

Pronkin, P. G.; Tatikolov, A. S.

2017-01-01

The influence of the formation of noncovalent intermolecular complexes with bovine serum albumin (BSA) on the spectral and fluorescent properties of the anionic oxacarbocyanine dye 3,3'-di-(γ-sulfopropyl)-5,5'-diphenyl-9-ethyloxacarbocyanine betaine (OCC) was studied. Binding of OCC to BSA increased significantly the dye fluorescence. Changes in the absorption and fluorescence spectra of OCC upon interaction with BSA argued in favor of a shift of the dye cis-trans equilibrium in the complex. The effects of adding albumin-denaturing compounds (urea, sodium dodecyl sulfate) on the spectral and fluorescent properties of the dye in the OCC-BSA complex were studied. It was concluded that OCC can act as a probe for albumins and can be used to study protein denaturing.

Emergent ultrafast phenomena in correlated oxides and heterostructures

NASA Astrophysics Data System (ADS)

Gandolfi, M.; Celardo, G. L.; Borgonovi, F.; Ferrini, G.; Avella, A.; Banfi, F.; Giannetti, C.

2017-03-01

The possibility of investigating the dynamics of solids on timescales faster than the thermalization of the internal degrees of freedom has disclosed novel non-equilibrium phenomena that have no counterpart at equilibrium. Transition metal oxides (TMOs) provide an interesting playground in which the correlations among the charges in the metal d-orbitals give rise to a wealth of intriguing electronic and thermodynamic properties involving the spin, charge, lattice and orbital orders. Furthermore, the physical properties of TMOs can be engineered at the atomic level, thus providing the platform to investigate the transport phenomena on timescales of the order of the intrinsic decoherence time of the charge excitations. Here, we review and discuss three paradigmatic examples of transient emerging properties that are expected to open new fields of research: (i) the creation of non-thermal magnetic states in spin-orbit Mott insulators; (ii) the possible exploitation of quantum paths for the transport and collection of charge excitations in heterostructures; (iii) the transient wave-like behavior of the temperature field in strongly anisotropic TMOs.

Economic impacts of a California tsunami

USGS Publications Warehouse

Rose, Adam; Wing, Ian Sue; Wei, Dan; Wein, Anne

2016-01-01

The economic consequences of a tsunami scenario for Southern California are estimated using computable general equilibrium analysis. The economy is modeled as a set of interconnected supply chains interacting through markets but with explicit constraints stemming from property damage and business downtime. Economic impacts are measured by the reduction of Gross Domestic Product for Southern California, Rest of California, and U.S. economies. For California, total economic impacts represent the general equilibrium (essentially quantity and price multiplier) effects of lost production in industries upstream and downstream in the supply-chain of sectors that are directly impacted by port cargo disruptions at Port of Los Angeles and Port of Long Beach (POLA/POLB), property damage along the coast, and evacuation of potentially inundated areas. These impacts are estimated to be $2.2 billion from port disruptions, $0.9 billion from property damages, and $2.8 billion from evacuations. Various economic-resilience tactics can potentially reduce the direct and total impacts by 80–85%.

Vibrational and thermodynamic properties of β-HMX: a first-principles investigation.

PubMed

Wu, Zhongqing; Kalia, Rajiv K; Nakano, Aiichiro; Vashishta, Priya

2011-05-28

Thermodynamic properties of β-HMX crystal are investigated using the quasi-harmonic approximation and density functional theory within the local density approximation (LDA), generalized gradient approximation (GGA), and GGA + empirical van der Waals (vdW) correction. It is found that GGA well describes the thermal expansion coefficient and heat capacity but fails to produce correct bulk modulus and equilibrium volume. The vdW correction improves the bulk modulus and volume, but worsens the thermal expansion coefficient and heat capacity. In contrast, LDA describes all thermodynamic properties with reasonable accuracy, and overall is a good exchange-correlation functional for β-HMX molecular crystal. The results also demonstrate significant contributions of phonons to the equation of state. The static calculation of equilibrium volume for β-HMX differs from the room-temperature value incorporating lattice vibrations by over 5%. Therefore, for molecular crystals, it is essential to include phonon contributions when calculated equation of state is compared with experimental data at ambient condition. © 2011 American Institute of Physics

Effect of stress on the diffusion kinetics of methane during gas desorption in coal matrix under different equilibrium pressures

NASA Astrophysics Data System (ADS)

Li, Chengwu; Xue, Honglai; Hu, Po; Guan, Cheng; Liu, Wenbiao

2018-06-01

Stress has a significant influence on gas diffusion, which is a key factor for methane recovery in coal mines. In this study, a series of experiments were performed to investigate effect of stress on the gas diffusivity during desorption in tectonic coal. Additionally, the desorbed data were modeled using the unipore and bidisperse models. The results show that the bidisperse model better describes the diffusion kinetics than the unipore model in this study. Additionally, the modeling results using the bidisperse approach suggest that the stress impact on the macropore diffusivity is greater than the stress on the micropore diffusivity. Under the same equilibrium pressure, the diffusivity varies with stress according to a four-stage function, which shows an ‘M-shape’. As the equilibrium gas pressure increased from 0.6 to 1.7 MPa, the critical point between stage 2 and stage 3 and between stage 3 and stage 4 transferred to a low stress. This difference is attributed to the gas pressure effects on the physical and mechanical properties of coal. These observations indicate that both the stress and gas pressure can significantly impact gas diffusion and may have significant implications on methane recovery in coal mines.

Random bursts determine dynamics of active filaments.

PubMed

Weber, Christoph A; Suzuki, Ryo; Schaller, Volker; Aranson, Igor S; Bausch, Andreas R; Frey, Erwin

2015-08-25

Constituents of living or synthetic active matter have access to a local energy supply that serves to keep the system out of thermal equilibrium. The statistical properties of such fluctuating active systems differ from those of their equilibrium counterparts. Using the actin filament gliding assay as a model, we studied how nonthermal distributions emerge in active matter. We found that the basic mechanism involves the interplay between local and random injection of energy, acting as an analog of a thermal heat bath, and nonequilibrium energy dissipation processes associated with sudden jump-like changes in the system's dynamic variables. We show here how such a mechanism leads to a nonthermal distribution of filament curvatures with a non-Gaussian shape. The experimental curvature statistics and filament relaxation dynamics are reproduced quantitatively by stochastic computer simulations and a simple kinetic model.

Information thermodynamics of near-equilibrium computation

NASA Astrophysics Data System (ADS)

Prokopenko, Mikhail; Einav, Itai

2015-06-01

In studying fundamental physical limits and properties of computational processes, one is faced with the challenges of interpreting primitive information-processing functions through well-defined information-theoretic as well as thermodynamic quantities. In particular, transfer entropy, characterizing the function of computational transmission and its predictability, is known to peak near critical regimes. We focus on a thermodynamic interpretation of transfer entropy aiming to explain the underlying critical behavior by associating information flows intrinsic to computational transmission with particular physical fluxes. Specifically, in isothermal systems near thermodynamic equilibrium, the gradient of the average transfer entropy is shown to be dynamically related to Fisher information and the curvature of system's entropy. This relationship explicitly connects the predictability, sensitivity, and uncertainty of computational processes intrinsic to complex systems and allows us to consider thermodynamic interpretations of several important extreme cases and trade-offs.

Random bursts determine dynamics of active filaments

PubMed Central

Weber, Christoph A.; Suzuki, Ryo; Schaller, Volker; Aranson, Igor S.; Bausch, Andreas R.; Frey, Erwin

2015-01-01

Constituents of living or synthetic active matter have access to a local energy supply that serves to keep the system out of thermal equilibrium. The statistical properties of such fluctuating active systems differ from those of their equilibrium counterparts. Using the actin filament gliding assay as a model, we studied how nonthermal distributions emerge in active matter. We found that the basic mechanism involves the interplay between local and random injection of energy, acting as an analog of a thermal heat bath, and nonequilibrium energy dissipation processes associated with sudden jump-like changes in the system’s dynamic variables. We show here how such a mechanism leads to a nonthermal distribution of filament curvatures with a non-Gaussian shape. The experimental curvature statistics and filament relaxation dynamics are reproduced quantitatively by stochastic computer simulations and a simple kinetic model. PMID:26261319

Mass-action equilibrium and non-specific interactions in protein binding networks

NASA Astrophysics Data System (ADS)

Maslov, Sergei

2009-03-01

Large-scale protein binding networks serve as a paradigm of complex properties of living cells. These networks are naturally weighted with edges characterized by binding strength and protein-nodes -- by their concentrations. However, the state-of-the-art high-throughput experimental techniques generate just a binary (yes or no) information about individual interactions. As a result, most of the previous research concentrated just on topology of these networks. In a series of recent publications [1-4] my collaborators and I went beyond purely topological studies and calculated the mass-action equilibrium of a genome-wide binding network using experimentally determined protein concentrations, localizations, and reliable binding interactions in baker's yeast. We then studied how this equilibrium responds to large perturbations [1-2] and noise [3] in concentrations of proteins. We demonstrated that the change in the equilibrium concentration of a protein exponentially decays (and sign-alternates) with its network distance away from the perturbed node. This explains why, despite a globally connected topology, individual functional modules in such networks are able to operate fairly independently. In a separate study [4] we quantified the interplay between specific and non-specific binding interactions under crowded conditions inside living cells. We show how the need to limit the waste of resources constrains the number of types and concentrations of proteins that are present at the same time and at the same place in yeast cells. [1] S Maslov, I. Ispolatov, PNAS 104:13655 (2007). [2] S. Maslov, K. Sneppen, I. Ispolatov, New J. of Phys. 9: 273 (2007). [3] K-K. Yan, D. Walker, S. Maslov, PRL accepted (2008). [4] J. Zhang, S. Maslov, and E. I. Shakhnovich, Mol Syst Biol 4, 210 (2008).

Nicholas Metropolis Award for Outstanding Doctoral Thesis Work in Computational Physics Lecture: The Janus computer, a new window into spin-glass physics

NASA Astrophysics Data System (ADS)

Yllanes, David

2013-03-01

Spin glasses are a longstanding model for the sluggish dynamics that appears at the glass transition. They enjoy a privileged status in this context, as they provide the simplest model system both for theoretical and experimental studies of glassy dynamics. However, in spite of forty years of intensive investigation, spin glasses still pose a formidable challenge to theoretical, computational and experimental physics. The main difficulty lies in their incredibly slow dynamics. A recent breakthrough has been made possible by our custom-built computer, Janus, designed and built in a collaboration formed by five universities in Spain and Italy. By employing a purpose-driven architecture, capable of fully exploiting the parallelization possibilities intrinsic to these simulations, Janus outperforms conventional computers by several orders of magnitude. After a brief introduction to spin glasses, the talk will focus on the new physics unearthed by Janus. In particular, we recall our numerical study of the nonequilibrium dynamics of the Edwards-Anderson Ising Spin Glass, for a time that spans eleven orders of magnitude, thus approaching the experimentally relevant scale (i.e. seconds). We have also studied the equilibrium properties of the spin-glass phase, with an emphasis on the quantitative matching between non-equilibrium and equilibrium correlation functions, through a time-length dictionary. Last but not least, we have clarified the existence of a glass transition in the presence of a magnetic field for a finite-range spin glass (the so-called de Almeida-Thouless line). We will finally mention some of the currently ongoing work of the collaboration, such as the characterization of the non-equilibrium dynamics in a magnetic field and the existence of a statics-dynamics dictionary in these conditions.

Developing Structure-Property Relationships in Branched Wormlike Micelles via Advanced Rheological and Neutron Scattering Techniques

NASA Astrophysics Data System (ADS)

Calabrese, Michelle A.

Surfactant wormlike micelles (WLMs) are of particular scientific interest due to their ability to branch, break, and reform under shear, which can lead to shear banding flow instabilities. The tunable self-assembly of WLMs makes them ubiquitous in applications ranging from consumer products to energy recovery fluids. Altering the topology of WLMs by inducing branching provides a microstructural pathway to design and optimize the flow properties for such targeted applications. The goal of this thesis is to understand the role of micellar branching on the resulting equilibrium and non-equilibrium properties, while advancing instrumentation and analysis methods in rheology and neutron scattering. The degree of branching in the mixed cationic/anionic surfactant solutions is controlled by the addition of sodium tosylate. The equilibrium properties are characterized via small angle neutron scattering (SANS), linear viscoelastic rheology, neutron spin echo, and dynamic light scattering. Combining rheology with spatiotemporally-resolved SANS enables unambiguous identification of non-equilibrium rheological and scattering signatures of branching and shear banding. The nonlinear WLM response is characterized via flow-SANS under steady shear, shear startup, and large amplitude oscillatory shear. New methods of time-resolved data analysis are developed, which improve experimental resolution by several-fold. Shear-induced orientation is a complex function of branching level, radial position, and deformation type. The structural mechanisms behind shear band formation are elucidated for steady and dynamic flows, which depend on branching level. Shear banding disappears at high branching levels for all deformation types. These responses are used to validate constitutive modeling predictions of dynamic shear banding for the first time. Finally, quantitative metrics to predict shear banding from rheology or flow-induced orientation are developed. Together, advanced rheological and neutron techniques provide a platform for creating structure-property relationships that predict flow and structural phenomena in WLMs and other soft materials. These methods have enabled characteristic differences in linear versus branched WLMs to be determined. This research is part of a broader effort to characterize branching in polymers and self-assembled systems, and may aid in the formulation of WLMs for specific applications. Finally, this work provides a basis for testing and developing microstructure-based constitutive equations that incorporate micellar breakage and branching.

The H[subscript 3]PO[subscript 4] Acid Ionization Reactions: A Capstone Multiconcept Thermodynamics General Chemistry Laboratory Exercise

ERIC Educational Resources Information Center

Nyasulu, Frazier; Barlag, Rebecca; Wise, Lindy; McMills, Lauren

2013-01-01

The thermodynamic properties of weak acid ionization reactions are determined. The thermodynamic properties are corresponding values of the absolute temperature (T), the weak acid equilibrium constant (K[subscript a]), the enthalpy of ionization (delta[subscript i]H[degrees]), and the entropy of ionization (delta[subscript i]S[degrees]). The…

Adaptive behaviour and multiple equilibrium states in a predator-prey model.

