Low-z gas stripper as an alternative to carbon foils for the acceleration of high-power uranium beams

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

Okuno, H.; Hershcovitch, A.; Fukunishi, N.

2011-04-23

The RIKEN accelerator complex started feeding the next-generation exotic beam facility radioisotope beam factory (RIBF) with heavy-ion beams from 2007 after the successful commissioning of RIBF at the end of 2006. Many improvements made from 2007 to 2010 were instrumental in increasing the intensity of various heavy-ion beams. However, the available beam intensity of very heavy ion beams, especially uranium beams, is far below our goal of 1 p{mu}A (6 x 10{sup 12} particles/s). In order to achieve this goal, upgrade programs are already in progress; the programs include the construction of a new 28-GHz superconducting electron cyclotron resonance ionmore » source and a new injector linac. However, the most serious problem, that of a charge stripper for high-power uranium beams, still remains unsolved, despite extensive research and development work using large foils mounted on a rotating cylinder and a N{sup 2} gas stripper. A gas stripper is free from problems related to lifetime, though the equilibrium charge state in this stripper is considerably lower than that in a carbon foil, owing to the absence of the density effect. Nevertheless, the merits of gas strippers motivated us to develop a low-Z gas stripper to achieve a higher equilibrium charge state even in gases. We measured the electron-loss and electron-capture cross sections of uranium ions in He gas as a function of their charge state at 11, 14, and 15 MeV/nucleon. The equilibrium charge states extracted from the intersection of the lines of the two cross sections were promisingly higher than those in N{sub 2} gas by more than 10. Simple simulations of charge development along the stripper thickness were performed by assuming the measured cross sections. The simulation results show that about 1 mg/cm{sup 2} of He gas should be accumulated to achieve a charge state higher than that of N{sub 2} gas, notwithstanding the difficulty in accumulation of this helium amount owing to its fast dispersion. However, we now believe that the following two solutions can overcome this difficulty: a gas cell with a very large differential pumping system and a gas cell with a plasma window. Their merits and demerits are discussed in the paper.« less

Steady-State Electrodiffusion from the Nernst-Planck Equation Coupled to Local Equilibrium Monte Carlo Simulations.

PubMed

Boda, Dezső; Gillespie, Dirk

2012-03-13

We propose a procedure to compute the steady-state transport of charged particles based on the Nernst-Planck (NP) equation of electrodiffusion. To close the NP equation and to establish a relation between the concentration and electrochemical potential profiles, we introduce the Local Equilibrium Monte Carlo (LEMC) method. In this method, Grand Canonical Monte Carlo simulations are performed using the electrochemical potential specified for the distinct volume elements. An iteration procedure that self-consistently solves the NP and flux continuity equations with LEMC is shown to converge quickly. This NP+LEMC technique can be used in systems with diffusion of charged or uncharged particles in complex three-dimensional geometries, including systems with low concentrations and small applied voltages that are difficult for other particle simulation techniques.

Analyzing the equilibrium states of a quasi-neutral spatially inhomogeneous system of charges above a liquid dielectric film based on the first principles of quantum statistics

NASA Astrophysics Data System (ADS)

Lytvynenko, D. M.; Slyusarenko, Yu V.

2017-08-01

A theory of quasi-neutral equilibrium states of charges above a liquid dielectric surface is developed. This theory is based on the first principles of quantum statistics for systems comprising many identical particles. The proposed approach involves applying the variational principle, modified for the considered systems, and the Thomas-Fermi model. In the terms of the developed theory self-consistency equations are obtained. These equations provide the relation between the main parameters describing the system: the potential of the static electric field, the distribution function of charges and the surface profile of the liquid dielectric. The equations are used to study the phase transition in the system to a spatially periodic state. The proposed method can be applied in analyzing the properties of the phase transition in the system in relation to the spatially periodic states of wave type. Using the analytical and numerical methods, we perform a detailed study of the dependence of the critical parameters of such a phase transition on the thickness of the liquid dielectric film. Some stability criteria for the new asymmetric phase of the studied system are discussed.

Conducting ion tracks generated by charge-selected swift heavy ions

NASA Astrophysics Data System (ADS)

Gupta, Srashti; Gehrke, H. G.; Krauser, J.; Trautmann, C.; Severin, D.; Bender, M.; Rothard, H.; Hofsäss, H.

2016-08-01

Conducting ion tracks in tetrahedral amorphous carbon (ta-C) thin films were generated by irradiation with swift heavy ions of well-defined charge state. The conductivity of tracks and the surface topography of the films, showing characteristic hillocks at each track position, were investigated using conductive atomic force microscopy measurements. The dependence of track conductivity and hillock size on the charge state of the ions was studied using 4.6 MeV/u Pb ions of charge state 53+, 56+ and 60+ provided by GANIL, as well as 4.8 MeV/u Bi and Au ions of charge state from 50+ to 61+ and 4.2 MeV/u 238U ions in equilibrium charge state provided by UNILAC of GSI. For the charge state selection at GSI, an additional stripper-foil system was installed at the M-branch that now allows routine irradiations with ions of selected charge states. The conductivity of tracks in ta-C increases significantly when the charge state increases from 51+ to 60+. However, the conductivity of individual tracks on the same sample still shows large variations, indicating that tracks formed in ta-C are either inhomogeneous or the conductivity is limited by the interface between ion track and Si substrate.

Ionic charge state measurements during He(+)-rich solar particle events

NASA Technical Reports Server (NTRS)

Hovestadt, D.; Klecker, B.; Scholer, M.; Gloeckler, G.

1984-01-01

Ionic charge state measurements of carbon, oxygen, and iron in He(+)-rich energetic particle events are presented. The data have been obtained with the Max-Planck-Institut/University of Maryland sensor system on the ISEE 3 spacecraft. The ionic charge states cannot be explained in terms of a model in which the coronal temperature determines a charge equilibrium which is subsequently frozen-in nor in terms of charge exchange during transition through coronal matter after acceleration. It is concluded that the acceleration and probably also the injection process is biased against particles with high mass-to-charge ratios. The plasma injected into the acceleration process must consist of material of cold (not greater than 8.5 x 10 to the 4th K) as well as hot (2.5 x 10 to the 6th K) origin. The cold material must be more abundant than the hot material.

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.

Measurements of charge state distributions of 0.74 and 1.4 MeV /u heavy ions passing through dilute gases

NASA Astrophysics Data System (ADS)

Scharrer, P.; Düllmann, Ch. E.; Barth, W.; Khuyagbaatar, J.; Yakushev, A.; Bevcic, M.; Gerhard, P.; Groening, L.; Horn, K. P.; Jäger, E.; Krier, J.; Vormann, H.

2017-04-01

In many modern heavy-ion accelerator facilities, gas strippers are used to increase the projectile charge state for improving the acceleration efficiency of ion beams to higher energies. For this application, the knowledge on the behavior of charge state distributions of heavy-ions after passing through dilute gases is of special interest. Charge state distributions of uranium (238U), bismuth (209Bi), titanium (50Ti), and argon (40Ar) ion beams with energies of 0.74 MeV /u and 1.4 MeV /u after passing through hydrogen (H2 ), helium (He), carbon dioxide (CO2 ), nitrogen (N2 ), oxygen (O2 ), neon (Ne), and argon (Ar) gases were measured. Gas stripper target thicknesses up to 100 μ g /cm2 were applied. The observed behavior of the charge state distributions, including their width and mean charge state, are discussed. The measurements show the highest equilibrium charge state at 1.4 MeV /u for 238U on H2 gas of 29.2 ±1.2 . Narrow charge state distributions are observed for 238U and 209Bi on H2 and He gas, which are highly beneficial, e.g., for the production of beams of high intensities in accelerators.

Out-of-equilibrium spin transport in mesoscopic superconductors.

PubMed

Quay, C H L; Aprili, M

2018-08-06

The excitations in conventional superconductors, Bogoliubov quasi-particles, are spin-[Formula: see text] fermions but their charge is energy-dependent and, in fact, zero at the gap edge. Therefore, in superconductors (unlike normal metals) spin and charge degrees of freedom may be separated. In this article, we review spin injection into conventional superconductors and focus on recent experiments on mesoscopic superconductors. We show how quasi-particle spin transport and out-of-equilibrium spin-dependent superconductivity can be triggered using the Zeeman splitting of the quasi-particle density of states in thin-film superconductors with small spin-mixing scattering. Finally, we address the spin dynamics and the feedback of quasi-particle spin imbalances on the amplitude of the superconducting energy gap.This article is part of the theme issue 'Andreev bound states'. © 2018 The Author(s).

An Balancing Strategy Based on SOC for Lithium-Ion Battery Pack

NASA Astrophysics Data System (ADS)

Li, Peng

2017-09-01

According to the two kinds of working state of a battery pack, we designed a balancing strategy based on SOC, and expounds the working principle of balanced control strategy: the battery is charging, the battery charged state of the highest monomer battery is balanced discharge, strong single battery charging current decreases, while the other single cell in the same group is not affected; the battery is in a discharge or static state, single cell battery is the weakest balanced charge, while the other single cell in the same group are not affected. In this paper, we design a kind of lithium ion battery charging and discharging equalizer based on Buck chopper circuit and Boost-Buck chopper circuit. The equalizer is balanced charging and discharging experiments of series four lithium iron phosphate battery, the experimental results show that this equalizer has not only improved the degree not equilibrium between single cells, and improve the battery charge and discharge capacity.

The Long-Term Performance of Small-Cell Batteries Without Cell-Balancing Electronics

NASA Technical Reports Server (NTRS)

Pearson, C.; Thwaite, C.; Curzon, D.; Rao, G.

2006-01-01

Tests approx.8 yrs ago showed Sony HC do not imbalance. AEA developed a theory (ESPC 2002): a) Self-discharge (SD) decreases with state-of-charge (SOC); b) Cells diverge to a state of dynamic equilibrium; c) Equilibrium spread depends on cell SD uniformity. Balancing model verified against test data. Short-term measures of SD difficult in Sony cells and very small values, depends on technique. Long-term evidence supports lower SD at low SD. Battery testing best proof of performance, typically mission specific tests.

Effects of Excess Carriers on Charged Defect Concentrations in Wide Bandgap Semiconductors

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

Alberi, Kirstin M; Scarpulla, Michael A.