PubMed

Pimenov, Alexander; Kelly, Thomas C; Korobeinikov, Andrei; O'Callaghan, Michael J A; Rachinskii, Dmitrii

2015-05-01

There is evidence that multiple stable equilibrium states are possible in real-life ecological systems. Phenomenological mathematical models which exhibit such properties can be constructed rather straightforwardly. For instance, for a predator-prey system this result can be achieved through the use of non-monotonic functional response for the predator. However, while formal formulation of such a model is not a problem, the biological justification for such functional responses and models is usually inconclusive. In this note, we explore a conjecture that a multitude of equilibrium states can be caused by an adaptation of animal behaviour to changes of environmental conditions. In order to verify this hypothesis, we consider a simple predator-prey model, which is a straightforward extension of the classic Lotka-Volterra predator-prey model. In this model, we made an intuitively transparent assumption that the prey can change a mode of behaviour in response to the pressure of predation, choosing either "safe" of "risky" (or "business as usual") behaviour. In order to avoid a situation where one of the modes gives an absolute advantage, we introduce the concept of the "cost of a policy" into the model. A simple conceptual two-dimensional predator-prey model, which is minimal with this property, and is not relying on odd functional responses, higher dimensionality or behaviour change for the predator, exhibits two stable co-existing equilibrium states with basins of attraction separated by a separatrix of a saddle point. Copyright © 2015 Elsevier Inc. All rights reserved.

Interaction potentials and transport properties of Ba, Ba+, and Ba2+ in rare gases from He to Xe

NASA Astrophysics Data System (ADS)

Buchachenko, Alexei A.; Viehland, Larry A.

2018-04-01

A highly accurate, consistent set of ab initio interaction potentials is obtained for the title systems at the coupled cluster with singles, doubles, and non-iterative triples level of theory with extrapolation to the complete basis set limit. These potentials are shown to be more reliable than the previous potentials based on their long-range behavior, equilibrium properties, collision cross sections, and transport properties.

A molecular dynamics computer simulation study of room-temperature ionic liquids. II. Equilibrium and nonequilibrium solvation dynamics.

PubMed

Shim, Y; Choi, M Y; Kim, Hyung J

2005-01-22

The molecular dynamics (MD) simulation study of solvation structure and free energetics in 1-ethyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium hexafluorophosphate using a probe solute in the preceding article [Y. Shim, M. Y. Choi and H. J. Kim, J. Chem. Phys. 122, 044510 (2005)] is extended to investigate dynamic properties of these liquids. Solvent fluctuation dynamics near equilibrium are studied via MD and associated time-dependent friction is analyzed via the generalized Langevin equation. Nonequilibrium solvent relaxation following an instantaneous change in the solute charge distribution and accompanying solvent structure reorganization are also investigated. Both equilibrium and nonequilibrium solvation dynamics are characterized by at least two vastly different time scales--a subpicosecond inertial regime followed by a slow diffusive regime. Solvent regions contributing to the subpicosecond nonequilibrium relaxation are found to vary significantly with initial solvation configurations, especially near the solute. If the solvent density near the solute is sufficiently high at the outset of the relaxation, subpicosecond dynamics are mainly governed by the motions of a few ions close to the solute. By contrast, in the case of a low local density, solvent ions located not only close to but also relatively far from the solute participate in the subpicosecond relaxation. Despite this difference, linear response holds reasonably well in both ionic liquids. (c) 2005 American Institute of Physics.

The metallofullerene field-induced single-ion magnet HoSc2 N@C80.

PubMed

Dreiser, Jan; Westerström, Rasmus; Zhang, Yang; Popov, Alexey A; Dunsch, Lothar; Krämer, Karl; Liu, Shi-Xia; Decurtins, Silvio; Greber, Thomas

2014-10-13

The low-temperature magnetic properties of the endohedral metallofullerene HoSc2 N@C80 have been studied by superconducting quantum interference device (SQUID) magnetometry. Alternating current (ac) susceptibility measurements reveal that this molecule exhibits slow relaxation of magnetization in a small applied field with timescales in the order of milliseconds. The equilibrium magnetic properties of HoSc2 N@C80 indicate strong magnetic anisotropy. The large differences in magnetization relaxation times between the present compound and the previously investigated DySc2 N@C80 are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymeric Thin Films for Organic Electronics: Properties and Adaptive Structures

PubMed Central

Cataldo, Sebastiano; Pignataro, Bruno

2013-01-01

This review deals with the correlation between morphology, structure and performance of organic electronic devices including thin film transistors and solar cells. In particular, we report on solution processed devices going into the role of the 3D supramolecular organization in determining their electronic properties. A selection of case studies from recent literature are reviewed, relying on solution methods for organic thin-film deposition which allow fine control of the supramolecular aggregation of polymers confined at surfaces in nanoscopic layers. A special focus is given to issues exploiting morphological structures stemming from the intrinsic polymeric dynamic adaptation under non-equilibrium conditions. PMID:28809362

Properties of small Ar sub N-1 K/+/ ionic clusters

NASA Technical Reports Server (NTRS)

Etters, R. D.; Danilowicz, R.; Dugan, J.

1977-01-01

A self-consistent formalism is developed that, based upon a many-body potential, dynamically determines the thermodynamic properties of ionic clusters without an a priori designation of the equilibrium structures. Aggregates consisting of a single closed shell K(+) ion and N-1 isoelectronic argon atoms were studied. The clusters form crystallites at low temperatures, and melting transitions and spontaneous dissociations are indicated. The results confirm experimental evidence that shows that ionic clusters become less stable with increasing N. The crystallite structures formed by four different clusters are isosceles triangle, skewed form, octahedron with ion in the middle, and icosahedron with the ion in the middle.

Adsorption of cyanogen chloride on the surface of boron nitride nanotubes for CNCl sensing

NASA Astrophysics Data System (ADS)

Movlarooy, Tayebeh; Fadradi, Mahboobeh Amiri

2018-05-01

The adsorption of CNCl gas, on the surface of boron nitride nanotubes in pure form, as well as doped with Al and Ga, based on the density functional theory (DFT) has been studied. The electron and structural properties of pristine and doped nanotubes have been investigated. By calculating the adsorption energy, the most stable positions and the equilibrium distance are obtained, and charge transferred and electronic properties have been calculated. The most stable molecule adsorption position for pure nanotube is obtained at the center of the hexagon and for doped nanotube above the impurity atom from N side.

Comparison of a model vapor deposited glass films to equilibrium glass films

NASA Astrophysics Data System (ADS)

Flenner, Elijah; Berthier, Ludovic; Charbonneau, Patrick; Zamponi, Francesco

Vapor deposition of particles onto a substrate held at around 85% of the glass transition temperature can create glasses with increased density, enthalpy, kinetic stability, and mechanical stability compared to an ordinary glass created by cooling. It is estimated that an ordinary glass would need to age thousands of years to reach the kinetic stability of a vapor deposited glass, and a natural question is how close to the equilibrium is the vapor deposited glass. To understand the process, algorithms akin to vapor deposition are used to create simulated glasses that have a higher kinetic stability than their annealed counterpart, although these glasses may not be well equilibrated either. Here we use novel models optimized for a swap Monte Carlo algorithm in order to create equilibrium glass films and compare their properties with those of glasses obtained from vapor deposition algorithms. This approach allows us to directly assess the non-equilibrium nature of vapor-deposited ultrastable glasses. Simons Collaboration on Cracking the Glass Problem and NSF Grant No. DMR 1608086.

Light-induced electronic non-equilibrium in plasmonic particles.

PubMed

Kornbluth, Mordechai; Nitzan, Abraham; Seideman, Tamar

2013-05-07

We consider the transient non-equilibrium electronic distribution that is created in a metal nanoparticle upon plasmon excitation. Following light absorption, the created plasmons decohere within a few femtoseconds, producing uncorrelated electron-hole pairs. The corresponding non-thermal electronic distribution evolves in response to the photo-exciting pulse and to subsequent relaxation processes. First, on the femtosecond timescale, the electronic subsystem relaxes to a Fermi-Dirac distribution characterized by an electronic temperature. Next, within picoseconds, thermalization with the underlying lattice phonons leads to a hot particle in internal equilibrium that subsequently equilibrates with the environment. Here we focus on the early stage of this multistep relaxation process, and on the properties of the ensuing non-equilibrium electronic distribution. We consider the form of this distribution as derived from the balance between the optical absorption and the subsequent relaxation processes, and discuss its implication for (a) heating of illuminated plasmonic particles, (b) the possibility to optically induce current in junctions, and (c) the prospect for experimental observation of such light-driven transport phenomena.

A procedure to find thermodynamic equilibrium constants for CO2 and CH4 adsorption on activated carbon.

PubMed

Trinh, T T; van Erp, T S; Bedeaux, D; Kjelstrup, S; Grande, C A

2015-03-28

Thermodynamic equilibrium for adsorption means that the chemical potential of gas and adsorbed phase are equal. A precise knowledge of the chemical potential is, however, often lacking, because the activity coefficient of the adsorbate is not known. Adsorption isotherms are therefore commonly fitted to ideal models such as the Langmuir, Sips or Henry models. We propose here a new procedure to find the activity coefficient and the equilibrium constant for adsorption which uses the thermodynamic factor. Instead of fitting the data to a model, we calculate the thermodynamic factor and use this to find first the activity coefficient. We show, using published molecular simulation data, how this procedure gives the thermodynamic equilibrium constant and enthalpies of adsorption for CO2(g) on graphite. We also use published experimental data to find similar thermodynamic properties of CO2(g) and of CH4(g) adsorbed on activated carbon. The procedure gives a higher accuracy in the determination of enthalpies of adsorption than ideal models do.

Equilibrium Contact Angle and Adsorption Layer Properties with Surfactants.

PubMed

Thiele, Uwe; Snoeijer, Jacco H; Trinschek, Sarah; John, Karin

2018-06-19

The three-phase contact line of a droplet on a smooth surface can be characterized by the Young equation. It relates the interfacial energies to the macroscopic contact angle θ e . On the mesoscale, wettability is modeled by a film-height-dependent wetting energy f( h). Macro- and mesoscale descriptions are consistent if γ cos θ e = γ + f( h a ), where γ and h a are the liquid-gas interface energy and the thickness of the equilibrium liquid adsorption layer, respectively. Here, we derive a similar consistency condition for the case of a liquid covered by an insoluble surfactant. At equilibrium, the surfactant is spatially inhomogeneously distributed, implying a nontrivial dependence of θ e on surfactant concentration. We derive macroscopic and mesoscopic descriptions of a contact line at equilibrium and show that they are consistent only if a particular dependence of the wetting energy on the surfactant concentration is imposed. This is illustrated by a simple example of dilute surfactants, for which we show excellent agreement between theory and time-dependent numerical simulations.

Ultrafast visualization of the structural evolution of dense hydrogen towards warm dense matter

NASA Astrophysics Data System (ADS)

Fletcher, Luke

2016-10-01

Hot dense hydrogen far from equilibrium is ubiquitous in nature occurring during some of the most violent and least understood events in our universe such as during star formation, supernova explosions, and the creation of cosmic rays. It is also a state of matter important for applications in inertial confinement fusion research and in laser particle acceleration. Rapid progress occurred in recent years characterizing the high-pressure structural properties of dense hydrogen under static or dynamic compression. Here, we show that spectrally and angularly resolved x-ray scattering measure the thermodynamic properties of dense hydrogen and resolve the ultrafast evolution and relaxation towards thermodynamic equilibrium. These studies apply ultra-bright x-ray pulses from the Linac Coherent Light (LCLS) source. The interaction of rapidly heated cryogenic hydrogen with a high-peak power optical laser is visualized with intense LCLS x-ray pulses in a high-repetition rate pump-probe setting. We demonstrate that electron-ion coupling is affected by the small number of particles in the Debye screening cloud resulting in much slower ion temperature equilibration than predicted by standard theory. This work was supported by the DOE Office of Science, Fusion Energy Science under FWP 100182.

Influence of surface morphology on adsorption of potassium stearate molecules on diamond-like carbon substrate: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Guo, Shusen; Cao, Yongzhi; Sun, Tao; Zhang, Junjie; Gu, Le; Zhang, Chuanwei; Xu, Zhiqiang

2018-05-01

Molecular dynamics (MD) simulations were used to provide insights into the influence of nano-scale surface morphology on adsorptive behavior of Potassium stearate molecules on diamond-like carbon (DLC) substrates. Particular focus was given to explain that how the distinctive geometric properties of different surface morphologies affect the equilibrium structures and substrate-molecules interactions of monolayers, which was achieved through adsorptive analysis methods including adsorptive process, density profile, density distribution and surface potential energy. Analysis on surface potential energy demonstrated that the adsorptivity of amorphous smooth substrate is uniformly distributed over the surface, while DLC substrates with different surface morphologies appear to be more potentially corrugated, which improves the adsorptivity significantly. Because of the large distance of molecules from carbon atoms located at the square groove bottom, substrate-molecules interactions vanish significantly, and thus potassium stearate molecules cannot penetrate completely into the square groove. It can be observed that the equilibrium substrate-molecules interactions of triangle groove and semi-circle groove are much more powerful than that of square groove due to geometrically advantageous properties. These findings provided key information of optimally design of solid substrates with controllable adsorptivity.

Dynamic equilibrium of heterogeneous and interconvertible multipotent hematopoietic cell subsets

PubMed Central

Weston, Wendy; Zayas, Jennifer; Perez, Ruben; George, John; Jurecic, Roland

2014-01-01

Populations of hematopoietic stem cells and progenitors are quite heterogeneous and consist of multiple cell subsets with distinct phenotypic and functional characteristics. Some of these subsets also appear to be interconvertible and oscillate between functionally distinct states. The multipotent hematopoietic cell line EML has emerged as a unique model to study the heterogeneity and interconvertibility of multipotent hematopoietic cells. Here we describe extensive phenotypic and functional heterogeneity of EML cells which stems from the coexistence of multiple cell subsets. Each of these subsets is phenotypically and functionally heterogeneous, and displays distinct multilineage differentiation potential, cell cycle profile, proliferation kinetics, and expression pattern of HSC markers and some of the key lineage-associated transcription factors. Analysis of their maintenance revealed that on a population level all EML cell subsets exhibit cell-autonomous interconvertible properties, with the capacity to generate all other subsets and re-establish complete parental EML cell population. Moreover, all EML cell subsets generated during multiple cell generations maintain their distinct phenotypic and functional signatures and interconvertible properties. The model of EML cell line suggests that interconvertible multipotent hematopoietic cell subsets coexist in a homeostatically maintained dynamic equilibrium which is regulated by currently unknown cell-intrinsic mechanisms. PMID:24903657

Dynamic equilibrium of heterogeneous and interconvertible multipotent hematopoietic cell subsets.