Unintentional doping and doping limits in semiconductors are typically caused by compensating defects with low formation energies. Since the formation enthalpy of a charged defect depends linearly on the Fermi level, doping limits can be especially pronounced in wide bandgap semiconductors where the Fermi level can vary substantially. Introduction of non-equilibrium carrier concentrations during growth or processing alters the chemical potentials of band carriers and allows populations of charged defects to be modified in ways impossible at thermal equilibrium. We demonstrate that in the presence of excess carriers, the rates of carrier capture and emission involving a defect charge transitionmore » level determine the admixture of electron and hole quasi-Fermi levels involved in the formation enthalpy of non-zero charge defect states. To understand the range of possible responses, we investigate the behavior of a single donor-like defect as functions of extrinsic doping and charge transition level energy. We find that that excess carriers will increase the formation enthalpy of compensating defects for most values of the charge transition level in the bandgap. Thus, it may be possible to use non-equilibrium carrier concentrations to overcome limitations on doping imposed by native defects. Cases also exist in which the concentration of defects with the same charge polarity as the majority dopant is either left unchanged or actually increases. This surprising effect arises when emission rates are suppressed relative to the capture rates and is most pronounced in wide bandgap semiconductors. We provide guidelines for carrying out experimental tests of this model.« less

Effects of excess carriers on charged defect concentrations in wide bandgap semiconductors

NASA Astrophysics Data System (ADS)

Alberi, Kirstin; Scarpulla, Michael A.

2018-05-01

Unintentional doping and doping limits in semiconductors are typically caused by compensating defects with low formation energies. Since the formation enthalpy of a charged defect depends linearly on the Fermi level, doping limits can be especially pronounced in wide bandgap semiconductors where the Fermi level can vary substantially. Introduction of non-equilibrium carrier concentrations during growth or processing alters the chemical potentials of band carriers and allows populations of charged defects to be modified in ways impossible at thermal equilibrium. We demonstrate that in the presence of excess carriers, the rates of carrier capture and emission involving a defect charge transition level determine the admixture of electron and hole quasi-Fermi levels involved in the formation enthalpy of non-zero charge defect states. To understand the range of possible responses, we investigate the behavior of a single donor-like defect as functions of extrinsic doping and charge transition level energy. We find that that excess carriers will increase the formation enthalpy of compensating defects for most values of the charge transition level in the bandgap. Thus, it may be possible to use non-equilibrium carrier concentrations to overcome limitations on doping imposed by native defects. Cases also exist in which the concentration of defects with the same charge polarity as the majority dopant is either left unchanged or actually increases. This surprising effect arises when emission rates are suppressed relative to the capture rates and is most pronounced in wide bandgap semiconductors. We provide guidelines for carrying out experimental tests of this model.

Kinetics of wet sodium vapor complex plasma

NASA Astrophysics Data System (ADS)

Mishra, S. K.; Sodha, M. S.

2014-04-01

In this paper, we have investigated the kinetics of wet (partially condensed) Sodium vapor, which comprises of electrons, ions, neutral atoms, and Sodium droplets (i) in thermal equilibrium and (ii) when irradiated by light. The formulation includes the balance of charge over the droplets, number balance of the plasma constituents, and energy balance of the electrons. In order to evaluate the droplet charge, a phenomenon for de-charging of the droplets, viz., evaporation of positive Sodium ions from the surface has been considered in addition to electron emission and electron/ion accretion. The analysis has been utilized to evaluate the steady state parameters of such complex plasmas (i) in thermal equilibrium and (ii) when irradiated; the results have been graphically illustrated. As a significant outcome irradiated, Sodium droplets are seen to acquire large positive potential, with consequent enhancement in the electron density.

Equilibrium Fluctuation Relations for Voltage Coupling in Membrane Proteins

PubMed Central

Kim, Ilsoo; Warshel, Arieh

2015-01-01

A general theoretical framework is developed to account for the effects of an external potential on the energetics of membrane proteins. The framework is based on the free energy relation between two (forward/backward) probability densities, which was recently generalized to non-equilibrium processes, culminating in the work-fluctuation theorem. Starting from the probability densities of the conformational states along the reaction coordinate of “voltage coupling”, we investigate several interconnected free energy relations between these two conformational states, considering voltage activation of ion channels. The free energy difference at zero membrane potential (i.e., between the two “non-equilibrium” conformational states) is shown to be equivalent to the free energy difference between the two “equilibrium” conformational states along the one-dimensional reaction coordinate of voltage coupling. Furthermore, the requirement that the application of linear response approximation to the free energy functions (free energies) of voltage coupling should satisfy the general free energy relations, yields a novel expression for the gating charge in terms of other experimentally measurable quantities. This connection is familiar in statistical mechanics, known as the equilibrium fluctuation-response relation. The theory is illustrated by considering the movement of a unit charge within the membrane under the influence of an external potential, using a coarse-graining (CG) model of membrane proteins, which includes the membrane, the electrolytes and the electrodes. The CG model yields Marcus–type voltage dependent free energy parabolas for the two conformational states, which allow for quantitative estimations of an equilibrium free energy difference, a free energy of barrier, and the voltage dependency of channel activation (Q-V curve) for the unit charge movement. In addition, our analysis offers a quantitative rationale for the correlation between the free energy landscapes (parabolas) and the Q-V curve, upon site-directed mutagenesis or drug binding. Taken together, by introducing the voltage coupling as a reaction coordinate of energy gab, the present theory offers a firm physical foundation from the equilibrium theory of statistical mechanics for the thermodynamic models of voltage activation in voltage-sensitive membrane proteins. This formulation also provides a powerful bridge between the CG model and the conventional macroscopic treatments, offering an intuitive and quantitative framework for a better understating of the structure-function correlations of voltage gating in ion channels as well as electrogenic phenomena in ion pumps and transporters. PMID:26290960

Microcanonical and resource-theoretic derivations of the thermal state of a quantum system with noncommuting charges

PubMed Central

Yunger Halpern, Nicole; Faist, Philippe; Oppenheim, Jonathan; Winter, Andreas

2016-01-01

The grand canonical ensemble lies at the core of quantum and classical statistical mechanics. A small system thermalizes to this ensemble while exchanging heat and particles with a bath. A quantum system may exchange quantities represented by operators that fail to commute. Whether such a system thermalizes and what form the thermal state has are questions about truly quantum thermodynamics. Here we investigate this thermal state from three perspectives. First, we introduce an approximate microcanonical ensemble. If this ensemble characterizes the system-and-bath composite, tracing out the bath yields the system's thermal state. This state is expected to be the equilibrium point, we argue, of typical dynamics. Finally, we define a resource-theory model for thermodynamic exchanges of noncommuting observables. Complete passivity—the inability to extract work from equilibrium states—implies the thermal state's form, too. Our work opens new avenues into equilibrium in the presence of quantum noncommutation. PMID:27384494

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.

Transition metal ions in ZnO: Effects of intrashell coulomb repulsion on electronic properties

NASA Astrophysics Data System (ADS)

Ciechan, A.; Bogusławski, P.

2018-05-01

Electronic structure of the transition metal (TM) dopants in ZnO is calculated by first principles approach. Analysis of the results is focused on the properties determined by the intrashell Coulomb coupling. The role of both direct and exchange interaction channel is analyzed. The coupling is manifested in the strong charge state dependence of the TM gap levels, which leads to the metastability of photoexcited Mn, and determines the accessible equilibrium charge states of TM ions. The varying magnitude of the exchange coupling is reflected in the dependence of the spin splitting energy on the chemical identity across the 3d series, as well as the charge state dependence of spin-up spin-down exchange splitting.

On the equilibrium charge density at tilt grain boundaries

NASA Astrophysics Data System (ADS)

Srikant, V.; Clarke, D. R.

1998-05-01

The equilibrium charge density and free energy of tilt grain boundaries as a function of their misorientation is computed using a Monte Carlo simulation that takes into account both the electrostatic and configurational energies associated with charges at the grain boundary. The computed equilibrium charge density increases with the grain-boundary angle and approaches a saturation value. The equilibrium charge density at large-angle grain boundaries compares well with experimental values for large-angle tilt boundaries in GaAs. The computed grain-boundary electrostatic energy is in agreement with the analytical solution to a one-dimensional Poisson equation at high donor densities but indicates that the analytical solution overestimates the electrostatic energy at lower donor densities.

Charge-equilibrium and radiation of low-energy cosmic rays passing through interstellar medium

NASA Technical Reports Server (NTRS)

Rule, D. W.; Omidvar, K.

1977-01-01

The charge equilibrium and radiation of an oxygen and an iron beam in the MeV per nucleon energy range, representing a typical beam of low-energy cosmic rays passing through the interstellar medium, is considered. Electron loss of the beam has been taken into account by means of the First Born approximation allowing for the target atom to remain unexcited, or to be excited to all possible states. Electron capture cross sections have been calculated by means of the scaled Oppenheimer-Brinkman-Kramers approximation, taking into account all atomic shells of the target atoms. Radiation of the beam due to electron capture into the excited states of the ion, collisional excitation and collisional inner-shell ionization of the ions has been considered. Effective X-ray production cross sections and multiplicities for the most energetic X-ray lines emitted by the Fe and O beams have been calculated.

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.

An allosteric model of the molecular interactions of excitation- contraction coupling in skeletal muscle

PubMed Central

1993-01-01

A contact interaction is proposed to exist between the voltage sensor of the transverse tubular membrane of skeletal muscle and the calcium release channel of the sarcoplasmic reticulum. This interaction is given a quantitative formulation inspired in the Monod, Wyman, and Changeux model of allosteric transitions in hemoglobin (Monod, J., J. Wyman, and J.-P. Changeux. 1965. Journal of Molecular Biology. 12:88- 118), and analogous to one proposed by Marks and Jones for voltage- dependent Ca channels (Marks, T. N., and S. W. Jones. 1992. Journal of General Physiology. 99:367-390). The allosteric protein is the calcium release channel, a homotetramer, with two accessible states, closed and open. The kinetics and equilibrium of this transition are modulated by voltage sensors (dihydropyridine receptors) pictured as four units per release channel, each undergoing independent voltage-driven transitions between two states (resting and activating). For each voltage sensor that moves to the activating state, the tendency of the channel to open increases by an equal (large) factor. The equilibrium and kinetic equations of the model are solved and shown to reproduce well a number of experimentally measured relationships including: charge movement (Q) vs. voltage, open probability of the release channel (Po) vs. voltage, the transfer function relationship Po vs. Q, and the kinetics of charge movement, release activation, and deactivation. The main consequence of the assumption of allosteric coupling is that primary effects on the release channel are transmitted backward to the voltage sensor and give secondary effects. Thus, the model reproduces well the effects of perchlorate, described in the two previous articles, under the assumption that the primary effect is to increase the intrinsic tendency of the release channel to open, with no direct effects on the voltage sensor. This modification of the open-closed equilibrium of the release channel causes a shift in the equilibrium dependency of charge movement with voltage. The paradoxical slowing of charge movement by perchlorate also results from reciprocal effects of the channel on the allosterically coupled voltage sensors. The observations of the previous articles plus the simulations in this article constitute functional evidence of allosteric transmission. PMID:8245819

Attraction of likely charged nano-sized grains in dust-electron plasmas

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

Vishnyakov, Vladimir I., E-mail: eksvar@ukr.net

2016-01-15

Dust-electron plasma, which contains only the dust grains and electrons, emitted by them, is studied. Assumption of almost uniform spatial electrons distribution, which deviates from the uniformity only near the dust grains, leads to the grain charge division into two parts: first part is the individual for each grain “visible” charge and the second part is the common charge of the neutralized background. The visible grain charge can be both negative and positive, while the total grain charge is only positive. The attraction of likely charged grains is possible, because the grain interaction is determined by the visible charges. Themore » equilibrium state between attraction and repulsion of grains is demonstrated.« less

Classical molecular dynamics simulations for non-equilibrium correlated plasmas

NASA Astrophysics Data System (ADS)

Ferri, S.; Calisti, A.; Talin, B.

2017-03-01

A classical molecular dynamics model was recently extended to simulate neutral multi-component plasmas where various charge states of the same atom and electrons coexist. It is used to investigate the plasma effects on the ion charge and on the ionization potential in dense plasmas. Different simulated statistical properties will show that the concept of isolated particles is lost in such correlated plasmas. The charge equilibration is discussed for a carbon plasma at solid density and investigation on the charge distribution and on the ionization potential depression (IPD) for aluminum plasmas is discussed with reference to existing experiments.

Preface to Special Topic: Collective Effects in Particle Beams and Nonneutral Plasmas

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

Gilson, Erik P.; Qin, Hong

Nonneutral plasmas are plasma systems in which there is no overall charge neutrality, including the limit of systems that are fully unneutralized in which there are particles of only a single sign of charge. Here, examples of nonneutral plasmas include charged-particle beams, pure electron plasmas, pure positron plasmas, and pure-ion plasmas consisting of a variety of ion charge states in a single trap. A key feature of nonneutral plasmas which distinguishes them from quasineutral plasmas is that their self-electric and self-magnetic fields can play a dominant role in the behavior of the system. Moreover, single-component plasmas can be confined inmore » states of global thermal equilibrium, enabling detailed theoretical and experimental studies of fundamental plasma phenomena and precise testing of models.« less

Preface to Special Topic: Collective Effects in Particle Beams and Nonneutral Plasmas

DOE PAGES

Gilson, Erik P.; Qin, Hong

2018-01-30

Nonneutral plasmas are plasma systems in which there is no overall charge neutrality, including the limit of systems that are fully unneutralized in which there are particles of only a single sign of charge. Here, examples of nonneutral plasmas include charged-particle beams, pure electron plasmas, pure positron plasmas, and pure-ion plasmas consisting of a variety of ion charge states in a single trap. A key feature of nonneutral plasmas which distinguishes them from quasineutral plasmas is that their self-electric and self-magnetic fields can play a dominant role in the behavior of the system. Moreover, single-component plasmas can be confined inmore » states of global thermal equilibrium, enabling detailed theoretical and experimental studies of fundamental plasma phenomena and precise testing of models.« less

Consequences of acid strength for isomerization and elimination catalysis on solid acids.

PubMed

Macht, Josef; Carr, Robert T; Iglesia, Enrique

2009-05-13

We address here the manner in which acid catalysis senses the strength of solid acids. Acid strengths for Keggin polyoxometalate (POM) clusters and zeolites, chosen because of their accurately known structures, are described rigorously by their deprotonation energies (DPE). Mechanistic interpretations of the measured dynamics of alkane isomerization and alkanol dehydration are used to obtain rate and equilibrium constants and energies for intermediates and transition states and to relate them to acid strength. n-Hexane isomerization rates were limited by isomerization of alkoxide intermediates on bifunctional metal-acid mixtures designed to maintain alkane-alkene equilibrium. Isomerization rate constants were normalized by the number of accessible protons, measured by titration with 2,6-di-tert-butylpyridine during catalysis. Equilibrium constants for alkoxides formed by protonation of n-hexene increased slightly with deprotonation energies (DPE), while isomerization rate constants decreased and activation barriers increased with increasing DPE, as also shown for alkanol dehydration reactions. These trends are consistent with thermochemical analyses of the transition states involved in isomerization and elimination steps. For all reactions, barriers increased by less than the concomitant increase in DPE upon changes in composition, because electrostatic stabilization of ion-pairs at the relevant transition states becomes more effective for weaker acids, as a result of their higher charge density at the anionic conjugate base. Alkoxide isomerization barriers were more sensitive to DPE than for elimination from H-bonded alkanols, the step that limits 2-butanol and 1-butanol dehydration rates; the latter two reactions showed similar DPE sensitivities, despite significant differences in their rates and activation barriers, indicating that slower reactions are not necessarily more sensitive to acid strength, but instead reflect the involvement of more unstable organic cations at their transition states. These compensating effects from electrostatic stabilization depend on how similar the charge density in these organic cations is to that in the proton removed. Cations with more localized charge favor strong electrostatic interactions with anions and form more stable ionic structures than do cations with more diffuse charges. Ion-pairs at elimination transition states contain cations with higher local charge density at the sp(2) carbon than for isomerization transition states; as a result, these ion-pairs recover a larger fraction of the deprotonation energy, and, consequently, their reactions become less sensitive to acid strength. These concepts lead us to conclude that the energetic difficulty of a catalytic reaction, imposed by gas-phase reactant proton affinities in transition state analogues, does not determine its sensitivity to the acid strength of solid catalysts.

Relativistic polytropic spheres with electric charge: Compact stars, compactness and mass bounds, and quasiblack hole configurations

NASA Astrophysics Data System (ADS)

Arbañil, José D. V.; Zanchin, Vilson T.

2018-05-01

We study the static equilibrium configurations of uncharged and charged spheres composed by a relativistic polytropic fluid, and we compare with those of spheres composed by a nonrelativistic polytropic fluid, the later case being already studied in a previous work [J. D. Arbañil, P. S. Lemos, and V. T. Zanchin, Phys. Rev. D 88, 084023 (2013), 10.1103/PhysRevD.88.084023]. An equation of state connecting the pressure p and the energy density ρ is assumed. In the nonrelativistic fluid case, the connection is through a nonrelativistic polytropic equation of state, p =ω ργ , with ω and γ being respectively the polytropic constant and the polytropic exponent. In the relativistic fluid case, the connection is through a relativistic polytropic equation of state, p =ω δγ, with δ =ρ -p /(γ -1 ), and δ being the rest-mass density of the fluid. For the electric charge distribution, we assume that the charge density ρe is proportional to the energy density ρ , ρe=α ρ , with α being a constant such that 0 ≤|α |≤1 . The study is developed by integrating numerically the hydrostatic equilibrium equation. Some properties of the charged spheres such as the gravitational mass, the total electric charge, the radius, the surface redshift, and the speed of sound are analyzed by varying the central rest-mass density, the charge fraction, and the polytropic exponent. In addition, some limits that arise in general relativity, such as the Chandrasekhar limit, the Oppenheimer-Volkoff limit, the Buchdahl bound, and the Buchdahl-Andréasson bound are studied. It is confirmed that charged relativistic polytropic spheres with γ →∞ and α →1 saturate the Buchdahl-Andréasson bound, thus indicating that it reaches the quasiblack hole configuration. We show by means of numerical analysis that, as expected, the major differences between the two cases appear in the high energy density region.

Lysozyme adsorption in pH-responsive hydrogel thin-films: the non-trivial role of acid-base equilibrium.

PubMed

Narambuena, Claudio F; Longo, Gabriel S; Szleifer, Igal

2015-09-07

We develop and apply a molecular theory to study the adsorption of lysozyme on weak polyacid hydrogel films. The theory explicitly accounts for the conformation of the network, the structure of the proteins, the size and shape of all the molecular species, their interactions as well as the chemical equilibrium of each titratable unit of both the protein and the polymer network. The driving forces for adsorption are the electrostatic attractions between the negatively charged network and the positively charged protein. The adsorption is a non-monotonic function of the solution pH, with a maximum in the region between pH 8 and 9 depending on the salt concentration of the solution. The non-monotonic adsorption is the result of increasing negative charge of the network with pH, while the positive charge of the protein decreases. At low pH the network is roughly electroneutral, while at sufficiently high pH the protein is negatively charged. Upon adsorption, the acid-base equilibrium of the different amino acids of the protein shifts in a nontrivial fashion that depends critically on the particular kind of residue and solution composition. Thus, the proteins regulate their charge and enhance adsorption under a wide range of conditions. In particular, adsorption is predicted above the protein isoelectric point where both the solution lysozyme and the polymer network are negatively charged. This behavior occurs because the pH in the interior of the gel is significantly lower than that in the bulk solution and it is also regulated by the adsorption of the protein in order to optimize protein-gel interactions. Under high pH conditions we predict that the protein changes its charge from negative in the solution to positive within the gel. The change occurs within a few nanometers at the interface of the hydrogel film. Our predictions show the non-trivial interplay between acid-base equilibrium, physical interactions and molecular organization under nanoconfined conditions, which leads to non-trivial adsorption behavior that is qualitatively different from what would be predicted from the state of the proteins in the bulk solution.

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.

Electro-convective versus electroosmotic instability in concentration polarization.

PubMed

Rubinstein, Isaak; Zaltzman, Boris

2007-10-31

Electro-convection is reviewed as a mechanism of mixing in the diffusion layer of a strong electrolyte adjacent to a charge-selective solid, such as an ion exchange (electrodialysis) membrane or an electrode. Two types of electro-convection in strong electrolytes may be distinguished: bulk electro-convection, due to the action of the electric field upon the residual space charge of a quasi-electro-neutral bulk solution, and convection induced by electroosmotic slip, due to electric forces acting in the thin electric double layer of either quasi-equilibrium or non-equilibrium type near the solid/liquid interface. According to recent studies, the latter appears to be the likely source of mixing in the diffusion layer, leading to 'over-limiting' conductance in electrodialysis. Electro-convection near a planar uniform charge selective solid/liquid interface sets on as a result of hydrodynamic instability of one-dimensional steady state electric conduction through such an interface. We compare the results of linear stability analysis obtained for instabilities of this kind appearing in the full electro-convective and limiting non-equilibrium electroosmotic formulations. The short- and long-wave aspects of these instabilities are discussed along with the wave number selection principles.

Resolving the excited state equilibrium of peridinin in solution.