PubMed

Weston, Wendy; Zayas, Jennifer; Perez, Ruben; George, John; Jurecic, Roland

2014-06-06

Populations of hematopoietic stem cells and progenitors are quite heterogeneous and consist of multiple cell subsets with distinct phenotypic and functional characteristics. Some of these subsets also appear to be interconvertible and oscillate between functionally distinct states. The multipotent hematopoietic cell line EML has emerged as a unique model to study the heterogeneity and interconvertibility of multipotent hematopoietic cells. Here we describe extensive phenotypic and functional heterogeneity of EML cells which stems from the coexistence of multiple cell subsets. Each of these subsets is phenotypically and functionally heterogeneous, and displays distinct multilineage differentiation potential, cell cycle profile, proliferation kinetics, and expression pattern of HSC markers and some of the key lineage-associated transcription factors. Analysis of their maintenance revealed that on a population level all EML cell subsets exhibit cell-autonomous interconvertible properties, with the capacity to generate all other subsets and re-establish complete parental EML cell population. Moreover, all EML cell subsets generated during multiple cell generations maintain their distinct phenotypic and functional signatures and interconvertible properties. The model of EML cell line suggests that interconvertible multipotent hematopoietic cell subsets coexist in a homeostatically maintained dynamic equilibrium which is regulated by currently unknown cell-intrinsic mechanisms.

Solubilizing properties of new surface-active agents, products of catalytic oxyethylation of cholic acid.

PubMed

Kołodziejczyk, Michał Krzysztof; Nachajski, Michal Jakub; Lukosek, Marek; Zgoda, Marian Mikołaj

2013-01-01

Solubilizing properties of aqueous solutions of a series of surface-active agents, products of oxyethylation of cholic acid, were examined in the present study. The content of oxyethylated segments determined by means of the 1H NMR method enabled the verification of the molecular mass of surfactants along with the calculation of the structural hydrophilic-lipophilic balance (HLB), the solubility parameter delta1/2, and the required solubility level of balance HLB(R). Viscosimetric measurements enabled the calculation of the limiting viscosity number, the content-average molecular mass, the effective volume, the hydrodynamic radius of the surfactant micelle and their equilibrium adducts with rutin, diclofenac and loratadine (BCS Class II and III). By means of the spectrophotometric method (UV) the amount of the solubilized diclofenac, loratadine and rutin (rutoside) was determined in the equilibrium system (saturated solution) in the environment of aqueous solutions of cholic acid derivatives of n(TE) = 20-70. The obtained results serve as a basis for determining the solubilization mechanism of lipophilic therapeutic products and indirectly for estimating the influence of the above process on pharmaceutical as well as biological availability of a micellar adduct from model drug forms (Lindbladt lithogenolitic index).

Calculation of individual isotope equilibrium constants for geochemical reactions

USGS Publications Warehouse

Thorstenson, D.C.; Parkhurst, D.L.

2004-01-01

Theory is derived from the work of Urey (Urey H. C. [1947] The thermodynamic properties of isotopic substances. J. Chem. Soc. 562-581) to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by ?? = (Kex)1/n, where n is the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example 13C16O18O and 1H2H18O. The equilibrium constants of the isotope exchange reactions can be expressed as ratios of individual isotope equilibrium constants for geochemical reactions. Knowledge of the equilibrium constant for the dominant isotopic species can then be used to calculate the individual isotope equilibrium constants. Individual isotope equilibrium constants are calculated for the reaction CO2g = CO2aq for all species that can be formed from 12C, 13C, 16O, and 18O; for the reaction between 12C18 O2aq and 1H218Ol; and among the various 1H, 2H, 16O, and 18O species of H2O. This is a subset of a larger number of equilibrium constants calculated elsewhere (Thorstenson D. C. and Parkhurst D. L. [2002] Calculation of individual isotope equilibrium constants for implementation in geochemical models. Water-Resources Investigation Report 02-4172. U.S. Geological Survey). Activity coefficients, activity-concentration conventions for the isotopic variants of H2O in the solvent 1H216Ol, and salt effects on isotope fractionation have been included in the derivations. The effects of nonideality are small because of the chemical similarity of different isotopic species of the same molecule or ion. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. The derivations can be extended to calculation of individual isotope equilibrium constants for ion pairs and equilibrium constants for isotopic species of other chemical elements. The individual isotope approach calculates the same phase isotopic compositions as existing methods, but also provides concentrations of individual species, which are needed in calculations of mass-dependent effects in transport processes. The equilibrium constants derived in this paper are used to calculate the example of gas-water equilibrium for CO2 in an acidic aqueous solution. ?? 2004 Elsevier Ltd.

Cancer -- Pathological Breakdown of Coherent Energy States

NASA Astrophysics Data System (ADS)

Pokorný, Jiří Pokorný, Jan; Kobilková, Jitka; Jandová, Anna; Vrba, Jan; Vrba, Jan

The fundamental property of biological systems is a coherent state far from thermodynamic equilibrium excited and sustained by energy supply. Mitochondria in eukaryotic cells produce energy and form conditions for excitation of oscillations in microtubules. Microtubule polar oscillations generate a coherent state far from thermodynamic equilibrium which makes possible cooperation of cells in the tissue. Mitochondrial dysfunction (the Warburg effect) in cancer development breaks down energy of the coherent state far from thermodynamic equilibrium and excludes the afflicted cell from the ordered multicellular tissue system. Cancer lowering of energy and coherence of the state far from thermodynamic equilibrium is the biggest difference from the healthy cells. Cancer treatment should target mitochondrial dysfunction to restore the coherent state far from thermodynamic equilibrium, apoptotic pathway, and subordination of the cell in the tissue. A vast variety of genetic changes and other disturbances in different cancers can result in several triggers of mitochondrial dysfunction. In cancers with the Warburg effect, mitochondrial dysfunction can be treated by inhibition of four isoforms of pyruvate dehydrogenase kinases. Treatment of the reverse Warburg effect cancers would be more complicated. Disturbances of cellular electromagnetic activity by conducting and asbestos fibers present a special problem of treatment.

Non-equilibrium condensation of supercritical carbon dioxide in a converging-diverging nozzle

NASA Astrophysics Data System (ADS)

Ameli, Alireza; Afzalifar, Ali; Turunen-Saaresti, Teemu

2017-03-01

Carbon dioxide (CO2) is a promising alternative as a working fluid for future energy conversion and refrigeration cycles. CO2 has low global warming potential compared to refrigerants and supercritical CO2 Brayton cycle ought to have better efficiency than today’s counter parts. However, there are several issues concerning behaviour of supercritical CO2 in aforementioned applications. One of these issues arises due to non-equilibrium condensation of CO2 for some operating conditions in supercritical compressors. This paper investigates the non-equilibrium condensation of carbon dioxide in the course of an expansion from supercritical stagnation conditions in a converging-diverging nozzle. An external look-up table was implemented, using an in-house FORTRAN code, to calculate the fluid properties in supercritical, metastable and saturated regions. This look-up table is coupled with the flow solver and the non-equilibrium condensation model is introduced to the solver using user defined expressions. Numerical results are compared with the experimental measurements. In agreement with the experiment, the distribution of Mach number in the nozzle shows that the flow becomes supersonic in upstream region near the throat where speed of sound is minimum also the equilibrium reestablishment occurs at the outlet boundary condition.

Mechanical approach to chemical transport

PubMed Central

Kocherginsky, Nikolai; Gruebele, Martin

2016-01-01

Nonequilibrium thermodynamics describes the rates of transport phenomena with the aid of various thermodynamic forces, but often the phenomenological transport coefficients are not known, and the description is not easily connected with equilibrium relations. We present a simple and intuitive model to address these issues. Our model is based on Lagrangian dynamics for chemical systems with dissipation, so one may think of the model as physicochemical mechanics. Using one main equation, the model allows a systematic derivation of all transport and equilibrium equations, subject to the limitation that heat generated or absorbed in the system must be small for the model to be valid. A table with all major examples of transport and equilibrium processes described using physicochemical mechanics is given. In equilibrium, physicochemical mechanics reduces to standard thermodynamics and the Gibbs–Duhem relation, and we show that the First and Second Laws of thermodynamics are satisfied for our system plus bath model. Out of equilibrium, our model provides relationships between transport coefficients and describes system evolution in the presence of several simultaneous external fields. The model also leads to an extension of the Onsager–Casimir reciprocal relations for properties simultaneously transported by many components. PMID:27647899

Numerical simulation of a two-sex human papillomavirus (HPV) vaccination model

NASA Astrophysics Data System (ADS)

Suryani, I.; Adi-Kusumo, F.

2014-02-01

Human Papillomavirus (HPV) is a major cause of cervical cancer, precancerous lesions, cancer and other disease. HPV is the most common sexually transmitted infection. Although HPV virus primarily affects woman but it can also affects man because it cause of cancer of the anus, vulva, vagina, penis and some other cancers. HPV vaccines now used to prevent cervical cancer and genital warts because the vaccine protect against four types of HPV that most commonly cause disease are types 6, 11, 16, and 18. This paper is sequel work of Elbasha (2008). Difference with Elbasha (2008) are give alternative proof global stability, numerical simulation and interpretation. Global stability of the equilibrium on the model of a two-sex HPV vaccination were explored by using Lyapunov. Although we use the same lyapunov function, we use the largest invariant set to proof the global stability. The result show that the global stability of the equilibrium depends on the effective reproduction number (R). If R < 1 then the infection-free equilibrium is asymptotically stable globally. If R > 1 then endemic equilibrium have globally asymptotically stable properties. Then equilibrium proceed with the interpretation of numerical simulation.

Thermal Equilibrium of a Macroscopic Quantum System in a Pure State.

PubMed

Goldstein, Sheldon; Huse, David A; Lebowitz, Joel L; Tumulka, Roderich

2015-09-04

We consider the notion of thermal equilibrium for an individual closed macroscopic quantum system in a pure state, i.e., described by a wave function. The macroscopic properties in thermal equilibrium of such a system, determined by its wave function, must be the same as those obtained from thermodynamics, e.g., spatial uniformity of temperature and chemical potential. When this is true we say that the system is in macroscopic thermal equilibrium (MATE). Such a system may, however, not be in microscopic thermal equilibrium (MITE). The latter requires that the reduced density matrices of small subsystems be close to those obtained from the microcanonical, equivalently the canonical, ensemble for the whole system. The distinction between MITE and MATE is particularly relevant for systems with many-body localization for which the energy eigenfuctions fail to be in MITE while necessarily most of them, but not all, are in MATE. We note, however, that for generic macroscopic systems, including those with MBL, most wave functions in an energy shell are in both MATE and MITE. For a classical macroscopic system, MATE holds for most phase points on the energy surface, but MITE fails to hold for any phase point.

A well-balanced finite volume scheme for the Euler equations with gravitation. The exact preservation of hydrostatic equilibrium with arbitrary entropy stratification

NASA Astrophysics Data System (ADS)

Käppeli, R.; Mishra, S.

2016-03-01

Context. Many problems in astrophysics feature flows which are close to hydrostatic equilibrium. However, standard numerical schemes for compressible hydrodynamics may be deficient in approximating this stationary state, where the pressure gradient is nearly balanced by gravitational forces. Aims: We aim to develop a second-order well-balanced scheme for the Euler equations. The scheme is designed to mimic a discrete version of the hydrostatic balance. It therefore can resolve a discrete hydrostatic equilibrium exactly (up to machine precision) and propagate perturbations, on top of this equilibrium, very accurately. Methods: A local second-order hydrostatic equilibrium preserving pressure reconstruction is developed. Combined with a standard central gravitational source term discretization and numerical fluxes that resolve stationary contact discontinuities exactly, the well-balanced property is achieved. Results: The resulting well-balanced scheme is robust and simple enough to be very easily implemented within any existing computer code that solves time explicitly or implicitly the compressible hydrodynamics equations. We demonstrate the performance of the well-balanced scheme for several astrophysically relevant applications: wave propagation in stellar atmospheres, a toy model for core-collapse supernovae, convection in carbon shell burning, and a realistic proto-neutron star.

Temperature in and out of equilibrium: A review of concepts, tools and attempts

NASA Astrophysics Data System (ADS)

Puglisi, A.; Sarracino, A.; Vulpiani, A.

2017-11-01

We review the general aspects of the concept of temperature in equilibrium and non-equilibrium statistical mechanics. Although temperature is an old and well-established notion, it still presents controversial facets. After a short historical survey of the key role of temperature in thermodynamics and statistical mechanics, we tackle a series of issues which have been recently reconsidered. In particular, we discuss different definitions and their relevance for energy fluctuations. The interest in such a topic has been triggered by the recent observation of negative temperatures in condensed matter experiments. Moreover, the ability to manipulate systems at the micro and nano-scale urges to understand and clarify some aspects related to the statistical properties of small systems (as the issue of temperature's ;fluctuations;). We also discuss the notion of temperature in a dynamical context, within the theory of linear response for Hamiltonian systems at equilibrium and stochastic models with detailed balance, and the generalized fluctuation-response relations, which provide a hint for an extension of the definition of temperature in far-from-equilibrium systems. To conclude we consider non-Hamiltonian systems, such as granular materials, turbulence and active matter, where a general theoretical framework is still lacking.

Stability and bifurcation in a model for the dynamics of stem-like cells in leukemia under treatment

NASA Astrophysics Data System (ADS)

Rǎdulescu, I. R.; Cândea, D.; Halanay, A.

2012-11-01

A mathematical model for the dynamics of leukemic cells during treatment is introduced. Delay differential equations are used to model cells' evolution and are based on the Mackey-Glass approach, incorporating Goldie-Coldman law. Since resistance is propagated by cells that have the capacity of self-renewal, a population of stem-like cells is studied. Equilibrium points are calculated and their stability properties are investigated.

{Phi}{sup 4} kinks: Statistical mechanics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Habib, S.

1995-12-31

Some recent investigations of the thermal equilibrium properties of kinks in a 1+1-dimensional, classical {phi}{sup 4} field theory are reviewed. The distribution function, kink density, correlation function, and certain thermodynamic quantities were studied both theoretically and via large scale simulations. A simple double Gaussian variational approach within the transfer operator formalism was shown to give good results in the intermediate temperature range where the dilute gas theory is known to fail.