PubMed

Papagiannakis, Emmanouil; Larsen, Delmar S; van Stokkum, Ivo H M; Vengris, Mikas; Hiller, Roger G; van Grondelle, Rienk

2004-12-14

The carotenoid peridinin is abundant in the biosphere, as it is the main pigment bound by the light-harvesting complexes of dinoflagellates, where it collects blue and green sunlight and transfers energy to chlorophyll a with high efficiency. Its molecular structure is particularly complex, giving rise to an intricate excited state manifold, which includes a state with charge-transfer character. To disentangle the excited states of peridinin and understand their function in vivo, we applied dispersed pump-probe and pump-dump-probe spectroscopy. The preferential depletion of population from the intramolecular charge transfer state by the dump pulse demonstrates that the S(1) and this charge transfer state are distinct entities. The ensuing dump-induced dynamics illustrates the equilibration of the two states which occurs on the time scale of a few picoseconds. Additionally, the dump pulse populates a short-lived ground state intermediate, which is suggestive of a complex relaxation pathway, probably including structural reorientation or solvation of the ground state. These findings indicate that the unique intramolecular charge transfer state of peridinin is an efficient energy donor to chlorophyll a in the peridinin-chlorophyll-protein complex and thus plays a significant role in global light harvesting.

Equilibrium charge state distributions of Ni, Co, and Cu beams in molybdenum foil at 2 MeV/u

NASA Astrophysics Data System (ADS)

Gastis, Panagiotis; Perdikakis, George; Robertson, Daniel; Bauder, Will; Skulski, Michael; Collon, Phillipe; Anderson, Tyler; Ostdiek, Karen; Aprahamian, Ani; Lu, Wenting; Almus, Robert

2015-10-01

The charge states of heavy-ions are important for the study of nuclear reactions in inverse kinematics when electromagnetic recoil mass spectrometers are used. The passage of recoil products through a material, like the windows of gas cells or charge state boosters, results a charge state distribution (CSD) in the exit. This distribution must be known for the extraction of any cross section since only few charge-state can be transmitted through a magnetic separator separator for a given setting. The calculation of CSDs for heavy ions is challenging. Currently we rely on semi-empirical models with unknown accuracy for ion/target combinations in the Z > 20 region. In the present study were measured the CSDs of the stable 60Ni, 59Co, and 63Cu beams while passing through a 1 μm molybdenum foil. The beam energies were 1.84 MeV/u, 2.09 MeV/u, and 2.11 MeV/u for the 60Ni, 59Co, and 63Cu respectively. The results of this study mainly check the accuracy of the semi-empirical models used by the program LISE++, on calculating CSDs for ion/target combinations of Z > 20. In addition, other empirical models on calculating mean charge states were compared and checked.

Charge transfer induced by MoO3 at boron subphthalocyanine chloride/α-sexithiophene heterojunction interface

NASA Astrophysics Data System (ADS)

Foggiatto, Alexandre L.; Sakurai, Takeaki

2018-03-01

The energy-level alignment of boron subphthalocyanine chloride (SubPc)/α-sexithiophene (6T) grown on MoO3 was investigated using ultraviolet and X-ray photoelectron spectroscopy (UPS and XPS). We demonstrated that the p-doping effect generated by the MoO3 layer can induce charge transfer at the organic-organic heterojunction interface. After the deposition of 6T on MoO3, the fermi level becomes pinned close to the 6T highest occupied molecular orbital (HOMO) level and when SubPc is deposited, owing to its tail states, charge transfer occurs in order to achieve thermodynamic equilibrium. We also demonstrated that the charge transfer can be reduced by annealing the film. We suggested that the reduction of the misalignment on the film induces a reduction in the density of gap states, which controls the charge transfer.

Cytochrome c at charged interfaces studied by resonance Raman and surface-enhanced resonance Raman spectroscopy

NASA Astrophysics Data System (ADS)

Hildebrandt, Peter

1991-05-01

The effect of electrostatic fields on the structure of cytochrome c bound to charged interfaces was studied by resonance Raman and surface enhanced resonance Raman spectroscopy. Binding of this heme protein to the Ag electrode or heteropolytungstates which may be regarded as simple model systems for biological interfaces establishes an equilibrium between two conformational states (I II). In state I the structure and the redox potential are the same as for the uncomplexed cytochrome c. In state II however the heme pocket assumes an open structure and the axial iron Met80 bond is weakened leading to thennal coordination equilibrium between the fivecoordinated high spin and the sixcoordinated low spin configuration. These structural changes are accompanied by a decrease of the redox potential by 420 mV. The structural rearrangement of the heme pocket in state II is presumably initiated by the dissociation of the internal salt bridge of Lys13 due to electrostatic interactions with the negatively charged surfaces of the model systems. From detailed Raman spectroscopic studies characteristic spectral properties of the states I and II were identified. Based on these findings the interactions of cytochrome c with phospholipid vesicles as well as with its physiological reaction partner cytocbrome c oxidase were analysed. A systematic study of the cytochmme c/phospholipid system by varying the lipid composition and the temperature revealed mutual structural changes in both the lipid and the protein structure.

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

Zhang, Z. D.; Wang, J.; Department of Chemistry, SUNY Stony Brook, New York 11794

We established a theoretical framework in terms of the curl flux, population landscape, and coherence for non-equilibrium quantum systems at steady state, through exploring the energy and charge transport in molecular processes. The curl quantum flux plays the key role in determining transport properties and the system reaches equilibrium when flux vanishes. The novel curl quantum flux reflects the degree of non-equilibriumness and the time-irreversibility. We found an analytical expression for the quantum flux and its relationship to the environmental pumping (non-equilibriumness quantified by the voltage away from the equilibrium) and the quantum tunneling. Furthermore, we investigated another quantum signature,more » the coherence, quantitatively measured by the non-zero off diagonal element of the density matrix. Populations of states give the probabilities of individual states and therefore quantify the population landscape. Both curl flux and coherence depend on steady state population landscape. Besides the environment-assistance which can give dramatic enhancement of coherence and quantum flux with high voltage at a fixed tunneling strength, the quantum flux is promoted by the coherence in the regime of small tunneling while reduced by the coherence in the regime of large tunneling, due to the non-monotonic relationship between the coherence and tunneling. This is in contrast to the previously found linear relationship. For the systems coupled to bosonic (photonic and phononic) reservoirs the flux is significantly promoted at large voltage while for fermionic (electronic) reservoirs the flux reaches a saturation after a significant enhancement at large voltage due to the Pauli exclusion principle. In view of the system as a quantum heat engine, we studied the non-equilibrium thermodynamics and established the analytical connections of curl quantum flux to the transport quantities such as energy (charge) transfer efficiency, chemical reaction efficiency, energy dissipation, heat and electric currents observed in the experiments. We observed a perfect transfer efficiency in chemical reactions at high voltage (chemical potential difference). Our theoretical predicted behavior of the electric current with respect to the voltage is in good agreements with the recent experiments on electron transfer in single molecules.« less

Contribution of Charged Groups to the Enthalpic Stabilization of the Folded States of Globular Proteins

PubMed Central

Dadarlat, Voichita M.; Post, Carol Beth

2016-01-01

In this paper we use the results from all atom MD simulations of proteins and peptides to assess individual contribution of charged atomic groups to the enthalpic stability of the native state of globular proteins and investigate how the distribution of charged atomic groups in terms of solvent accessibility relates to protein enthalpic stability. The contributions of charged groups is calculated using a comparison of nonbonded interaction energy terms from equilibrium simulations of charged amino acid dipeptides in water (the “unfolded state”) and charged amino acids in globular proteins (the “folded state”). Contrary to expectation, the analysis shows that many buried, charged atomic groups contribute favorably to protein enthalpic stability. The strongest enthalpic contributions favoring the folded state come from the carboxylate (COO−) groups of either Glu or Asp. The contributions from Arg guanidinium groups are generally somewhat stabilizing, while NH3+ groups from Lys contribute little toward stabilizing the folded state. The average enthalpic gain due to the transfer of a methyl group in an apolar amino acid from solution to the protein interior is described for comparison. Notably, charged groups that are less exposed to solvent contribute more favorably to protein native-state enthalpic stability than charged groups that are solvent exposed. While solvent reorganization/release has favorable contributions to folding for all charged atomic groups, the variation in folded state stability among proteins comes mainly from the change in the nonbonded interaction energy of charged groups between the unfolded and folded states. A key outcome is that the calculated enthalpic stabilization is found to be inversely proportional to the excess charge density on the surface, in support of an hypothesis proposed previously. PMID:18303881

Properties of quasiparticles in Luttinger liquid

NASA Astrophysics Data System (ADS)

Koutouza, Andrei Boris

In this dissertation we first explain why the Fermi liquid theory breaks down in one dimension and introduce the concept of Luttinger Liquid and the idea of bozonization. In the second part, we study the tunneling through an impurity in a quantum wire with arbitrary Luttinger interaction parameter. By combining the integrable approach, developed in the case of quantum Hall edge states, with the introduction of radiative boundary conditions to describe the adiabatic coupling to the reservoirs, we are able to obtain the exact equilibrium and non-equilibrium current. One of the most striking features observed is the appearance of negative differential conductances out of equilibrium in the strongly interacting regime g < 0.2. In spite of the various charging effects, a remarkable form of duality is still observed. In the third part, the tunneling between edge states in the Fractional Quantum Hall Effect is studied and the shot noise is computed to determine the charge of the carriers in the system. We show that the inclusion of irrelevant terms in the Hamiltonian, describing tunneling between edge states in the fractional quantum Hall effect affect crucially the determination of charge through shot noise measurements. We show, for instance, that certain combinations of relevant and irrelevant terms can lead to an effective measured charge e in the strong backscattering limit and an effective measured charge e in the weak backscattering limit, in sharp contrast with standard perturbative expectations. This provides a possible scenario to explain the experimental observations by Heiblum et al. [35], which are so far not understood. And finally, the scattering amplitudes at a point contact between a Fermi liquid and a Luttinger liquid will be considered, and calculated in the certain cases, using the form-factors technique. These include the reflection and transmission amplitudes at a point contact between a Fermi liquid and a g = 1/3 Luttinger liquid for the processes 2e → 2e, and e → e. These results are obtained in closed form, and give rise to rather simple expressions for the probabilities of the most basic processes of non-Fermi liquid physics at these special values of the couplings.

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.

Fuel-Mediated Transient Clustering of Colloidal Building Blocks.

PubMed

van Ravensteijn, Bas G P; Hendriksen, Wouter E; Eelkema, Rienk; van Esch, Jan H; Kegel, Willem K

2017-07-26

Fuel-driven assembly operates under the continuous influx of energy and results in superstructures that exist out of equilibrium. Such dissipative processes provide a route toward structures and transient behavior unreachable by conventional equilibrium self-assembly. Although perfected in biological systems like microtubules, this class of assembly is only sparsely used in synthetic or colloidal analogues. Here, we present a novel colloidal system that shows transient clustering driven by a chemical fuel. Addition of fuel causes an increase in hydrophobicity of the building blocks by actively removing surface charges, thereby driving their aggregation. Depletion of fuel causes reappearance of the charged moieties and leads to disassembly of the formed clusters. This reassures that the system returns to its initial, equilibrium state. By taking advantage of the cyclic nature of our system, we show that clustering can be induced several times by simple injection of new fuel. The fuel-mediated assembly of colloidal building blocks presented here opens new avenues to the complex landscape of nonequilibrium colloidal structures, guided by biological design principles.

Oppositely charged colloids out of equilibrium

NASA Astrophysics Data System (ADS)

Vissers, T.

2010-11-01

Colloids are particles with a size in the range of a few nanometers up to several micrometers. Similar to atomic and molecular systems, they can form gases, liquids, solids, gels and glasses. Colloids can be used as model systems because, unlike molecules, they are sufficiently large to be studied directly with light microscopy and move sufficiently slow to study their dynamics. In this thesis, we study binary systems of polymethylmethacrylate (PMMA) colloidal particles suspended in low-polar solvent mixtures. Since the ions can still partially dissociate, a surface charge builds up which causes electrostatic interactions between the colloids. By carefully tuning the conditions inside the suspension, we make two kinds of particles oppositely charged. To study our samples, we use Confocal Laser Scanning Microscopy (CLSM). The positively and negatively charged particles can be distinguished by a different fluorescent dye. Colloids constantly experience a random motion resulting from random kicks of surrounding solvent molecules. When the attractions between the oppositely charged particles are weak, the particles can attach and detach many times and explore a lot of possible configurations and the system can reach thermodynamic equilibrium. For example, colloidal ‘ionic’ crystals consisting of thousands to millions of particles can form under the right conditions. When the attractions are strong, the system can become kinetically trapped inside a gel-like state. We observe that when the interactions change again, crystals can even emerge again from this gel-like phase. By using local order parameters, we quantitatively study the crystallization of colloidal particles and identify growth defects inside the crystals. We also study the effect of gravity on the growth of ionic crystals by using a rotating stage. We find that sedimentation can completely inhibit crystal growth and plays an important role in crystallization from the gel-like state. The surface potential and charge are studied by electrophoresis. Here, the velocity of the particles is measured while they are moving in an electric field. Using our real-space CLSM setup, we find that for a single-component system, the charge on the particles decreases with increasing volume fraction. Apart from structures that oppositely charged particles form close to thermodynamic equilibrium, we also study pattern formation when the system is driven out of equilibrium by an electric field. When oppositely charged particles are driven in opposite directions, the collisions between them cause particle of the same kind to form lanes. By combining our CLSM experiments with Brownian dynamics computer simulations, we study the structure and the dynamics of the suspension on the single-particle level. We find that the number of particles in a lane increases continuously with the field strength. By studying the dynamics and fluctuations parallel and perpendicular to the electric field direction, we identify the key mechanism of lane-formation. We show that pattern formation can easily become more complicated when we introduce alternating current (AC) fields. In addition to the formation of lanes parallel to the field-axis, bands of like-charged particles can form perpendicular to it. When the particles are sufficiently mobile, the system can be remixed again by changing the frequency. When AC-fields with higher field strengths are used, we show that complex patterns, including rotating instabilities, can emerge. The results in this thesis yield fundamental insight in electrophoresis, crystallization and pattern formation when systems are driven out of equilibrium. The results on lane- and band-formation can be relevant for the design of electronic ink (e-ink), where electrically driven oppositely charged particles are used to change the image on a piece of electronic paper.

Contribution of Electrostatics in the Fibril Stability of a Model Ionic-Complementary Peptide.

PubMed

Owczarz, Marta; Casalini, Tommaso; Motta, Anna C; Morbidelli, Massimo; Arosio, Paolo

2015-12-14

In this work we quantified the role of electrostatic interactions in the self-assembly of a model amphiphilic peptide (RADA 16-I) into fibrillar structures by a combination of size exclusion chromatography and molecular simulations. For the peptide under investigation, it is found that a net charge of +0.75 represents the ideal condition to promote the formation of regular amyloid fibrils. Lower net charges favor the formation of amorphous precipitates, while larger net charges destabilize the fibrillar aggregates and promote a reversible dissociation of monomers from the ends of the fibrils. By quantifying the dependence of the equilibrium constant of this reversible reaction on the pH value and the peptide net charge, we show that electrostatic interactions contribute largely to the free energy of fibril formation. The addition of both salt and a charged destabilizer (guanidinium hydrochloride) at moderate concentration (0.3-1 M) shifts the monomer-fibril equilibrium toward the fibrillar state. Whereas the first effect can be explained by charge screening of electrostatic repulsion only, the promotion of fibril formation in the presence of guanidinium hydrochloride is also attributed to modifications of the peptide conformation. The results of this work indicate that the global peptide net charge is a key property that correlates well with the fibril stability, although the peptide conformation and the surface charge distribution also contribute to the aggregation propensity.

Light charged clusters emitted in 32 MeV/nucleon Xe,124136+Sn,112124 reactions: Chemical equilibrium and production of 3He and 6He

NASA Astrophysics Data System (ADS)

Bougault, R.; Bonnet, E.; Borderie, B.; Chbihi, A.; Dell'Aquila, D.; Fable, Q.; Francalanza, L.; Frankland, J. D.; Galichet, E.; Gruyer, D.; Guinet, D.; Henri, M.; La Commara, M.; Le Neindre, N.; Lombardo, I.; Lopez, O.; Manduci, L.; Marini, P.; Pârlog, M.; Roy, R.; Saint-Onge, P.; Verde, G.; Vient, E.; Vigilante, M.; Indra Collaboration

2018-02-01

Background: The isovector part of the nuclear equation of state remains partly unknown and is the subject of many studies. The degree of equilibration between the two main collision partners in heavy ion reactions may be used to study the equation of state since it is connected to isospin (N /Z ) transport properties of nuclear matter. Purpose: We aim to test chemical equilibrium attainment by measuring isotopic characteristics of emitted elements as a function of impact parameter. Method: We study four Xe,124136+Sn,112124 reactions at 32 MeV/nucleon. The data were acquired with the INDRA detector at the GANIL (Caen, France) facility. Combined (projectile+target) systems are identical for two studied reactions, therefore it is possible to study the path towards chemical equilibrium from different neutron to proton ratio (N /Z ) entrance channels. The study is limited to identified isotopes detected in the forward part of the center of mass in order to focus on the evolution of projectile-like fragment isotopic content and the benefit of excellent detection performances of the forward part of the apparatus. Results: Light charged particle productions, multiplicities, and abundance ratios dependence against impact parameter are studied. It is measured to almost identical mean characteristics for the two 124Xe+124Sn and 136Xe+112Sn systems for central collisions. Comparing all four studied systems it is shown that mean values evolve from projectile N /Z to projectile+target N /Z dependence. Those identical mean characteristics concern all light charged particles except 3He whose mean behavior is strongly different. Conclusions: Our inclusive analysis (no event selection) shows that N /Z equilibration between the projectile-like and the target-like is realized to a high degree for central collisions. The light charged particle production mean value difference between 124Xe+124Sn and 136Xe+112Sn systems for central collisions is of the order of a few %. This slight difference could be explained by pre-equilibrium particle emission whose intensity may differ for the two reactions. This point is demonstrated using 3He mean characteristics whose production takes place before chemical equilibrium attainment. The realized N /Z balance between projectile-like and target-like does not imply a pure two-body mechanism. Indeed a midrapidity production of light charged particle does exist and its N /Z is different as compared to the projectile-like one: it is n enriched. This point is touched using 6He midrapidity production which is favored by the drift phenomenon.

Glutamate Induced Thermal Equilibrium Intermediate and Counteracting Effect on Chemical Denaturation of Proteins.

PubMed

Anumalla, Bramhini; Prabhu, N Prakash

2018-01-25

When organisms are subjected to stress conditions, one of their adaptive responses is accumulation of small organic molecules called osmolytes. These osmolytes affect the structure and stability of the biological macromolecules including proteins. The present study examines the effect of a negatively charged amino acid osmolyte, glutamate (Glu), on two model proteins, ribonuclease A (RNase A) and α-lactalbumin (α-LA), which have positive and negative surface charges at pH 7, respectively. These proteins follow two-state unfolding transitions during both heat and chemical induced denaturation processes. The addition of Glu stabilizes the proteins against temperature and induces an early equilibrium intermediate during unfolding. The stability is found to be enthalpy-driven, and the free energy of stabilization is more for α-LA compared to RNase A. The decrease in the partial molar volume and compressibility of both of the proteins in the presence of Glu suggests that the proteins attain a more compact state through surface hydration which could provide a more stable conformation. This is also supported by molecule dynamic simulation studies which demonstrate that the water density around the proteins is increased upon the addition of Glu. Further, the intermediates could be completely destabilized by lower concentrations (∼0.5 M) of guanidinium chloride and salt. However, urea subverts the Glu-induced intermediate formed by α-LA, whereas it only slightly destabilizes in the case of RNase A which has a positive surface charge and could possess charge-charge interactions with Glu. This suggests that, apart from hydration, columbic interactions might also contribute to the stability of the intermediate. Gdm-induced denaturation of RNase A and α-LA in the absence and the presence of Glu at different temperatures was carried out. These results also show the Glu-induced stabilization of both of the proteins; however, all of the unfolding transitions followed two-state transitions during chemical denaturation. The extent of stability exerted by Glu is higher for RNase A at higher temperature, whereas it provides more stability for α-LA at lower temperature. Thus, the experiments indicate that Glu induces a thermal equilibrium intermediate and increases the thermodynamic stability of proteins irrespective of their surface charges. The extent of stability varies between the proteins in a temperature-dependent manner.

Charging of Interstellar Dust Grains in the out-of-equilibrium Heliosheath Plasma traced by IBEX ENAs

NASA Astrophysics Data System (ADS)

Frisch, P. C.; Ogasawara, K.; Livadiotis, G.; Slavin, J. D.; McComas, D. J.; Funsten, H. O.; Schwadron, N.; Heerikhuisen, J.

2017-12-01

Dusty bow waves are common around stars and anticipated around the heliosphere due to the deficit of low-mass interstellar dust grains in the inner heliosphere. Interstellar grains entering the heliosphere must first cross barriers of non-Maxwellian plasma in the heliosheath regions where collisional charging of grains is highly effective. IBEX measures 0.1-6 keV ENAs in the heliosheath plasma, providing an in situ sample of the heliosheath plasma thermodynamics that can be used for grain-charging calculations. Plasma in three-quarters of the sky can be described with a stationary state kappa-distribution, giving predictions for kappa, kappa-distribution temperature, and plasma density [1]. This thermodynamic description allows a more realistic evaluation of the dominant heliosheath electron and ion currents, and hence also grain gyroradii and exclusion from the heliosphere. At the highest temperatures ion collisional currents dominate grain charging; at lower temperatures collisional electron currents are more important together with the photoelectric ejection of electrons. An absence of data on the thermodynamical state of heliosheath electrons has led to the assumption of similar thermodynamic parameters for the electron and ion populations. The balance between electron, proton and photoionization currents on the grains then yield the equilibrium grain charges. Grain gyroradii calculated based on these charging currents differentiate between interstellar grains able to penetrate the heliosphere, versus those that are excluded, and allow predictions of properties of the dusty bow wave likely to be present around the heliosphere. The smallest grains are excluded and grains at the high latitude edges of the described regions tend to have systematically lower grain potentials. Grain charging calculations utilize the modeling of [2]. [1] Livadiotis et al., ApJ 734, 1 (2011). [2] Weingartner Draine, ApJSS 263 (2001)

Explosion and Final State of an Unstable Reissner-Nordström Black Hole.