Relationship Between the Leachability Characteristics of Unique Energetic Compounds and Soil Properties

DTIC Science & Technology

1993-02-01

from Army ammunition plants . While these researchers determined that near-equilibrium conditions were obtained in less than 2 h, continued disappearance...undertaken to provide a direct comparison to TNT sorption study results performed with selected Army Ammunition Plant soils by Pennington and Patrick...moderate iron content (173 gmo (/g). TNT breakthrough in both experiments (v = 0.013 and 0.0029 cm/sec) reached a steady state concentration after 15

SPECIES - EVALUATING THERMODYNAMIC PROPERTIES, TRANSPORT PROPERTIES & EQUILIBRIUM CONSTANTS OF AN 11-SPECIES AIR MODEL

NASA Technical Reports Server (NTRS)

Thompson, R. A.

1994-01-01

Accurate numerical prediction of high-temperature, chemically reacting flowfields requires a knowledge of the physical properties and reaction kinetics for the species involved in the reacting gas mixture. Assuming an 11-species air model at temperatures below 30,000 degrees Kelvin, SPECIES (Computer Codes for the Evaluation of Thermodynamic Properties, Transport Properties, and Equilibrium Constants of an 11-Species Air Model) computes values for the species thermodynamic and transport properties, diffusion coefficients and collision cross sections for any combination of the eleven species, and reaction rates for the twenty reactions normally occurring. The species represented in the model are diatomic nitrogen, diatomic oxygen, atomic nitrogen, atomic oxygen, nitric oxide, ionized nitric oxide, the free electron, ionized atomic nitrogen, ionized atomic oxygen, ionized diatomic nitrogen, and ionized diatomic oxygen. Sixteen subroutines compute the following properties for both a single species, interaction pair, or reaction, and an array of all species, pairs, or reactions: species specific heat and static enthalpy, species viscosity, species frozen thermal conductivity, diffusion coefficient, collision cross section (OMEGA 1,1), collision cross section (OMEGA 2,2), collision cross section ratio, and equilibrium constant. The program uses least squares polynomial curve-fits of the most accurate data believed available to provide the requested values more quickly than is possible with table look-up methods. The subroutines for computing transport coefficients and collision cross sections use additional code to correct for any electron pressure when working with ionic species. SPECIES was developed on a SUN 3/280 computer running the SunOS 3.5 operating system. It is written in standard FORTRAN 77 for use on any machine, and requires roughly 92K memory. The standard distribution medium for SPECIES is a 5.25 inch 360K MS-DOS format diskette. The contents of the diskettes are compressed using the PKWARE archiving tools. The utility to unarchive the files, PKUNZIP.EXE, is included. This program was last updated in 1991. SUN and SunOS are registered trademarks of Sun Microsystems, Inc.

Gas-kinetic theory and Boltzmann equation of share price within an equilibrium market hypothesis and ad hoc strategy

NASA Astrophysics Data System (ADS)

Ausloos, M.

2000-09-01

Recent observations have indicated that the traditional equilibrium market hypothesis (EMH; also known as Efficient Market Hypothesis) is unrealistic. It is shown here that it is the analog of a Boltzmann equation in physics, thus having some bad properties of mean-field approximations like a Gaussian distribution of price fluctuations. A kinetic theory for prices can be simply derived, considering in a first approach that market actors have all identical relaxation times, and solved within a Chapman-Enskog like formalism. In closing the set of equations, (i) an equation of state with a pressure and (ii) the equilibrium (isothermal) equation for the price (taken as the order parameter) of a stock as a function of the volume of money available are obtained.

Local thermodynamic equilibrium in a laser-induced plasma evidenced by blackbody radiation

NASA Astrophysics Data System (ADS)

Hermann, Jörg; Grojo, David; Axente, Emanuel; Craciun, Valentin

2018-06-01

We show that the plasma produced by laser ablation of solid materials in specific conditions has an emission spectrum that is characterized by the saturation of the most intense spectral lines at the blackbody radiance. The blackbody temperature equals the excitation temperature of atoms and ions, proving directly and unambiguously a plasma in local thermodynamic equilibrium. The present investigations take benefit from the very rich and intense emission spectrum generated by ablation of a nickel-chromium-molybdenum alloy. This alternative and direct proof of the plasma equilibrium state re-opens the perspectives of quantitative material analyses via calibration-free laser-induced breakdown spectroscopy. Moreover, the unique properties of this laser-produced plasma promote its use as radiation standard for intensity calibration of spectroscopic instruments.

A Simple Method for Automated Equilibration Detection in Molecular Simulations.

PubMed

Chodera, John D

2016-04-12

Molecular simulations intended to compute equilibrium properties are often initiated from configurations that are highly atypical of equilibrium samples, a practice which can generate a distinct initial transient in mechanical observables computed from the simulation trajectory. Traditional practice in simulation data analysis recommends this initial portion be discarded to equilibration, but no simple, general, and automated procedure for this process exists. Here, we suggest a conceptually simple automated procedure that does not make strict assumptions about the distribution of the observable of interest in which the equilibration time is chosen to maximize the number of effectively uncorrelated samples in the production timespan used to compute equilibrium averages. We present a simple Python reference implementation of this procedure and demonstrate its utility on typical molecular simulation data.

A simple method for automated equilibration detection in molecular simulations

PubMed Central

Chodera, John D.

2016-01-01

Molecular simulations intended to compute equilibrium properties are often initiated from configurations that are highly atypical of equilibrium samples, a practice which can generate a distinct initial transient in mechanical observables computed from the simulation trajectory. Traditional practice in simulation data analysis recommends this initial portion be discarded to equilibration, but no simple, general, and automated procedure for this process exists. Here, we suggest a conceptually simple automated procedure that does not make strict assumptions about the distribution of the observable of interest, in which the equilibration time is chosen to maximize the number of effectively uncorrelated samples in the production timespan used to compute equilibrium averages. We present a simple Python reference implementation of this procedure, and demonstrate its utility on typical molecular simulation data. PMID:26771390

First-principles investigation for some physical properties of some fluoroperovskites compounds ABF3 (A = K, Na; B = Mg, Zn)

NASA Astrophysics Data System (ADS)

Bakri, Badis; Driss, Zied; Berri, Saadi; Khenata, Rabah

2017-12-01

In this work, the structural, electronic and optical properties of fluoroperovskite ABF3 (A = K, Na; B = Mg, Zn) were studied using two different approaches: the full-potential linearized augmented plane wave method and the pseudo-potential plane wave scheme in the frame of generalized gradient approximation features such as the lattice constant, bulk modulus and its pressure derivative are reported. The ground state properties of these compounds such as the equilibrium lattice constant and the bulk modulus are in good agreement with the experimental results. The first principles calculations were performed to study the electronic structures of ABF3(A = K, Na; B = Mg, Zn) compounds and the results indicated that these four compounds are indirect band gap insulators. The optical properties are analysed and the source of some peaks in the spectra is discussed. Besides, the dielectric function, refractive index and extinction coefficient for radiation up to 25 eV have also been reported and discussed.

A combustion model for studying the effects of ideal gas properties on jet noise

NASA Astrophysics Data System (ADS)

Jacobs, Jerin; Tinney, Charles

2016-11-01

A theoretical combustion model is developed to simulate the influence of ideal gas effects on various aeroacoustic parameters over a range of equivalence ratios. The motivation is to narrow the gap between laboratory and full-scale jet noise testing. The combustion model is used to model propane combustion in air and kerosene combustion in air. Gas properties from the combustion model are compared to real lab data acquired at the National Center for Physical Acoustics at the University of Mississippi as well as outputs from NASA's Chemical Equilibrium Analysis code. Different jet properties are then studied over a range of equivalence ratios and pressure ratios for propane combustion in air, kerosene combustion in air and heated air. The findings reveal negligible differences between the three constituents where the density and sound speed ratios are concerned. Albeit, the area ratio required for perfectly expanded flow is shown to be more sensitive to gas properties, relative to changes in the temperature ratio.

A theoretical study for electronic and transport properties of covalent functionalized MoS2 monolayer

NASA Astrophysics Data System (ADS)

Gao, Lijuan; Yang, Zhao-Di; Zhang, Guiling

2017-06-01

The geometries, electronic and electron transport properties of a series of functionalized MoS2 monolayers were investigated using density-functional theory (DFT) and the non-equilibrium Green's function (NEGF) methods. n-Propyl, n-trisilicyl, phenyl, p-nitrophenyl and p-methoxyphenyl are chosen as electron-donating groups. The results show covalent functionalization with electron-donating groups could make a transformation from typical semiconducting to metallic properties for appearance of midgap level across the Fermi level (Ef). The calculations of transport properties for two-probe devices indicate that conductivities of functionalized systems are obviously enhanced relative to pristine MoS2 monolayer. Grafted groups contribute to the major transport path and play an important role in enhancing conductivity. The NDR effect is found. The influence of grafted density is also studied. Larger grafted density leads to wider bandwidth of midgap level, larger current response of I-V curves and larger current difference between peak and valley.

49 CFR 178.940 - Standards for flexible Large Packagings.

Code of Federal Regulations, 2010 CFR

2010-10-01

... as measured originally on the material conditioned to equilibrium at 67 percent relative humidity or... the resistance to aging, provided they do not adversely affect the physical or chemical properties of...

Dynamic Self-Consistent Field Theories for Polymer Blends and Block Copolymers

NASA Astrophysics Data System (ADS)

Kawakatsu, Toshihiro

Understanding the behavior of the phase separated domain structures and rheological properties of multi-component polymeric systems require detailed information on the dynamics of domains and that of conformations of constituent polymer chains. Self-consistent field (SCF) theory is a useful tool to treat such a problem because the conformation entropy of polymer chains in inhomogeneous systems can be evaluated quantitatively using this theory. However, when we turn our attention to the dynamic properties in a non-equilibrium state, the basic assumption of the SCF theory, i.e. the assumption of equilibrium chain conformation, breaks down. In order to avoid such a difficulty, dynamic SCF theories were developed. In this chapter, we give a brief review of the recent developments of dynamic SCF theories, and discuss where the cutting-edge of this theory is.

Transport properties of interacting magnetic islands in tokamak plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gianakon, T.A.; Callen, J.D.; Hegna, C.C.

1993-10-01

This paper explores the equilibrium and transient transport properties of a mixed magnetic topology model for tokamak equilibria. The magnetic topology is composed of a discrete set of mostly non-overlapping magnetic islands centered on the low-order rational surfaces. Transport across the island regions is fast due to parallel transport along the stochastic magnetic field lines about the separatrix of each island. Transport between island regions is assumed to be slow due to a low residual cross-field transport. In equilibrium, such a model leads to: a nonlinear dependence of the heat flux on the pressure gradient; a power balance diffusion coefficientmore » which increases from core to edge; and profile resiliency. Transiently, such a model also exhibits a heat pulse diffusion coefficient larger than the power balance diffusion coefficient.« less

Tables and charts of equilibrium normal shock and shock tube solutions for pure CO2 with velocities to 16 km/second

NASA Technical Reports Server (NTRS)

Miller, C. G., III; Wilder, S. E.

1974-01-01

Equilibrium thermodynamic and flow properties are presented in tabulated and graphical form for moving, standing, and reflected normal shock waves in pure CO2, representative of Mars and Venus atmospheres. Properties include pressure, temperature, density, enthalpy, speed of sound, entropy, molecular weight ratio, isentropic exponent, velocity and species mole fractions. Incident (moving) shock velocities are varied from 1 to 16 km/sec for a range of initial pressure of 5 Newtons per square meter to 500 kilo Newtons per square meter. The present results are applicable to shock tube flows, and to free-flight conditions for a blunt body at high velocities. Working charts illustrating idealized shock-tube performance with CO2 test gas and heated helium and hydrogen driver gases are also presented.

Two-component Fermi-liquid theory - Equilibrium properties of liquid metallic hydrogen

NASA Technical Reports Server (NTRS)

Oliva, J.; Ashcroft, N. W.

1981-01-01

It is reported that the transition of condensed hydrogen from an insulating molecular crystal phase to a metallic liquid phase, at zero temperature and high pressure, appears possible. Liquid metallic hydrogen (LMH), comprising interpenetrating proton and electron fluids, would constitute a two-component Fermi liquid with both a very high component-mass ratio and long-range, species-dependent bare interactions. The low-temperature equilibrium properties of LMH are examined by means of a generalization to the case of two components of the phenomenological Landau Fermi-liquid theory, and the low-temperature specific heat, compressibility, thermal expansion coefficient and spin susceptibility are given. It is found that the specific heat and the thermal expansion coefficient are vastly greater in the liquid than in the corresponding solid, due to the presence of proton quasiparticle excitations in the liquid.

Effects of plasticizers on sorption and optical properties of gum cordia based edible film.

PubMed

Haq, Muhammad Abdul; Jafri, Feroz Alam; Hasnain, Abid

2016-06-01

The present study aimed to characterize a biodegradable film produced from the polysaccharide of an indigenous plant Cordia myxa. Effect of plasticizer type (Glycerol, Sorbitol, PEG200 and PEG 400) and concentration (0-30 %) was studied on sorption and optical properties of the casted film. Increase in plasticizer concentration resulted in increase in equilibrium moisture content of the film and was supported by GAB model of sorption indicating that isotherms were of Type II. The monolayer value increased with the increase in plasticizer concentration with a peak of 0.93 g.g-1 for glycerol. Addition of plasticizers improved the total color (ΔE) with glycerol showing the highest effects. All films showed resistance to UV light in the range of 280-200 nm. The polysaccharide of the fruit of C.myxa can be used to prepare an edible film with improved properties as compared to other available edible coatings.

Metal-organic complexes in geochemical processes: Estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures

NASA Astrophysics Data System (ADS)

Shock, Everetr L.; Koretsky, Carla M.

1995-04-01

Regression of standard state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state allows evaluation of standard partial molal entropies ( overlineSo) of aqueous metal-organic complexes involving monovalent organic acid ligands. These values of overlineSo provide the basis for correlations that can be used, together with correlation algorithms among standard partial molal properties of aqueous complexes and equation-of-state parameters, to estimate thermodynamic properties including equilibrium constants for complexes between aqueous metals and several monovalent organic acid ligands at the elevated pressures and temperatures of many geochemical processes which involve aqueous solutions. Data, parameters, and estimates are given for 270 formate, propanoate, n-butanoate, n-pentanoate, glycolate, lactate, glycinate, and alanate complexes, and a consistent algorithm is provided for making other estimates. Standard partial molal entropies of association ( Δ -Sro) for metal-monovalent organic acid ligand complexes fall into at least two groups dependent upon the type of functional groups present in the ligand. It is shown that isothermal correlations among equilibrium constants for complex formation are consistent with one another and with similar correlations for inorganic metal-ligand complexes. Additional correlations allow estimates of standard partial molal Gibbs free energies of association at 25°C and 1 bar which can be used in cases where no experimentally derived values are available.