PubMed

Sanchis-Gual, Nicolas; Degollado, Juan Carlos; Montero, Pedro J; Font, José A; Herdeiro, Carlos

2016-04-08

A Reissner-Nordström black hole (BH) is superradiantly unstable against spherical perturbations of a charged scalar field enclosed in a cavity, with a frequency lower than a critical value. We use numerical relativity techniques to follow the development of this unstable system-dubbed a charged BH bomb-into the nonlinear regime, solving the full Einstein-Maxwell-Klein-Gordon equations, in spherical symmetry. We show that (i) the process stops before all the charge is extracted from the BH, and (ii) the system settles down into a hairy BH: a charged horizon in equilibrium with a scalar field condensate, whose phase is oscillating at the (final) critical frequency. For a low scalar field charge q, the final state is approached smoothly and monotonically. For large q, however, the energy extraction overshoots, and an explosive phenomenon, akin to a bosenova, pushes some energy back into the BH. The charge extraction, by contrast, does not reverse.

The Nature of the Intramolecular Charge Transfer State in Peridinin

PubMed Central

Wagner, Nicole L.; Greco, Jordan A.; Enriquez, Miriam M.; Frank, Harry A.; Birge, Robert R.

2013-01-01

Experimental and theoretical evidence is presented that supports the theory that the intramolecular charge transfer (ICT) state of peridinin is an evolved state formed via excited-state bond-order reversal and solvent reorganization in polar media. The ICT state evolves in <100 fs and is characterized by a large dipole moment (∼35 D). The charge transfer character involves a shift of electron density within the polyene chain, and it does not involve participation of molecular orbitals localized in either of the β-rings. Charge is moved from the allenic side of the polyene into the furanic ring region and is accompanied by bond-order reversal in the central portion of the polyene chain. The electronic properties of the ICT state are generated via mixing of the “11Bu+” ionic state and the lowest-lying “21Ag–” covalent state. The resulting ICT state is primarily 1Bu+-like in character and exhibits not only a large oscillator strength but an unusually large doubly excited character. In most solvents, two populations exist in equilibrium, one with a lowest-lying ICT ionic state and a second with a lowest-lying “21Ag–” covalent state. The two populations are separated by a small barrier associated with solvent relaxation and cavity formation. PMID:23528091

Transmission and reflection of charge-density wave packets in a quantum Hall edge controlled by a metal gate

NASA Astrophysics Data System (ADS)

Matsuura, Masahiro; Mano, Takaaki; Noda, Takeshi; Shibata, Naokazu; Hotta, Masahiro; Yusa, Go

2018-02-01

Quantum energy teleportation (QET) is a proposed protocol related to quantum vacuum. The edge channels in a quantum Hall system are well suited for the experimental verification of QET. For this purpose, we examine a charge-density wave packet excited and detected by capacitively coupled front gate electrodes. We observe the waveform of the charge packet, which is proportional to the time derivative of the applied square voltage wave. Further, we study the transmission and reflection behaviors of the charge-density wave packet by applying a voltage to another front gate electrode to control the path of the edge state. We show that the threshold voltages where the dominant direction is switched in either transmission or reflection for dense and sparse wave packets are different from the threshold voltage where the current stops flowing in an equilibrium state.

Disordering of ultra thin WO3 films by high-energy ions

NASA Astrophysics Data System (ADS)

Matsunami, N.; Kato, M.; Sataka, M.; Okayasu, S.

2017-10-01

We have studied disordering or atomic structure modification of ultra thin WO3 films under impact of high-energy ions with non-equilibrium and equilibrium charge incidence, by means of X-ray diffraction (XRD). WO3 films were prepared by thermal oxidation of W deposited on MgO substrate. Film thickness obtained by Rutherford backscattering spectrometry (RBS) is as low as 2 nm. Smoothness of film surface was observed by atomic force microscopy. It is found that the ratio of XRD intensity degradation per 90 MeV Ni+10 ion (the incident charge is lower than the equilibrium charge) to that per 90 MeV Ni ion with the equilibrium charge depends on the film thickness. Also, film thickness dependence is observed for 100 MeV Xe+14. By comparison of the experimental result with a simple model calculation based on the assumption that the mean charge of ions along the depth follows a saturation curve with power-law approximation to the charge dependent electronic stopping power, the characteristic length attaining the equilibrium charge is obtained to be ∼7 nm for 90 MeV Ni+10 ion incidence or the electron loss cross section of ∼1016 cm2, demonstrating that disordering of ultra WO3 films has been observed and a fundamental quantity can be derived through material modification.

Mesoscopic Rings with Spin-Orbit Interactions

ERIC Educational Resources Information Center

Berche, Bertrand; Chatelain, Christophe; Medina, Ernesto

2010-01-01

A didactic description of charge and spin equilibrium currents on mesoscopic rings in the presence of spin-orbit interaction is presented. Emphasis is made on the non-trivial construction of the correct Hamiltonian in polar coordinates, the calculation of eigenvalues and eigenfunctions and the symmetries of the ground-state properties. Spin…

State-to-State Internal Energy Relaxation Following the Quantum-Kinetic Model in DSMC

NASA Technical Reports Server (NTRS)

Liechty, Derek S.

2014-01-01

A new model for chemical reactions, the Quantum-Kinetic (Q-K) model of Bird, has recently been introduced that does not depend on macroscopic rate equations or values of local flow field data. Subsequently, the Q-K model has been extended to include reactions involving charged species and electronic energy level transitions. Although this is a phenomenological model, it has been shown to accurately reproduce both equilibrium and non-equilibrium reaction rates. The usefulness of this model becomes clear as local flow conditions either exceed the conditions used to build previous models or when they depart from an equilibrium distribution. Presently, the applicability of the relaxation technique is investigated for the vibrational internal energy mode. The Forced Harmonic Oscillator (FHO) theory for vibrational energy level transitions is combined with the Q-K energy level transition model to accurately reproduce energy level transitions at a reduced computational cost compared to the older FHO models.

Quantum statistical mechanics of dense partially ionized hydrogen.

NASA Technical Reports Server (NTRS)

Dewitt, H. E.; Rogers, F. J.

1972-01-01

The theory of dense hydrogenic plasmas beginning with the two component quantum grand partition function is reviewed. It is shown that ionization equilibrium and molecular dissociation equilibrium can be treated in the same manner with proper consideration of all two-body states. A quantum perturbation expansion is used to give an accurate calculation of the equation of state of the gas for any degree of dissociation and ionization. In this theory, the effective interaction between any two charges is the dynamic screened potential obtained from the plasma dielectric function. We make the static approximation; and we carry out detailed numerical calculations with the bound and scattering states of the Debye potential, using the Beth-Uhlenbeck form of the quantum second virial coefficient. We compare our results with calculations from the Saha equation.

Charge equilibrium and radiation of low-energy cosmic rays passing through interstellar medium

NASA Technical Reports Server (NTRS)

Rule, D. W.; Omidvar, K.

1979-01-01

The charge equilibrium and radiation of an oxygen and an iron beam in the MeV per nucleon energy range, representing a typical beam of low-energy cosmic rays passing through the interstellar medium, are considered. Electron loss of the beam has been taken into account by means of the first Born approximation, allowing for the target atom to remain unexcited or to be excited to all possible states. Electron-capture cross sections have been calculated by means of the scaled Oppenheimer-Brinkman-Kramers approximation, taking into account all atomic shells of the target atoms and capture into all excited states of the projectile. The capture and loss cross sections are found to be within 20%-30% of the existing experimental values for most of the cases considered. Radiation of the beam due to electron capture into the excited states of the ion, collisional excitation, and collisional inner-shell ionization, taking into account the fluorescence yield of the ions, has been considered. Effective X-ray production cross sections and multiplicities for the most energetic X-ray lines emitted by the Fe and O beams have been calculated, and error estimates made for the results.

Conformal field theory out of equilibrium: a review

NASA Astrophysics Data System (ADS)

Bernard, Denis; Doyon, Benjamin

2016-06-01

We provide a pedagogical review of the main ideas and results in non-equilibrium conformal field theory and connected subjects. These concern the understanding of quantum transport and its statistics at and near critical points. Starting with phenomenological considerations, we explain the general framework, illustrated by the example of the Heisenberg quantum chain. We then introduce the main concepts underlying conformal field theory (CFT), the emergence of critical ballistic transport, and the CFT scattering construction of non-equilibrium steady states. Using this we review the theory for energy transport in homogeneous one-dimensional critical systems, including the complete description of its large deviations and the resulting (extended) fluctuation relations. We generalize some of these ideas to one-dimensional critical charge transport and to the presence of defects, as well as beyond one-dimensional criticality. We describe non-equilibrium transport in free-particle models, where connections are made with generalized Gibbs ensembles, and in higher-dimensional and non-integrable quantum field theories, where the use of the powerful hydrodynamic ideas for non-equilibrium steady states is explained. We finish with a list of open questions. The review does not assume any advanced prior knowledge of conformal field theory, large-deviation theory or hydrodynamics.

A method to determine residue-specific unfolded-state pKa values from analysis of stability changes in single mutant cycles.

PubMed

Shen, Jana K

2010-06-02

It is now widely recognized that the unfolded state of a protein in equilibrium with the native state under folding conditions may contain significant residual structures. However, due to technical difficulties residue-specific interactions in the unfolded state remain elusive. Here we introduce a method derived from the Wyman-Tanford theory to determine residue-specific pK(a)'s in the unfolded state. This method requires equilibrium stability measurements of the wild type and single-point mutants in which titrable residues are replaced with charge-neutral ones under two pH conditions. Application of the proposed approach reveals a highly depressed pK(a) for Asp8 in the unfolded state of the NTL9 protein. Knowledge of unfolded-state pK(a)'s enables quantitative estimation of the unfolded-state electrostatic effects on protein stability. It also provides valuable benchmarks for the improvement of force fields and validation of microscopic information from molecular dynamics simulations.

Enhanced pairing susceptibility in a photodoped two-orbital Hubbard model

NASA Astrophysics Data System (ADS)

Werner, Philipp; Strand, Hugo U. R.; Hoshino, Shintaro; Murakami, Yuta; Eckstein, Martin

2018-04-01

Local spin fluctuations provide the glue for orbital-singlet spin-triplet pairing in the doped Mott insulating regime of multiorbital Hubbard models. At large Hubbard repulsion U , the pairing susceptibility is nevertheless tiny because the pairing interaction cannot overcome the suppression of charge fluctuations. Using nonequilibrium dynamical mean field simulations of the two-orbital Hubbard model, we show that out of equilibrium the pairing susceptibility in this large-U regime can be strongly enhanced by creating a photoinduced population of the relevant charge states. This enhancement is supported by the long lifetime of photodoped charge carriers and a built-in cooling mechanism in multiorbital Hubbard systems.

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.

Quench dynamics in superconducting nanojunctions: Metastability and dynamical Yang-Lee zeros

NASA Astrophysics Data System (ADS)

Souto, R. Seoane; Martín-Rodero, A.; Yeyati, A. Levy

2017-10-01

We study the charge transfer dynamics following the formation of a phase or voltage biased superconducting nanojunction using a full counting statistics analysis. We demonstrate that the evolution of the zeros of the generating function allows one to identify the population of different many body states much in the same way as the accumulation of Yang-Lee zeros of the partition function in equilibrium statistical mechanics is connected to phase transitions. We give an exact expression connecting the dynamical zeros to the charge transfer cumulants and discuss when an approximation based on "dominant" zeros is valid. We show that, for generic values of the parameters, the system gets trapped into a metastable state characterized by a nonequilibrium population of the many body states which is dependent on the initial conditions. We study in particular the effect of the switching rates in the dynamics showing that, in contrast to intuition, the deviation from thermal equilibrium increases for the slower rates. In the voltage biased case the steady state is reached independent of the initial conditions. Our method allows us to obtain accurate results for the steady state current and noise in quantitative agreement with steady state methods developed to describe the multiple Andreev reflections regime. Finally, we discuss the system dynamics after a sudden voltage drop showing the possibility of tuning the many body states population by an appropriate choice of the initial voltage, providing a feasible experimental way to access the quench dynamics and control the state of the system.

Quantum Theory of Atoms in Molecules Charge-Charge Transfer-Dipolar Polarization Classification of Infrared Intensities.

PubMed

Duarte, Leonardo J; Richter, Wagner E; Silva, Arnaldo F; Bruns, Roy E

2017-10-26

Fundamental infrared vibrational transition intensities of gas-phase molecules are sensitive probes of changes in electronic structure accompanying small molecular distortions. Models containing charge, charge transfer, and dipolar polarization effects are necessary for a successful classification of the C-H, C-F, and C-Cl stretching and bending intensities. C-H stretching and in-plane bending vibrations involving sp 3 carbon atoms have small equilibrium charge contributions and are accurately modeled by the charge transfer-counterpolarization contribution and its interaction with equilibrium charge movement. Large C-F and C═O stretching intensities have dominant equilibrium charge movement contributions compared to their charge transfer-dipolar polarization ones and are accurately estimated by equilibrium charge and the interaction contribution. The C-F and C-Cl bending modes have charge and charge transfer-dipolar polarization contribution sums that are of similar size but opposite sign to their interaction values resulting in small intensities. Experimental in-plane C-H bends have small average intensities of 12.6 ± 10.4 km mol -1 owing to negligible charge contributions and charge transfer-counterpolarization cancellations, whereas their average out-of-plane experimental intensities are much larger, 65.7 ± 20.0 km mol -1 , as charge transfer is zero and only dipolar polarization takes place. The C-F bending intensities have large charge contributions but very small intensities. Their average experimental out-of-plane intensity of 9.9 ± 12.6 km mol -1 arises from the cancellation of large charge contributions by dipolar polarization contributions. The experimental average in-plane C-F bending intensity, 5.8 ± 7.3 km mol -1 , is also small owing to charge and charge transfer-counterpolarization sums being canceled by their interaction contributions. Models containing only atomic charges and their fluxes are incapable of describing electronic structure changes for simple molecular distortions that are of interest in classifying infrared intensities. One can expect dipolar polarization effects to also be important for larger distortions of chemical interest.

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.

Quantitative analysis of intramolecular exciplex and electron transfer in a double-linked zinc porphyrin-fullerene dyad.

PubMed

Al-Subi, Ali Hanoon; Niemi, Marja; Tkachenko, Nikolai V; Lemmetyinen, Helge

2012-10-04

Photoinduced charge transfer in a double-linked zinc porphyrin-fullerene dyad is studied. When the dyad is excited at the absorption band of the charge-transfer complex (780 nm), an intramolecular exciplex is formed, followed by the complete charge separated (CCS) state. By analyzing the results obtained from time-resolved transient absorption and emission decay measurements in a range of solvents with different polarities, we derived a dependence between the observable lifetimes and internal parameters controlling the reaction rate constants based on the semiquantum Marcus electron-transfer theory. The critical value of the solvent polarity was found to be ε(r) ≈ 6.5: in solvents with higher dielectric constants, the energy of the CCS state is lower than that of the exciplex and the relaxation takes place via the CCS state predominantly, whereas in solvents with lower polarities the energy of the CCS state is higher and the exciplex relaxes directly to the ground state. In solvents with moderate polarities the exciplex and the CCS state are in equilibrium and cannot be separated spectroscopically. The degree of the charge shift in the exciplex relative to that in the CCS state was estimated to be 0.55 ± 0.02. The electronic coupling matrix elements for the charge recombination process and for the direct relaxation of the exciplex to the ground state were found to be 0.012 ± 0.001 and 0.245 ± 0.022 eV, respectively.

Equilibrium lithium-ion transport between nanocrystalline lithium-inserted anatase TiO2 and the electrolyte.

PubMed

Ganapathy, Swapna; van Eck, Ernst R H; Kentgens, Arno P M; Mulder, Fokko M; Wagemaker, Marnix

2011-12-23

The power density of lithium-ion batteries requires the fast transfer of ions between the electrode and electrolyte. The achievable power density is directly related to the spontaneous equilibrium exchange of charged lithium ions across the electrolyte/electrode interface. Direct and unique characterization of this charge-transfer process is very difficult if not impossible, and consequently little is known about the solid/liquid ion transfer in lithium-ion-battery materials. Herein we report the direct observation by solid-state NMR spectroscopy of continuous lithium-ion exchange between the promising nanosized anatase TiO(2) electrode material and the electrolyte. Our results reveal that the energy barrier to charge transfer across the electrode/electrolyte interface is equal to or greater than the barrier to lithium-ion diffusion through the solid anatase matrix. The composition of the electrolyte and in turn the solid/electrolyte interface (SEI) has a significant effect on the electrolyte/electrode lithium-ion exchange; this suggests potential improvements in the power of batteries by optimizing the electrolyte composition. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quasi-Particle Relaxation and Quantum Femtosecond Magnetism in Non-Equilibrium Phases of Insulating Manganites

NASA Astrophysics Data System (ADS)

Perakis, Ilias; Kapetanakis, Myron; Lingos, Panagiotis; Barmparis, George; Patz, A.; Li, T.; Wang, Jigang

We study the role of spin quantum fluctuations driven by photoelectrons during 100fs photo-excitation of colossal magneto-resistive manganites in anti-ferromagnetic (AFM) charge-ordered insulating states with Jahn-Teller distortions. Our mean-field calculation of composite fermion excitations demonstrates that spin fluctuations reduce the energy gap by quasi-instantaneously deforming the AFM background, thus opening a conductive electronic pathway via FM correlation. We obtain two quasi-particle bands with distinct spin-charge dynamics and dependence on lattice distortions. To connect with fs-resolved spectroscopy experiments, we note the emergence of fs magnetization in the low-temperature magneto-optical signal, with threshold dependence on laser intensity characteristic of a photo-induced phase transition. Simultaneously, the differential reflectivity shows bi-exponential relaxation, with fs component, small at low intensity, exceeding ps component above threshold for fs AFM-to-FM switching. This suggests the emergence of a non-equilibrium metallic FM phase prior to establishment of a new lattice structure, linked with quantum magnetism via spin/charge/lattice couplings for weak magnetic fields.

Charge and pairing dynamics in the attractive Hubbard model: Mode coupling and the validity of linear-response theory

NASA Astrophysics Data System (ADS)

Bünemann, Jörg; Seibold, Götz

2017-12-01

Pump-probe experiments have turned out as a powerful tool in order to study the dynamics of competing orders in a large variety of materials. The corresponding analysis of the data often relies on standard linear-response theory generalized to nonequilibrium situations. Here we examine the validity of such an approach for the charge and pairing response of systems with charge-density wave and (or) superconducting (SC) order. Our investigations are based on the attractive Hubbard model which we study within the time-dependent Hartree-Fock approximation. In particular, we calculate the quench and pump-probe dynamics for SC and charge order parameters in order to analyze the frequency spectra and the coupling of the probe field to the specific excitations. Our calculations reveal that the "linear-response assumption" is justified for small to moderate nonequilibrium situations (i.e., pump pulses) in the case of a purely charge-ordered ground state. However, the pump-probe dynamics on top of a superconducting ground state is determined by phase and amplitude modes which get coupled far from the equilibrium state indicating the failure of the linear-response assumption.

Energy-Dependent Ionization States of Shock-Accelerated Particles in the Solar Corona

NASA Technical Reports Server (NTRS)

Reames, Donald V.; Ng, C. K.; Tylka, A. J.

2000-01-01

We examine the range of possible energy dependence of the ionization states of ions that are shock-accelerated from the ambient plasma of the solar corona. If acceleration begins in a region of moderate density, sufficiently low in the corona, ions above about 0.1 MeV/amu approach an equilibrium charge state that depends primarily upon their speed and only weakly on the plasma temperature. We suggest that the large variations of the charge states with energy for ions such as Si and Fe observed in the 1997 November 6 event are consistent with stripping in moderately dense coronal. plasma during shock acceleration. In the large solar-particle events studied previously, acceleration occurs sufficiently high in the corona that even Fe ions up to 600 MeV/amu are not stripped of electrons.

Specimen charging in X-ray absorption spectroscopy: correction of total electron yield data from stabilized zirconia in the energy range 250-915 eV.

PubMed

Vlachos, Dimitrios; Craven, Alan J; McComb, David W

2005-03-01

The effects of specimen charging on X-ray absorption spectroscopy using total electron yield have been investigated using powder samples of zirconia stabilized by a range of oxides. The stabilized zirconia powder was mixed with graphite to minimize the charging but significant modifications of the intensities of features in the X-ray absorption near-edge fine structure (XANES) still occurred. The time dependence of the charging was measured experimentally using a time scan, and an algorithm was developed to use this measured time dependence to correct the effects of the charging. The algorithm assumes that the system approaches the equilibrium state by an exponential decay. The corrected XANES show improved agreement with the electron energy-loss near-edge fine structure obtained from the same samples.