High-Performance Metal/Carbide Composites with Far-From-Equilibrium Compositions and Controlled Microstructures

PubMed Central

Hu, Liangfa; O’Neil, Morgan; Erturun, Veysel; Benitez, Rogelio; Proust, Gwénaëlle; Karaman, Ibrahim; Radovic, Miladin

2016-01-01

The prospect of extending existing metal-ceramic composites to those with the compositions that are far from thermodynamic equilibrium is examined. A current and pressure-assisted, rapid infiltration is proposed to fabricate composites, consisting of reactive metallic and ceramic phases with controlled microstructure and tunable properties. An aluminum (Al) alloy/Ti2AlC composite is selected as an example of the far-from-equilibrium systems to fabricate, because Ti2AlC exists only in a narrow region of the Ti-Al-C phase diagram and readily reacts with Al. This kind of reactive systems challenges conventional methods for successfully processing corresponding metal-ceramic composites. Al alloy/Ti2AlC composites with controlled microstructures, various volume ratios of constituents (40/60 and 27/73) and metallic phase sizes (42–83 μm, 77–276 μm, and 167–545 μm), are obtained using the Ti2AlC foams with different pore structures as preforms for molten metal (Al alloy) infiltration. The resulting composites are lightweight and display exceptional mechanical properties at both ambient and elevated temperatures. These structures achieve a compressive strength that is 10 times higher than the yield strength of the corresponding peak-aged Al alloy at ambient temperature and 14 times higher at 400 °C. Possible strengthening mechanisms are described, and further strategies for improving properties of those composites are proposed. PMID:27752106

Effect of alloy addition and growth conditions on the formation of Mg-based bioabsorbable thin films

NASA Astrophysics Data System (ADS)

Pursel, Sean M.; Petrilli, John D.; Horn, Mark W.; Shaw, Barbara A.

2008-08-01

Magnesium is an essential mineral in the human body and has recently been studied as a bioabsorbable material for use in cardiac stents. New areas of application can be found in bone plates, bone screws, and orthopedic implants. Magnesium alone has a corrosion rate much too high for use in such applications and has been alloyed with various elements to improve corrosion resistance. The use of vapor deposition to create Mg alloys for the above applications has not been attempted although certain properties of non-equilibrium alloys, namely corrosion resistance, can be improved. Using vapor deposition the characterization of the growth of magnesium alloy thin films has been done utilizing various alloying elements, substrate temperatures, post-deposition treatments, and substrate positions. The results point towards a growth mode controlled by crystallization of the Mg. Mg Sculptured thin films (STFs) are used to demonstrate these effects and potential solutions while also providing a route to control nanoscale surface morphology to enhance cell growth, cell attachment, and absorption properties. The results of the study are presented in terms of x-ray diffraction data, microscopy analysis of growth evolution, and corrosion testing. This magnesium alloy research utilizes a dual source deposition method that has also provided insight about some of the growth modes of other alloy STFs. Engineering of surface morphology using dip coatings and etching has been used in biomedical materials to enhance certain application specific surface properties. STF technology potentially provides a path to merge the advantages of non-equilibrium alloy formation and engineering nanoscale surface morphology.

First-principles study of the surface properties of U-Mo system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mei, Zhi-Gang; Liang, Linyun; Yacout, Abdellatif M.

U-Mo alloys are promising fuels for future high-performance research reactors with low enriched uranium. Surface properties, such as surface energy, are important inputs for mesoscale simulations (e.g., phase field method) of fission gas bubble behaviors in irradiated nuclear fuels. The lack of surface energies of U-Mo alloys prevents an accurate modeling of the morphology of gas bubbles and gas bubble-induced fuel swelling. To this end, we study the surface properties of U-Mo system, including bcc Mo, alpha-U, gamma-U, and gamma U-Mo alloys. All surfaces up to a maximum Miller index of three and two are calculated for cubic Mo andmore » gamma-U and non-cubic alpha-U, respectively. The equilibrium crystal shapes of bcc Mo, alpha-U and gamma-U are constructed using the calculated surface energies. The dominant surface orientations and the area fraction of each facet are determined from the constructed equilibrium crystal shape. The disordered gamma U-Mo alloys are simulated using the Special Quasirandom Structure method. The (1 1 0) and (1 0 0) surface energies of gamma U-7Mo and U-10Mo alloys are predicted to lie between those of gamma-U and bcc Mo, following a linear combination of the two constituents' surface energies. To better compare with future measurements of surface energies, the area fraction weighted surface energies of alpha-U, gamma-U and gamma U-7Mo and U-10Mo alloys are also predicted. (C) 2017 Published by Elsevier B.V.« less

Equilibrium Field Theoretic and Dynamic Mean Field Simulations of Inhomogeneous Polymeric Materials

NASA Astrophysics Data System (ADS)

Chao, Huikuan

Inhomogeneous polymeric materials is a large family of promising materials including but limited to block copolymers (BCPs), polymer nanocomposites (PNCs) and microscopically confined polymer films. The promising application of the materials originates from the materials' unique microstructures, which offer enhanced mechanical, thermal, optical and electrical properties to the materials. Due to the complex interactions and the large parameter space, behaviors of the microstructures formed by grafted nanoparticles and nanorods in PNCs are difficult to understand. Separately, because of relatively weak interactions, the microstructures are typically achieved through rapid processing that are kinetically controlled and beyond equilibrium. However, efficient simulation framework to study nonequilbrium dynamics of the materials is currently not available. To attack the first difficulty, I extended an efficient simulation framework, polymer nanocomposite field theory (PNC-FT), to incorporate grafted nanoparticles and nanorods. This extended framework is demonstrated against existing experimental studies and implemented to study how the nanoparticle design affects the nanoparticle distribution in binary homopolymer blends. The grafted nanoparticle model is also used as a platform to adopt an advanced optimization method to inversely design nanoparticles which are able to self-assemble into targeted two dimensional lattices. The nanorod model under PNC-FT framework is used to investigate the design of nanorod and block copolymer thin films to control the nanorod distribution. To attack the second difficulty, I established an efficient framework (SCMF-LD) based on a recently proposed dynamic mean field theory and used SCMF-LD to study how to kinetically control the nanoparticle distribution at the end of solvent annealing block copolymer thin films. The framework is then extended to incorporate hydrodynamics (SCMF-DPD) and the extended framework is implemented to study morphology development in phase inversion processing polymer thin films, where hydrodynamic effects play an important role. By exploring both equilibrium and nonequilibrium properties in a spectrum of inhomogeneous polymeric material systems, I successfully extended PNC-FT and established SCMF-LD and SCMF-DPD frameworks, which are expected to be efficient and powerful tools in studies of inhomogeneous polymeric material design and processing.

Properties of air-aluminum thermal plasmas

NASA Astrophysics Data System (ADS)

Cressault, Y.; Gleizes, A.; Riquel, G.

2012-07-01

We present the calculation and the main results of the properties of air-aluminum thermal plasmas, useful for complete modelling of arc systems involving aluminum contacts. The properties are calculated assuming thermal equilibrium and correspond to the equilibrium composition, thermodynamic functions, transport coefficients including diffusion coefficients and net emission coefficient representing the divergence of the radiative flux in the hottest plasma regions. The calculation is developed in the temperature range between 2000 and 30 000 K, for a pressure range from 0.1 to 1 bar and for several metal mass proportions. As in the case of other metals, the presence of aluminum vapours has a strong influence on three properties at intermediate temperatures: the electron number density, the electrical conductivity and the net emission coefficient. Some comparisons with other metal vapour (Cu, Fe and Ag) properties are made and show the original behaviour for Al-containing mixtures: mass density at high temperatures is low due to the low Al atomic mass; high electrical conductivity at T < 10 000 K due to low ionization potential (around 2 V less for Al than for the other metals); very strong self-absorption of ionized aluminum lines, leading to a net emission coefficient lower than that of pure air when T > 10 000 K, in contrast to copper or iron radiation.

The Conceptual Change Approach to Teaching Chemical Equilibrium

ERIC Educational Resources Information Center

Canpolat, Nurtac; Pinarbasi, Tacettin; Bayrakceken, Samih; Geban, Omer

2006-01-01

This study investigates the effect of a conceptual change approach over traditional instruction on students' understanding of chemical equilibrium concepts (e.g. dynamic nature of equilibrium, definition of equilibrium constant, heterogeneous equilibrium, qualitative interpreting of equilibrium constant, changing the reaction conditions). This…

Quantum Prisoners' Dilemma in Fluctuating Massless Scalar Field

NASA Astrophysics Data System (ADS)

Huang, Zhiming

2017-12-01

Quantum systems are easily affected by external environment. In this paper, we investigate the influences of external massless scalar field to quantum Prisoners' Dilemma (QPD) game. We firstly derive the master equation that describes the system evolution with initial maximally entangled state. Then, we discuss the effects of a fluctuating massless scalar field on the game's properties such as payoff, Nash equilibrium, and symmetry. We find that for different game strategies, vacuum fluctuation has different effects on payoff. Nash equilibrium is broken but the symmetry of the game is not violated.

Simple Chaotic Flow with Circle and Square Equilibrium

NASA Astrophysics Data System (ADS)

Gotthans, Tomas; Sprott, Julien Clinton; Petrzela, Jiri

Simple systems of third-order autonomous nonlinear differential equations can exhibit chaotic behavior. In this paper, we present a new class of chaotic flow with a square-shaped equilibrium. This unique property has apparently not yet been described. Such a system belongs to a newly introduced category of chaotic systems with hidden attractors that are interesting and important in engineering applications. The mathematical model is accompanied by an electrical circuit implementation, demonstrating structural stability of the strange attractor. The circuit is simulated with PSpice, constructed, and analyzed (measured).

Extrapolation to Nonequilibrium from Coarse-Grained Response Theory

NASA Astrophysics Data System (ADS)

Basu, Urna; Helden, Laurent; Krüger, Matthias

2018-05-01

Nonlinear response theory, in contrast to linear cases, involves (dynamical) details, and this makes application to many-body systems challenging. From the microscopic starting point we obtain an exact response theory for a small number of coarse-grained degrees of freedom. With it, an extrapolation scheme uses near-equilibrium measurements to predict far-from-equilibrium properties (here, second order responses). Because it does not involve system details, this approach can be applied to many-body systems. It is illustrated in a four-state model and in the near critical Ising model.

Ensemble inequivalence and Maxwell construction in the self-gravitating ring model

NASA Astrophysics Data System (ADS)

Rocha Filho, T. M.; Silvestre, C. H.; Amato, M. A.

2018-06-01

The statement that Gibbs equilibrium ensembles are equivalent is a base line in many approaches in the context of equilibrium statistical mechanics. However, as a known fact, for some physical systems this equivalence may not be true. In this paper we illustrate from first principles the inequivalence between the canonical and microcanonical ensembles for a system with long range interactions. We make use of molecular dynamics simulations and Monte Carlo simulations to explore the thermodynamics properties of the self-gravitating ring model and discuss on what conditions the Maxwell construction is applicable.

Extracting physics of life at the molecular level: A review of single-molecule data analyses.

PubMed

Colomb, Warren; Sarkar, Susanta K

2015-06-01

Studying individual biomolecules at the single-molecule level has proved very insightful recently. Single-molecule experiments allow us to probe both the equilibrium and nonequilibrium properties as well as make quantitative connections with ensemble experiments and equilibrium thermodynamics. However, it is important to be careful about the analysis of single-molecule data because of the noise present and the lack of theoretical framework for processes far away from equilibrium. Biomolecular motion, whether it is free in solution, on a substrate, or under force, involves thermal fluctuations in varying degrees, which makes the motion noisy. In addition, the noise from the experimental setup makes it even more complex. The details of biologically relevant interactions, conformational dynamics, and activities are hidden in the noisy single-molecule data. As such, extracting biological insights from noisy data is still an active area of research. In this review, we will focus on analyzing both fluorescence-based and force-based single-molecule experiments and gaining biological insights at the single-molecule level. Inherently nonequilibrium nature of biological processes will be highlighted. Simulated trajectories of biomolecular diffusion will be used to compare and validate various analysis techniques. Copyright © 2015 Elsevier B.V. All rights reserved.

Determining equilibrium osmolarity in poly(ethylene glycol)/chondrotin sulfate gels mimicking articular cartilage.

PubMed

Sircar, S; Aisenbrey, E; Bryant, S J; Bortz, D M

2015-01-07

We present an experimentally guided, multi-phase, multi-species polyelectrolyte gel model to make qualitative predictions on the equilibrium electro-chemical properties of articular cartilage. The mixture theory consists of two different types of polymers: poly(ethylene gylcol) (PEG), chondrotin sulfate (ChS), water (acting as solvent) and several different ions: H(+), Na(+), Cl(-). The polymer chains have covalent cross-links whose effect on the swelling kinetics is modeled via Doi rubber elasticity theory. Numerical studies on equilibrium polymer volume fraction and net osmolarity (difference in the solute concentration across the gel) show a complex interplay between ionic bath concentrations, pH, cross-link fraction and the average charge per monomer. Generally speaking, swelling is aided due to a higher average charge per monomer (or a higher particle fraction of ChS, the charged component of the polymer), low solute concentration in the bath, a high pH or a low cross-link fraction. A peculiar case arises at higher values of cross-link fraction, where it is observed that increasing the average charge per monomer leads to gel deswelling. Copyright © 2014 Elsevier Ltd. All rights reserved.

Predicting Keto-Enol Equilibrium from Combining UV/Visible Absorption Spectroscopy with Quantum Chemical Calculations of Vibronic Structures for Many Excited States. A Case Study on Salicylideneanilines.

PubMed

Zutterman, Freddy; Louant, Orian; Mercier, Gabriel; Leyssens, Tom; Champagne, Benoît

2018-06-21

Salicylideneanilines are characterized by a tautomer equilibrium, between an enol and a keto form of different colors, at the origin of their remarkable thermochromic, solvatochromic, and photochromic properties. The enol form is usually the most stable but appropriate choice of substituents and conditions (solvent, crystal, host compound) can displace the equilibrium toward the keto form so that there is a need for fast prediction of the keto:enol abundance ratio. Here we demonstrate the reliability of a combined theoretical-experimental method, based on comparing simulated and measured UV/visible absorption spectra, to determine this keto/enol ratio. The calculations of the excitation energies, oscillator strengths, and vibronic structures of both enol and keto forms are performed for all excited states absorbing in the relevant (visible and near-UV) wavelength range at the time-dependent density functional theory level by accounting for solvent effects using the polarizable continuum model. This approach is illustrated for two salicylideneaniline derivatives, which are present, in solution, under the form of keto-enol mixtures. The results are compared to those of chemometric analysis as well as ab initio predictions of the reaction free enthalpies.

Gyrokinetic Statistical Absolute Equilibrium and Turbulence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jian-Zhou Zhu and Gregory W. Hammett

2011-01-10

A paradigm based on the absolute equilibrium of Galerkin-truncated inviscid systems to aid in understanding turbulence [T.-D. Lee, "On some statistical properties of hydrodynamical and magnetohydrodynamical fields," Q. Appl. Math. 10, 69 (1952)] is taken to study gyrokinetic plasma turbulence: A finite set of Fourier modes of the collisionless gyrokinetic equations are kept and the statistical equilibria are calculated; possible implications for plasma turbulence in various situations are discussed. For the case of two spatial and one velocity dimension, in the calculation with discretization also of velocity v with N grid points (where N + 1 quantities are conserved, correspondingmore » to an energy invariant and N entropy-related invariants), the negative temperature states, corresponding to the condensation of the generalized energy into the lowest modes, are found. This indicates a generic feature of inverse energy cascade. Comparisons are made with some classical results, such as those of Charney-Hasegawa-Mima in the cold-ion limit. There is a universal shape for statistical equilibrium of gyrokinetics in three spatial and two velocity dimensions with just one conserved quantity. Possible physical relevance to turbulence, such as ITG zonal flows, and to a critical balance hypothesis are also discussed.« less

Simulating 3D Stellar Winds and Diffuse X-ray Emissions from Gases in Non-equilibrium Ionization State

NASA Astrophysics Data System (ADS)

Long, Min; Sun, Wei; Niu, Shu; Zhou, Xin; Ji, Li

2017-08-01

We investigate the physical properties of stellar winds launched in super stellar clusters (SSCs). Chandra observations have detected the presence of diffuse X-ray emission caused by hot gas from such winds in SSCs, and provide the best probe for understanding interactions between the stellar winds and the complex nursery regions. However, the details of the origin of cluster winds, the mass and energy ejection, the formation of diffuse X-ray emission, the fraction of winds contribution to the distribution of diffuse X-ray emission still remain unclear. We developed a multiphysics hydrodynamic model including self-gravity, head conduction and performed 3D simulations with an unprecedented grid resolution due to adaptive mesh refinement (AMR) capability in a case study of NGC 3603, as a supplement to the analysis of the archived 500 ks Chandra observations. The synthetic emission will be computed by assuming the gas in a non-equilibrium ionization (NEI) state indicated by Chandra observation, not coronal ionization equilibrium (CIE) that most works assumed, by using a customized NEI calculation module based on AtomDB. The results will be compared to the Chandra observations.

Quantification of the microphytobenthic primary production in european intertidal mudflats - A modelling approach

USGS Publications Warehouse

Guarini, J.-M.; Blanchard, G.F.; Gros, P.

2000-01-01

A deterministic model quantifying the dynamics of the microphytobenthic biomass in the first centimeter of the mud was formulated as part of the MAST-III/INTRMUD project. The main modelled processes are production by photosynthesis, active vertical migration of the microphytobenthos and global biomass losses, encompassing grazing, mortality and resuspension during immersion periods. The model emphasizes the role of the interface between mud and air, which is crucial for the production. The microalgal biofilm present at the mud surface during day-time emersion periods induces most of the differences between microphytobenthos and phytoplankton communities dynamics. The study of the mathematical properties of the system, under some simplifying assumptions, shows the convergence of the solutions to a stable cyclic equilibrium, in the whole observed range of the frequencies of the physical synchronizers of the production. Resilience time estimates suggest that microphytobenthic biomass attains an equilibrium rapidly, even after a strong perturbation. Around the equilibrium, the local model solutions agree fairly with the in situ observed dynamics of the total biomass. The sensitivity analysis suggests investigating the processes governing biomass losses, which are so far uncertain, and may further vary in space and time. (C) 2000 Elsevier Science Ltd.

First-principles study of anhydrite, polyhalite and carnallite

NASA Astrophysics Data System (ADS)

Weck, Philippe F.; Kim, Eunja; Jové-Colón, Carlos F.; Sassani, David C.

2014-02-01

We report density functional calculations of the structures and properties of anhydrite (CaSO4), polyhalite (K2SO4·MgSO4·2CaSO4·2H2O) and carnallite (KCl·MgCl2·6H2O). Densities of states are systematically investigated and phonon analysis using density functional perturbation theory is performed at constant equilibrium volume for anhydrite and polyhalite in order to derive their isochoric thermal properties. Thermal properties at constant atmospheric pressure are also calculated using the quasi-harmonic approximation. The computed molar entropy and isobaric heat capacity for anhydrite reproduce experimental data up to 800 K to within 3% and 10%, respectively, while further experimental work is needed to assess our theoretical predictions for polyhalite.

Elastic properties of sulphur and selenium doped ternary PbTe alloys by first principles

NASA Astrophysics Data System (ADS)

Bali, Ashoka; Chetty, Raju; Mallik, Ramesh Chandra

2014-04-01

Lead telluride (PbTe) is an established thermoelectric material which can be alloyed with sulphur and selenium to further enhance the thermoelectric properties. Here, a first principles study of ternary alloys PbSxTe(1-x) and PbSexTe(1-x) (0≤x≤1) based on the Virtual Crystal Approximation (VCA) is presented for different ratios of the isoelectronic atoms in each series. Equilibrium lattice parameters and elastic constants have been calculated and compared with the reported data. Anisotropy parameter calculated from the stiffness constants showed a slight improvement in anisotropy of elastic properties of the alloys over undoped PbTe. Furthermore, the alloys satisfied the predicted stability criteria from the elastic constants, showing stable structures, which agreed with the previously reported experimental results.

Ab - initio study of rare earth magnesium alloy: TbMg

NASA Astrophysics Data System (ADS)

Kumari, Meena; Yadav, Priya; Nautiyal, Shashank; Verma, U. P.

2018-05-01

The structural, electronic and magnetic properties of TbMg were analyzed by using full-potential linearized augmented plane wave method. This intermetallic is stable in structure CsCl (B2 phase) with space group Pm-3m. In electronic properties, we show the electronic band structure and density of states plots. These plots show that this alloy have metallic character because there is no band gap between the valance band and conduction band at Fermi level. The structural properties, i.e. equilibrium lattice constant, bulk modulus and its pressure derivative, energy and volume show good agreement with available data. In this paper, we also present the total magnetic moment along with the magnetic moment on the atomic and interstitial sites of TbMg intermetallic in B2 phase.

First-principles study on the bulk and (1 1 1) surface half-metallicity of KS and RbS in CsCl structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Lei; Lei, Gang; Gao, Qiang

2015-08-15

Graphical abstract: Spin-polarized total and atomic DOS at S-(1 1 1) terminated slab and bulk in CsCl-type RbS. - Highlights: • The half metallic properties of CsCl-type RbS and KS have been studied. • The RbS's and KS's (1 1 1) slabs have been investigated. • Surface energy of RbS's and KS's (1 1 1) slabs are calculated. - Abstract: The electronic and magnetic properties of RbS and KS in CsCl structure have been investigated by using the full-potential local-orbital minimum-basis method. Calculating the relation between the total energies and lattice parameters for RbS and KS, we find out thatmore » the equilibrium lattice parameters are 4.02 Å and 3.84 Å for RbS and KS, respectively. According to our calculations in generalized gradient approximation approximation, both RbS and KS are half-metallic ferromagnets with the magnetic moments of 1 μ{sub B} per formula unit, and band gap of 4.287 eV for RbS and 4.395 eV for KS. We also have studied the electronic and magnetic properties of (1 1 1) surfaces of RbS and KS, and have found out that the half-metallicity of their bulk is preserved in all of those surfaces. Finally, through the calculations of formation energy of RbS and KS, it is found that their thin films are stable in the equilibrium conditions, and the Rb-terminated (1 1 1) slab of RbS and the K-terminated (1 1 1) slab of KS are more stable than their S-terminated (1 1 1) slabs. All of the above properties lead the compounds of RbS and KS in CsCl structure to be promising candidates for spintronic applications.« less

Thermodynamic Bethe ansatz for non-equilibrium steady states: exact energy current and fluctuations in integrable QFT

NASA Astrophysics Data System (ADS)

Castro-Alvaredo, Olalla; Chen, Yixiong; Doyon, Benjamin; Hoogeveen, Marianne

2014-03-01

We evaluate the exact energy current and scaled cumulant generating function (related to the large-deviation function) in non-equilibrium steady states with energy flow, in any integrable model of relativistic quantum field theory (IQFT) with diagonal scattering. Our derivations are based on various recent results of Bernard and Doyon. The steady states are built by connecting homogeneously two infinite halves of the system thermalized at different temperatures Tl, Tr, and waiting for a long time. We evaluate the current J(Tl, Tr) using the exact QFT density matrix describing these non-equilibrium steady states and using Zamolodchikov’s method of the thermodynamic Bethe ansatz (TBA). The scaled cumulant generating function is obtained from the extended fluctuation relations which hold in integrable models. We verify our formula in particular by showing that the conformal field theory (CFT) result is obtained in the high-temperature limit. We analyze numerically our non-equilibrium steady-state TBA equations for three models: the sinh-Gordon model, the roaming trajectories model, and the sine-Gordon model at a particular reflectionless point. Based on the numerics, we conjecture that an infinite family of non-equilibrium c-functions, associated with the scaled cumulants, can be defined, which we interpret physically. We study the full scaled distribution function and find that it can be described by a set of independent Poisson processes. Finally, we show that the ‘additivity’ property of the current, which is known to hold in CFT and was proposed to hold more generally, does not hold in general IQFT—that is, J(Tl, Tr) is not of the form f(Tl) - f(Tr).

Dynamical coupling between magnetic equilibrium and transport in tokamak scenario modelling, with application to current ramps

NASA Astrophysics Data System (ADS)

Fable, E.; Angioni, C.; Ivanov, A. A.; Lackner, K.; Maj, O.; Medvedev, S. Yu; Pautasso, G.; Pereverzev, G. V.; Treutterer, W.; the ASDEX Upgrade Team

2013-07-01

The modelling of tokamak scenarios requires the simultaneous solution of both the time evolution of the plasma kinetic profiles and of the magnetic equilibrium. Their dynamical coupling involves additional complications, which are not present when the two physical problems are solved separately. Difficulties arise in maintaining consistency in the time evolution among quantities which appear in both the transport and the Grad-Shafranov equations, specifically the poloidal and toroidal magnetic fluxes as a function of each other and of the geometry. The required consistency can be obtained by means of iteration cycles, which are performed outside the equilibrium code and which can have different convergence properties depending on the chosen numerical scheme. When these external iterations are performed, the stability of the coupled system becomes a concern. In contrast, if these iterations are not performed, the coupled system is numerically stable, but can become physically inconsistent. By employing a novel scheme (Fable E et al 2012 Nucl. Fusion submitted), which ensures stability and physical consistency among the same quantities that appear in both the transport and magnetic equilibrium equations, a newly developed version of the ASTRA transport code (Pereverzev G V et al 1991 IPP Report 5/42), which is coupled to the SPIDER equilibrium code (Ivanov A A et al 2005 32nd EPS Conf. on Plasma Physics (Tarragona, 27 June-1 July) vol 29C (ECA) P-5.063), in both prescribed- and free-boundary modes is presented here for the first time. The ASTRA-SPIDER coupled system is then applied to the specific study of the modelling of controlled current ramp-up in ASDEX Upgrade discharges.

DC electrophoresis and viscosity of realistic salt-free concentrated suspensions: non-equilibrium dissociation-association processes.

PubMed

Ruiz-Reina, Emilio; Carrique, Félix; Lechuga, Luis

2014-03-01

Most of the suspensions usually found in industrial applications are concentrated, aqueous and in contact with the atmospheric CO2. The case of suspensions with a high concentration of added salt is relatively well understood and has been considered in many studies. In this work we are concerned with the case of concentrated suspensions that have no ions different than: (1) those stemming from the charged colloidal particles (the added counterions, that counterbalance their surface charge); (2) the H(+) and OH(-) ions from water dissociation, and (3) the ions generated by the atmospheric CO2 contamination. We call this kind of systems "realistic salt-free suspensions". We show some theoretical results about the electrophoretic mobility of a colloidal particle and the electroviscous effect of realistic salt-free concentrated suspensions. The theoretical framework is based on a cell model that accounts for particle-particle interactions in concentrated suspensions, which has been successfully applied to many different phenomena in concentrated suspensions. On the other hand, the water dissociation and CO2 contamination can be described following two different levels of approximation: (a) by local equilibrium mass-action equations, because it is supposed that the reactions are so fast that chemical equilibrium is attained everywhere in the suspension, or (b) by non-equilibrium dissociation-association kinetic equations, because it is considered that some reactions are not rapid enough to ensure local chemical equilibrium. Both approaches give rise to different results in the range from dilute to semidilute suspensions, causing possible discrepancies when comparing standard theories and experiments concerning transport properties of realistic salt-free suspensions. Copyright © 2013 Elsevier Inc. All rights reserved.

Equilibrium-phase MR angiography: Comparison of unspecific extracellular and protein-binding gadolinium-based contrast media with respect to image quality.

PubMed

Erb-Eigner, Katharina; Taupitz, Matthias; Asbach, Patrick

2016-01-01

The purpose of this study was to compare contrast and image quality of whole-body equilibrium-phase high-spatial-resolution MR angiography using a non-protein-binding unspecific extracellular gadolinium-based contrast medium with that of two contrast media with different protein-binding properties. 45 patients were examined using either 15 mL of gadobutrol (non-protein-binding, n = 15), 32 mL of gadobenate dimeglumine (weakly protein binding, n = 15) or 11 mL gadofosveset trisodium (protein binding, n = 15) followed by equilibrium-phase high-spatial-resolution MR-angiography of four consecutive anatomic regions. The time elapsed between the contrast injection and the beginning of the equilibrium-phase image acquisition in the respective region was measured and was up to 21 min. Signal intensity was measured in two vessels per region and in muscle tissue. Relative contrast (RC) values were calculated. Vessel contrast, artifacts and image quality were rated by two radiologists in consensus on a five-point scale. Compared with gadobutrol, gadofosveset trisodium revealed significantly higher RC values only when acquired later than 15 min after bolus injection. Otherwise, no significant differences between the three contrast media were found regarding vascular contrast and image quality. Equilibrium-phase high-spatial-resolution MR-angiography using a weakly protein-binding or even non-protein-binding contrast medium is equivalent to using a stronger protein-binding contrast medium when image acquisition is within the first 15 min after contrast injection, and allows depiction of the vasculature with high contrast and image quality. The protein-binding contrast medium was superior for imaging only later than 15 min after contrast medium injection. Copyright © 2015 John Wiley & Sons, Ltd.

Calculating phase diagrams using PANDAT and panengine

NASA Astrophysics Data System (ADS)

Chen, S.-L.; Zhang, F.; Xie, F.-Y.; Daniel, S.; Yan, X.-Y.; Chang, Y. A.; Schmid-Fetzer, R.; Oates, W. A.

2003-12-01

Knowledge of phase equilibria or phase diagrams and thermodynamic properties is important in alloy design and materials-processing simulation. In principle, stable phase equilibrium is uniquely determined by the thermodynamic properties of the system, such as the Gibbs energy functions of the phases. PANDAT, a new computer software package for multicomponent phase-diagram calculation, was developed under the guidance of this principle.

Microscale Mechanics of Actin Networks During Dynamic Assembly and Dissociation

NASA Astrophysics Data System (ADS)

Gurmessa, Bekele; Robertson-Anderson, Rae; Ross, Jennifer; Nguyen, Dan; Saleh, Omar

Actin is one of the key components of the cytoskeleton, enabling cells to move and divide while maintaining shape by dynamic polymerization, dissociation and crosslinking. Actin polymerization and network formation is driven by ATP hydrolysis and varies depending on the concentrations of actin monomers and crosslinking proteins. The viscoelastic properties of steady-state actin networks have been well-characterized, yet the mechanical properties of these non-equilibrium systems during dynamic assembly and disassembly remain to be understood. We use semipermeable microfluidic devices to induce in situ dissolution and re-polymerization of entangled and crosslinked actin networks, by varying ATP concentrations in real-time, while measuring the mechanical properties during disassembly and re-assembly. We use optical tweezers to sinusoidally oscillate embedded microspheres and measure the resulting force at set time-intervals and in different regions of the network during cyclic assembly/disassembly. We determine the time-dependent viscoelastic properties of non-equilibrium network intermediates and the reproducibility and homogeneity of network formation and dissolution. Results inform the role that cytoskeleton reorganization plays in the dynamic multifunctional mechanics of cells. NSF CAREER Award (DMR-1255446) and a Scialog Collaborative Innovation Award funded by Research Corporation for Scientific Advancement (Grant No. 24192).

Initial correlations in open-systems dynamics: The Jaynes-Cummings model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smirne, Andrea; Vacchini, Bassano; INFN, Sezione di Milano, Via Celoria 16, I-20133 Milano

2010-12-15

Employing the trace distance as a measure for the distinguishability of quantum states, we study the influence of initial correlations on the dynamics of open systems. We concentrate on the Jaynes-Cummings model for which the knowledge of the exact joint dynamics of system and reservoir allows the treatment of initial states with arbitrary correlations. As a measure for the correlations in the initial state we consider the trace distance between the system-environment state and the product of its marginal states. In particular, we examine the correlations contained in the thermal equilibrium state for the total system, analyze their dependence onmore » the temperature and on the coupling strength, and demonstrate their connection to the entanglement properties of the eigenstates of the Hamiltonian. A detailed study of the time dependence of the distinguishability of the open system states evolving from the thermal equilibrium state and its corresponding uncorrelated product state shows that the open system dynamically uncovers typical features of the initial correlations.« less

On Determination of the Equation of State of Colloidal Suspensions

NASA Astrophysics Data System (ADS)

Sirorattanakul, Krittanon; Huang, Hao; Uhl, Christopher; Ou-Yang, Daniel

Colloidal suspensions are the main ingredients for a variety of materials in our daily life, e.g., milk, salad dressing, skin lotions and paint for wall coatings. Material properties of these systems require an understanding of the equation of state of these materials. Our project aims to experimentally determine the equation of state of colloidal suspensions by microfluidics, dielectrophoresis (DEP) and optical imaging. We use fluorescent polystyrene latexes as a model system for this study. Placing semi-permeable membranes between microfluidics channels, which made from PDMS, we control the particle concentration and ionic strengths of the suspension. We use osmotic equilibrium equation to analyze the particle concentration distribution in a potential force field created by DEP. We use confocal optical imaging to measure the spatial distribution of the particle concentration. We compare the results of our experimental study with data obtained by computer simulation of osmotic equilibrium of interacting colloids. NSF DMR-0923299, Emulsion Polymer Institute, Department of Physics, Bioengineering Program of Lehigh University.

Numerical Experiments Based on the Catastrophe Model of Solar Eruptions

NASA Astrophysics Data System (ADS)

Xie, X. Y.; Ziegler, U.; Mei, Z. X.; Wu, N.; Lin, J.

2017-11-01

On the basis of the catastrophe model developed by Isenberg et al., we use the NIRVANA code to perform the magnetohydrodynamics (MHD) numerical experiments to look into various behaviors of the coronal magnetic configuration that includes a current-carrying flux rope used to model the prominence levitating in the corona. These behaviors include the evolution in equilibrium heights of the flux rope versus the change in the background magnetic field, the corresponding internal equilibrium of the flux rope, dynamic properties of the flux rope after the system loses equilibrium, as well as the impact of the referential radius on the equilibrium heights of the flux rope. In our calculations, an empirical model of the coronal density distribution given by Sittler & Guhathakurta is used, and the physical diffusion is included. Our experiments show that the deviation of simulations in the equilibrium heights from the theoretical results exists, but is not apparent, and the evolutionary features of the two results are similar. If the flux rope is initially locate at the stable branch of the theoretical equilibrium curve, the flux rope will quickly reach the equilibrium position in the simulation after several rounds of oscillations as a result of the self-adjustment of the system; and the flux rope lose the equilibrium if the initial location of the flux rope is set at the critical point on the theoretical equilibrium curve. Correspondingly, the internal equilibrium of the flux rope can be reached as well, and the deviation from the theoretical results is somewhat apparent since the approximation of the small radius of the flux rope is lifted in our experiments, but such deviation does not affect the global equilibrium in the system. The impact of the referential radius on the equilibrium heights of the flux rope is consistent with the prediction of the theory. Our calculations indicate that the motion of the flux rope after the loss of equilibrium is consistent with which is predicted by the Lin-Forbes model and observations. Formation of the fast mode shock ahead of the flux rope is observed in our experiments. Outward motions of the flux rope are smooth, and magnetic energy is continuously converted into the other types of energy because both the diffusions are considered in calculations, and magnetic reconnection is allowed to occur successively in the current sheet behind the flux rope.

The Yambo code: a comprehensive tool to perform ab-initio simulations of equilibrium and out-of-equilibrium properties

NASA Astrophysics Data System (ADS)

Marini, Andrea

Density functional theory and many-body perturbation theory methods (such as GW and Bethe-Selpether equation) are standard approaches to the equilibrium ground and excited state properties of condensed matter systems, surfaces, molecules and other several kind of materials. At the same time ultra-fast optical spectroscopy is becoming a widely used and powerful tool for the observation of the out-of-equilibrium dynamical processes. In this case the theoretical tools (such as the Baym-Kadanoff equation) are well known but, only recently, have been merged with the ab-Initio approach. And, for this reason, highly parallel and efficient codes are lacking. Nevertheless, the combination of these two areas of research represents, for the ab-initio community, a challenging prespective as it requires the development of advanced theoretical, methodological and numerical tools. Yambo is a popular community software implementing the above methods using plane-waves and pseudo-potentials. Yambo is available to the community as open-source software, and oriented to high-performance computing. The Yambo project aims at making the simulation of these equilibrium and out-of-equilibrium complex processes available to a wide community of users. Indeed the code is used, in practice, in many countries and well beyond the European borders. Yambo is a member of the suite of codes of the MAX European Center of Excellence (Materials design at the exascale) . It is also used by the user facilities of the European Spectroscopy Facility and of the NFFA European Center (nanoscience foundries & fine analysis). In this talk I will discuss some recent numerical and methodological developments that have been implemented in Yambo towards to exploitation of next generation HPC supercomputers. In particular, I will present the hybrid MPI+OpenMP parallelization and the specific case of the response function calculation. I will also discuss the future plans of the Yambo project and its potential use as tool for science dissemination, also in third world countries. Etsf, MAX European Center of Excellence and NFFA European Center.

Simulation of electron-proton coupling with a Monte Carlo method: application to cytochrome c3 using continuum electrostatics.

PubMed Central

Baptista, A M; Martel, P J; Soares, C M

1999-01-01

A new method is presented for simulating the simultaneous binding equilibrium of electrons and protons on protein molecules, which makes it possible to study the full equilibrium thermodynamics of redox and protonation processes, including electron-proton coupling. The simulations using this method reflect directly the pH and electrostatic potential of the environment, thus providing a much closer and realistic connection with experimental parameters than do usual methods. By ignoring the full binding equilibrium, calculations usually overlook the twofold effect that binding fluctuations have on the behavior of redox proteins: first, they affect the energy of the system by creating partially occupied sites; second, they affect its entropy by introducing an additional empty/occupied site disorder (here named occupational entropy). The proposed method is applied to cytochrome c3 of Desulfovibrio vulgaris Hildenborough to study its redox properties and electron-proton coupling (redox-Bohr effect), using a continuum electrostatic method based on the linear Poisson-Boltzmann equation. Unlike previous studies using other methods, the full reduction order of the four hemes at physiological pH is successfully predicted. The sites more strongly involved in the redox-Bohr effect are identified by analysis of their titration curves/surfaces and the shifts of their midpoint redox potentials and pKa values. Site-site couplings are analyzed using statistical correlations, a method much more realistic than the usual analysis based on direct interactions. The site found to be more strongly involved in the redox-Bohr effect is propionate D of heme I, in agreement with previous studies; other likely candidates are His67, the N-terminus, and propionate D of heme IV. Even though the present study is limited to equilibrium conditions, the possible role of binding fluctuations in the concerted transfer of protons and electrons under nonequilibrium conditions is also discussed. The occupational entropy contributions to midpoint redox potentials and pKa values are computed and shown to be significant. PMID:10354425

First-principles study on electron transport properties of carbon-silicon mixed chains

NASA Astrophysics Data System (ADS)

Hu, Wei; Zhou, Qinghua; Liang, Yan; Liu, Wenhua; Wang, Tao; Wan, Haiqing

2018-03-01

In this paper, the transport properties of carbon-silicon mixed chains are studied by using the first-principles. We studied five atomic chain models. In these studies, we found that the equilibrium conductances of atomic chains appear to oscillate, the maximum conductance and the minimum conductance are more than twice the difference. Their I-V curves are linear and show the behavior of metal resistance, M5 system and M2 system current ratio is the largest in 0.9 V, which is 3.3, showing a good molecular switch behavior. In the case of bias, while the bias voltage increases, the transmission peaks move from the Fermi level. The resonance transmission peak height is reduced near the Fermi level. In the higher energy range, a large resonance transmission peak reappears, there is still no energy cut-off range.

Accurate transport properties for H–CO and H–CO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dagdigian, Paul J., E-mail: pjdagdigian@jhu.edu

2015-08-07

Transport properties for collisions of hydrogen atoms with CO and CO{sub 2} have been computed by means of quantum scattering calculations. The carbon oxides are important species in hydrocarbon combustion. The following potential energy surfaces (PES’s) for the interaction of the molecule fixed in its equilibrium geometry were employed: for H–CO, the PES was taken from the work of Song et al. [J. Phys. Chem. A 117, 7571 (2013)], while the PES for H–CO{sub 2} was computed in this study by a restricted coupled cluster method that included single, double, and (perturbatively) triple excitations. The computed transport properties were foundmore » to be significantly different from those computed by the conventional approach that employs isotropic Lennard-Jones (12-6) potentials. The effect of using the presently computed accurate transport properties in 1-dimensional combustion simulations of methane-air flames was investigated.« less

Comparison of Microinstability Properties for Stellarator Magnetic Geometries

DOE Office of Scientific and Technical Information (OSTI.GOV)

G. Rewoldt; L.-P. Ku; W.M. Tang

2005-06-16

The microinstability properties of seven distinct magnetic geometries corresponding to different operating and planned stellarators with differing symmetry properties are compared. Specifically, the kinetic stability properties (linear growth rates and real frequencies) of toroidal microinstabilities (driven by ion temperature gradients and trapped-electron dynamics) are compared, as parameters are varied. The familiar ballooning representation is used to enable efficient treatment of the spatial variations along the equilibrium magnetic field lines. These studies provide useful insights for understanding the differences in the relative strengths of the instabilities caused by the differing localizations of good and bad magnetic curvature and of the presencemore » of trapped particles. The associated differences in growth rates due to magnetic geometry are large for small values of the temperature gradient parameter n identical to d ln T/d ln n, whereas for large values of n, the mode is strongly unstable for all of the different magnetic geometries.« less

Transport properties of CNT/oligosilane/CNT heterojunctions

NASA Astrophysics Data System (ADS)

Yu, J.; Zhang, G. L.; Shang, Y.; Wang, K. D.; Zhang, H.; Sun, M.; Liu, B.; Zeng, T.

2013-02-01

Combining the non-equilibrium Green's function formalism with density functional theory, the transport properties of nine CNT/oligosilane/CNT heterojunctions were systematically studied. We have found that the incorporation of oligosilane linkage to the carbon nanotube mouth could significantly tune the transport properties compared with the pure oligosilane and pure CNT. The P- and B-dopings upon the oligosilane moiety could not only enhance the conductivity but also give rise to multiple negative differential resistance behavior for the CNT/oligosilane/CNT heterojunctions. The concentration of heteroatom plays an important role in the transport properties of the CNT/oligosilane/CNT heterojunctions, while the number of the oligosilane linkage exerts little effect on the conductivity. The B-doped CNT/oligosilane/CNT heterojunctions show higher conductivity than those of the P-doped ones. The p-n junction caused by B- and P-codopings exhibits a rectifying effect and the rectification ratio is up to 7.19.

Relativistic compact stars with charged anisotropic matter

NASA Astrophysics Data System (ADS)

Maurya, S. K.; Banerjee, Ayan; Channuie, Phongpichit

2018-05-01

In this article, we perform a detailed theoretical analysis of new exact solutions with anisotropic fluid distribution of matter for compact objects subject to hydrostatic equilibrium. We present a family solution to the Einstein-Maxwell equations describing a spherically symmetric, static distribution of a fluid with pressure anisotropy. We implement an embedding class one condition to obtain a relation between the metric functions. We generalize the properties of a spherical star with hydrostatic equilibrium using the generalised Tolman-Oppenheimer-Volkoff (TOV) equation. We match the interior solution to an exterior Reissner-Nordström one, and study the energy conditions, speed of sound, and mass-radius relation of the star. We also show that the obtained solutions are compatible with observational data for the compact object Her X-1. Regarding our results, the physical behaviour of the present model may serve for the modeling of ultra compact objects.

Computation of thermodynamic and transport properties to predict thermophoretic effects in an argon-krypton mixture

NASA Astrophysics Data System (ADS)

Miller, Nicholas A. T.; Daivis, Peter J.; Snook, Ian K.; Todd, B. D.

2013-10-01

Thermophoresis is the movement of molecules caused by a temperature gradient. Here we report the results of a study of thermophoresis using non-equilibrium molecular dynamics simulations of a confined argon-krypton fluid subject to two different temperatures at thermostated walls. The resulting temperature profile between the walls is used along with the Soret coefficient to predict the concentration profile that develops across the channel. We obtain the Soret coefficient by calculating the mutual diffusion and thermal diffusion coefficients. We report an appropriate method for calculating the transport coefficients for binary systems, using the Green-Kubo integrals and radial distribution functions obtained from equilibrium molecular dynamics simulations of the bulk fluid. Our method has the unique advantage of separating the mutual diffusion and thermal diffusion coefficients, and calculating the sign and magnitude of their individual contributions to thermophoresis in binary mixtures.

The calculation of the phase equilibrium of the multicomponent hydrocarbon systems

NASA Astrophysics Data System (ADS)

Molchanov, D. A.

2018-01-01

Hydrocarbon mixtures filtration process simulation development has resulted in use of cubic equations of state of the van der Waals type to describe the thermodynamic properties of natural fluids under real thermobaric conditions. Binary hydrocarbon systems allow to simulate the fluids of different types of reservoirs qualitatively, what makes it possible to carry out the experimental study of their filtration features. Exploitation of gas-condensate reservoirs shows the possibility of existence of various two-phase filtration regimes, including self-oscillatory one, which occurs under certain values of mixture composition, temperature and pressure drop. Plotting of the phase diagram of the model mixture is required to determine these values. A software package to calculate the vapor-liquid equilibrium of binary systems using cubic equation of state of the van der Waals type has been created. Phase diagrams of gas-condensate model mixtures have been calculated.

Stability properties and fast ion confinement of hybrid tokamak plasma configurations

NASA Astrophysics Data System (ADS)

Graves, J. P.; Brunetti, D.; Pfefferle, D.; Faustin, J. M. P.; Cooper, W. A.; Kleiner, A.; Lanthaler, S.; Patten, H. W.; Raghunathan, M.

2015-11-01

In hybrid scenarios with flat q just above unity, extremely fast growing tearing modes are born from toroidal sidebands of the near resonant ideal internal kink mode. New scalings of the growth rate with the magnetic Reynolds number arise from two fluid effects and sheared toroidal flow. Non-linear saturated 1/1 dominant modes obtained from initial value stability calculation agree with the amplitude of the 1/1 component of a 3D VMEC equilibrium calculation. Viable and realistic equilibrium representation of such internal kink modes allow fast ion studies to be accurately established. Calculations of MAST neutral beam ion distributions using the VENUS-LEVIS code show very good agreement of observed impaired core fast ion confinement when long lived modes occur. The 3D ICRH code SCENIC also enables the establishment of minority RF distributions in hybrid plasmas susceptible to saturated near resonant internal kink modes.

A novel energy conversion based method for velocity correction in molecular dynamics simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Hanhui; Collaborative Innovation Center of Advanced Aero-Engine, Hangzhou 310027; Liu, Ningning

2017-05-01

Molecular dynamics (MD) simulation has become an important tool for studying micro- or nano-scale dynamics and the statistical properties of fluids and solids. In MD simulations, there are mainly two approaches: equilibrium and non-equilibrium molecular dynamics (EMD and NEMD). In this paper, a new energy conversion based correction (ECBC) method for MD is developed. Unlike the traditional systematic correction based on macroscopic parameters, the ECBC method is developed strictly based on the physical interaction processes between the pair of molecules or atoms. The developed ECBC method can apply to EMD and NEMD directly. While using MD with this method, themore » difference between the EMD and NEMD is eliminated, and no macroscopic parameters such as external imposed potentials or coefficients are needed. With this method, many limits of using MD are lifted. The application scope of MD is greatly extended.« less

Hydrodynamics of a cold one-dimensional fluid: the problem of strong shock waves

NASA Astrophysics Data System (ADS)

Hurtado, Pablo I.

2005-03-01

We study a shock wave induced by an infinitely massive piston propagating into a one-dimensional cold gas. The cold gas is modelled as a collection of hard rods which are initially at rest, so the temperature is zero. Most of our results are based on simulations of a gas of rods with binary mass distribution, and we partcularly focus on the case of spatially alternating masses. We find that the properties of the resulting shock wave are in striking contrast with those predicted by hydrodynamic and kinetic approaches, e.g., the flow-field profiles relax algebraically toward their equilibrium values. In addition, most relevant observables characterizing local thermodynamic equilibrium and equipartition decay as a power law of the distance to the shock layer. The exponents of these power laws depend non-monotonously on the mass ratio. Similar interesting dependences on the mass ratio also characterize the shock width, density and temperature overshoots, etc.

Equilibrium Strategy and Population-Size Effects in Lowest Unique Bid Auctions

NASA Astrophysics Data System (ADS)

Pigolotti, Simone; Bernhardsson, Sebastian; Juul, Jeppe; Galster, Gorm; Vivo, Pierpaolo

2012-02-01

In lowest unique bid auctions, N players bid for an item. The winner is whoever places the lowest bid, provided that it is also unique. We use a grand canonical approach to derive an analytical expression for the equilibrium distribution of strategies. We then study the properties of the solution as a function of the mean number of players, and compare them with a large data set of internet auctions. The theory agrees with the data with striking accuracy for small population-size N, while for larger N a qualitatively different distribution is observed. We interpret this result as the emergence of two different regimes, one in which adaptation is feasible and one in which it is not. Our results question the actual possibility of a large population to adapt and find the optimal strategy when participating in a collective game.

Spreading of correlations in the Falicov-Kimball model

NASA Astrophysics Data System (ADS)

Herrmann, Andreas J.; Antipov, Andrey E.; Werner, Philipp

2018-04-01

We study dynamical properties of the one- and two-dimensional Falicov-Kimball model using lattice Monte Carlo simulations. In particular, we calculate the spreading of charge correlations in the equilibrium model and after an interaction quench. The results show a reduction of the light-cone velocity with interaction strength at low temperature, while the phase velocity increases. At higher temperature, the initial spreading is determined by the Fermi velocity of the noninteracting system and the maximum range of the correlations decreases with increasing interaction strength. Charge order correlations in the disorder potential enhance the range of the correlations. We also use the numerically exact lattice Monte Carlo results to benchmark the accuracy of equilibrium and nonequilibrium dynamical cluster approximation calculations. It is shown that the bias introduced by the mapping to a periodized cluster is substantial, and that from a numerical point of view, it is more efficient to simulate the lattice model directly.

Dynamical properties of α-amylase in the folded and unfolded state: the role of thermal equilibrium fluctuations for conformational entropy and protein stabilisation

NASA Astrophysics Data System (ADS)

Fitter, J.; Herrmann, R.; Hauß, T.; Lechner, R. E.; Dencher, N. A.

2001-07-01

A comparative analysis of thermal equilibrium fluctuations occurring in a mesophilic and in a thermophilic α-amylase was performed to study the effect of structural fluctuations on thermostability. The thermal fluctuations determining the conformational entropy of both enzymes have been characterised for the folded (at 30°C and 60°C) and for the unfolded state by applying neutron spectroscopy (at 30°C). The folded state shows a higher structural flexibility for the thermophilic protein as compared to the mesophilic homologue. In contrast, the unfolded state of both enzymes is rather similar with respect to the structural fluctuations. On the basis of this result, a mechanism characterised by entropic stabilisation (i.e., smaller Δ S for the unfolding transition of thermophilic α-amylase) can be assumed to be responsible for the higher thermostability of the thermophilic enzyme.

Head-on collision of multistate ultralight BEC dark matter configurations

NASA Astrophysics Data System (ADS)

Guzmán, F. S.; Avilez, Ana A.

2018-06-01

Density profiles of ultralight Bose-condensate dark matter inferred from numerical simulations of structure formation, ruled by the Gross-Pitaevskii-Poisson (GPP) system of equations, have a core-tail structure. Multistate equilibrium configurations of the GPP system, on the other hand, have a similar core-tail density profile. We now submit these multistate configurations to highly dynamical scenarios and show their potential as providers of appropriate density profiles of structures. We present the simulation of head-on collisions between two equilibrium configurations of the GPP system of equations, including the collision of ground state with multistate configurations. We study the regimes of solitonic and merger behavior and show generic properties of the dynamics of the system, including the relaxation process and attractor density profiles. We show that the merger of multistate configurations has the potential to produce core-tail density profiles, with the core dominated by the ground state and the halo dominated by an additional state.

Scheil-Gulliver Constituent Diagrams

NASA Astrophysics Data System (ADS)

Pelton, Arthur D.; Eriksson, Gunnar; Bale, Christopher W.

2017-06-01

During solidification of alloys, conditions often approach those of Scheil-Gulliver cooling in which it is assumed that solid phases, once precipitated, remain unchanged. That is, they no longer react with the liquid or with each other. In the case of equilibrium solidification, equilibrium phase diagrams provide a valuable means of visualizing the effects of composition changes upon the final microstructure. In the present study, we propose for the first time the concept of Scheil-Gulliver constituent diagrams which play the same role as that in the case of Scheil-Gulliver cooling. It is shown how these diagrams can be calculated and plotted by the currently available thermodynamic database computing systems that combine Gibbs energy minimization software with large databases of optimized thermodynamic properties of solutions and compounds. Examples calculated using the FactSage system are presented for the Al-Li and Al-Mg-Zn systems, and for the Au-Bi-Sb-Pb system and its binary and ternary subsystems.

Relationship between local structure and relaxation in out-of-equilibrium glassy systems

DOE PAGES

Schoenholz, Samuel S.; Cubuk, Ekin D.; Kaxiras, Efthimios; ...

2016-12-27

The dynamical glass transition is typically taken to be the temperature at which a glassy liquid is no longer able to equilibrate on experimental timescales. Consequently, the physical properties of these systems just above or below the dynamical glass transition, such as viscosity, can change by many orders of magnitude over long periods of time following external perturbation. During this progress toward equilibrium, glassy systems exhibit a history dependence that has complicated their study. In previous work, we bridged the gap between structure and dynamics in glassy liquids above their dynamical glass transition temperatures by introducing a scalar field calledmore » “softness,” a quantity obtained using machine-learning methods. Softness is designed to capture the hidden patterns in relative particle positions that correlate strongly with dynamical rearrangements of particle positions. Here we show that the out-of-equilibrium behavior of a model glass-forming system can be understood in terms of softness. We first demonstrate that the evolution of behavior following a temperature quench is a primarily structural phenomenon: The structure changes considerably, but the relationship between structure and dynamics remains invariant. We then show that the relaxation time can be robustly computed from structure as quantified by softness, with the same relation holding both in equilibrium and as the system ages. Together, these results show that the history dependence of the relaxation time in glasses requires knowledge only of the softness in addition to the usual state variables.« less

Calculation of the relative metastabilities of proteins using the CHNOSZ software package

PubMed Central

Dick, Jeffrey M

2008-01-01

Background Proteins of various compositions are required by organisms inhabiting different environments. The energetic demands for protein formation are a function of the compositions of proteins as well as geochemical variables including temperature, pressure, oxygen fugacity and pH. The purpose of this study was to explore the dependence of metastable equilibrium states of protein systems on changes in the geochemical variables. Results A software package called CHNOSZ implementing the revised Helgeson-Kirkham-Flowers (HKF) equations of state and group additivity for ionized unfolded aqueous proteins was developed. The program can be used to calculate standard molal Gibbs energies and other thermodynamic properties of reactions and to make chemical speciation and predominance diagrams that represent the metastable equilibrium distributions of proteins. The approach takes account of the chemical affinities of reactions in open systems characterized by the chemical potentials of basis species. The thermodynamic database included with the package permits application of the software to mineral and other inorganic systems as well as systems of proteins or other biomolecules. Conclusion Metastable equilibrium activity diagrams were generated for model cell-surface proteins from archaea and bacteria adapted to growth in environments that differ in temperature and chemical conditions. The predicted metastable equilibrium distributions of the proteins can be compared with the optimal growth temperatures of the organisms and with geochemical variables. The results suggest that a thermodynamic assessment of protein metastability may be useful for integrating bio- and geochemical observations. PMID:18834534

Relationship between local structure and relaxation in out-of-equilibrium glassy systems.

PubMed

Schoenholz, Samuel S; Cubuk, Ekin D; Kaxiras, Efthimios; Liu, Andrea J

2017-01-10

The dynamical glass transition is typically taken to be the temperature at which a glassy liquid is no longer able to equilibrate on experimental timescales. Consequently, the physical properties of these systems just above or below the dynamical glass transition, such as viscosity, can change by many orders of magnitude over long periods of time following external perturbation. During this progress toward equilibrium, glassy systems exhibit a history dependence that has complicated their study. In previous work, we bridged the gap between structure and dynamics in glassy liquids above their dynamical glass transition temperatures by introducing a scalar field called "softness," a quantity obtained using machine-learning methods. Softness is designed to capture the hidden patterns in relative particle positions that correlate strongly with dynamical rearrangements of particle positions. Here we show that the out-of-equilibrium behavior of a model glass-forming system can be understood in terms of softness. To do this we first demonstrate that the evolution of behavior following a temperature quench is a primarily structural phenomenon: The structure changes considerably, but the relationship between structure and dynamics remains invariant. We then show that the relaxation time can be robustly computed from structure as quantified by softness, with the same relation holding both in equilibrium and as the system ages. Together, these results show that the history dependence of the relaxation time in glasses requires knowledge only of the softness in addition to the usual state variables.