Rotating charged black holes accelerated by an electric field

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

Bicak, Jiri; Kofron, David; Max Planck Institute for Gravitational Physics, Albert Einstein Institute, Am Muehlenberg 1, D-14476 Golm

The Ernst method of removing nodal singularities from the charged C-metric representing a uniformly accelerated black hole with mass m, charge q and acceleration A by 'adding' an electric field E is generalized. Utilizing the new form of the C-metric found recently, Ernst's simple 'equilibrium condition' mA=qE valid for small accelerations is generalized for arbitrary A. The nodal singularity is removed also in the case of accelerating and rotating charged black holes, and the corresponding equilibrium condition is determined.

Anisotropic quantum quench in the presence of frustration or background gauge fields: A probe of bulk currents and topological chiral edge modes

NASA Astrophysics Data System (ADS)

Killi, Matthew; Trotzky, Stefan; Paramekanti, Arun

2012-12-01

Bosons and fermions, in the presence of frustration or background gauge fields, can form many-body ground states that support equilibrium charge or spin currents. Motivated by the experimental creation of frustration or synthetic gauge fields in ultracold atomic systems, we propose a general scheme by which making a sudden anisotropic quench of the atom tunneling across the lattice and tracking the ensuing density modulations provides a powerful and gauge-invariant route to probing diverse equilibrium current patterns. Using illustrative examples of trapped superfluid Bose and normal Fermi systems in the presence of artificial magnetic fluxes on square lattices, and frustrated bosons in a triangular lattice, we show that this scheme to probe equilibrium bulk current order works independent of particle statistics. We also show that such quenches can detect chiral edge modes in gapped topological states, such as quantum Hall or quantum spin Hall insulators.

Charged anisotropic matter with linear or nonlinear equation of state

NASA Astrophysics Data System (ADS)

Varela, Victor; Rahaman, Farook; Ray, Saibal; Chakraborty, Koushik; Kalam, Mehedi

2010-08-01

Ivanov pointed out substantial analytical difficulties associated with self-gravitating, static, isotropic fluid spheres when pressure explicitly depends on matter density. Simplifications achieved with the introduction of electric charge were noticed as well. We deal with self-gravitating, charged, anisotropic fluids and get even more flexibility in solving the Einstein-Maxwell equations. In order to discuss analytical solutions we extend Krori and Barua’s method to include pressure anisotropy and linear or nonlinear equations of state. The field equations are reduced to a system of three algebraic equations for the anisotropic pressures as well as matter and electrostatic energy densities. Attention is paid to compact sources characterized by positive matter density and positive radial pressure. Arising solutions satisfy the energy conditions of general relativity. Spheres with vanishing net charge contain fluid elements with unbounded proper charge density located at the fluid-vacuum interface. Notably the electric force acting on these fluid elements is finite, although the acting electric field is zero. Net charges can be huge (1019C) and maximum electric field intensities are very large (1023-1024statvolt/cm) even in the case of zero net charge. Inward-directed fluid forces caused by pressure anisotropy may allow equilibrium configurations with larger net charges and electric field intensities than those found in studies of charged isotropic fluids. Links of these results with charged strange quark stars as well as models of dark matter including massive charged particles are highlighted. The van der Waals equation of state leading to matter densities constrained by cubic polynomial equations is briefly considered. The fundamental question of stability is left open.

Rare earth substitutional impurities in germanium: A hybrid density functional theory study

NASA Astrophysics Data System (ADS)

Igumbor, E.; Omotoso, E.; Tunhuma, S. M.; Danga, H. T.; Meyer, W. E.

2017-10-01

The Heyd, Scuseria, and Ernzerhof (HSE06) hybrid functional by means of density functional theory has been used to model the electronic and structural properties of rare earth (RE) substitutional impurities in germanium (REGe) . The formation and charge state transition energies for the REGe (RE = Ce, Pr, Er and Eu) were calculated. The energy of formation for the neutral charge state of the REGe lies between -0.14 and 3.13 eV. The formation energy result shows that the Pr dopant in Ge (PrGe) has the lowest formation energy of -0.14 eV, and is most energetically favourable under equilibrium conditions. The REGe induced charge state transition levels within the band gap of Ge. Shallow acceptor levels were induced by both the Eu (EuGe) and Pr (PrGe) dopants in Ge. The CeGe and ErGe exhibited properties of negative-U ordering with effective-U values of -0.85 and -1.07 eV, respectively.

Experimental and theoretical investigation of radiation and dynamics properties in laser-produced carbon plasmas

NASA Astrophysics Data System (ADS)

Min, Qi; Su, Maogen; Wang, Bo; Cao, Shiquan; Sun, Duixiong; Dong, Chenzhong

2018-05-01

The radiation and dynamics properties of laser-produced carbon plasma in vacuum were studied experimentally with aid of a spatio-temporally resolved emission spectroscopy technique. In addition, a radiation hydrodynamics model based on the fluid dynamic equations and the radiative transfer equation was presented, and calculation of the charge states was performed within the time-dependent collisional radiative model. Detailed temporal and spatial evolution behavior about plasma parameters have been analyzed, such as velocity, electron temperature, charge state distribution, energy level population, and various atomic processes. At the same time, the effects of different atomic processes on the charge state distribution were examined. Finally, the validity of assuming a local thermodynamic equilibrium in the carbon plasma expansion was checked, and the results clearly indicate that the assumption was valid only at the initial (<80 ns) stage of plasma expansion. At longer delay times, it was not applicable near the plasma boundary because of a sharp drop of plasma temperature and electron density.

Equilibrium fluctuation relations for voltage coupling in membrane proteins.

PubMed

Kim, Ilsoo; Warshel, Arieh

2015-11-01

A general theoretical framework is developed to account for the effects of an external potential on the energetics of membrane proteins. The framework is based on the free energy relation between two (forward/backward) probability densities, which was recently generalized to non-equilibrium processes, culminating in the work-fluctuation theorem. Starting from the probability densities of the conformational states along the "voltage coupling" reaction coordinate, we investigate several interconnected free energy relations between these two conformational states, considering voltage activation of ion channels. The free energy difference between the two conformational states at zero (depolarization) membrane potential (i.e., known as the chemical component of free energy change in ion channels) is shown to be equivalent to the free energy difference between the two "equilibrium" (resting and activated) conformational states along the one-dimensional voltage couplin reaction coordinate. Furthermore, the requirement that the application of linear response approximation to the free energy functionals of voltage coupling should satisfy the general free energy relations, yields a novel closed-form expression for the gating charge in terms of other basic properties of ion channels. This connection is familiar in statistical mechanics, known as the equilibrium fluctuation-response relation. The theory is illustrated by considering the coupling of a unit charge to the external voltage in the two sites near the surface of membrane, representing the activated and resting states. This is done using a coarse-graining (CG) model of membrane proteins, which includes the membrane, the electrolytes and the electrodes. The CG model yields Marcus-type voltage dependent free energy parabolas for the response of the electrostatic environment (electrolytes etc.) to the transition from the initial to the final configuratinal states, leading to equilibrium free energy difference and free energy barrier that follow the trend of the equilibrium fluctuation relation and the Marcus theory of electron transfer. These energetics also allow for a direct estimation of the voltage dependence of channel activation (Q-V curve), offering a quantitative rationale for a correlation between the voltage dependence parabolas and the Q-V curve, upon site-directed mutagenesis or drug binding. Taken together, by introducing the voltage coupling as the energy gap reaction coordinate, our framework brings new perspectives to the thermodynamic models of voltage activation in voltage-sensitive membrane proteins, offering an a framework for a better understating of the structure-function correlations of voltage gating in ion channels as well as electrogenic phenomena in ion pumps and transporters. Significantly, this formulation also provides a powerful bridge between the CG model of voltage coupling and the conventional macroscopic treatments. Copyright © 2015 Elsevier B.V. All rights reserved.

The mean ionic charges of N, Ne, MG, SI and S in solar energetic particle events

NASA Technical Reports Server (NTRS)

Luhn, A.; Hovestadt, D.; Klecker, B.; Scholer, M.; Gloeckler, G.; Ipavich, F. M.; Galvin, A. B.; Fan, C. Y.; Fisk, L. A.

1985-01-01

The mean ionic charges of nitrogen, neon, magnesium, silicon, and sulfur in solar flare particle events were determined for 12 flares during the time interval from September 1978 to September 1979. The observations were carried out with the MPI/UoMd ULEZEQ Sensor on the ISEE-3 satellite comparing the results with mean charge states established in a hot coronal plasma under equilibrium conditions, different temperatures for different elements are discussed. These range from approx. 2 million K to 7 million K in a single flare. From flare to flare the variation in temperature for each element is less than the variation between different ion species.

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.

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.

Thermodynamics of energy, charge, and spin currents in a thermoelectric quantum-dot spin valve

NASA Astrophysics Data System (ADS)

Tang, Gaomin; Thingna, Juzar; Wang, Jian

2018-04-01

We provide a thermodynamically consistent description of energy, charge, and spin transfers in a thermoelectric quantum-dot spin valve in the collinear configuration based on nonequilibrium Green's function and full counting statistics. We use the fluctuation theorem symmetry and the concept of entropy production to characterize the efficiency with which thermal gradients can transduce charges or spins against their chemical potentials, arbitrary far from equilibrium. Close to equilibrium, we recover the Onsager reciprocal relations and the connection to linear response notions of performance such as the figure of merit. We also identify regimes where work extraction is more efficient far then close from equilibrium.

Operation of a quantum dot in the finite-state machine mode: Single-electron dynamic memory

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

Klymenko, M. V.; Klein, M.; Levine, R. D.

2016-07-14

A single electron dynamic memory is designed based on the non-equilibrium dynamics of charge states in electrostatically defined metallic quantum dots. Using the orthodox theory for computing the transfer rates and a master equation, we model the dynamical response of devices consisting of a charge sensor coupled to either a single and or a double quantum dot subjected to a pulsed gate voltage. We show that transition rates between charge states in metallic quantum dots are characterized by an asymmetry that can be controlled by the gate voltage. This effect is more pronounced when the switching between charge states correspondsmore » to a Markovian process involving electron transport through a chain of several quantum dots. By simulating the dynamics of electron transport we demonstrate that the quantum box operates as a finite-state machine that can be addressed by choosing suitable shapes and switching rates of the gate pulses. We further show that writing times in the ns range and retention memory times six orders of magnitude longer, in the ms range, can be achieved on the double quantum dot system using experimentally feasible parameters, thereby demonstrating that the device can operate as a dynamic single electron memory.« less

Partial Model of Insulator/Insulator Contact Charging

NASA Technical Reports Server (NTRS)

Hogue, Michael; Calle, C. I.; Buhler, C. R.; Mucciolo, E. R.

2005-01-01

Two papers present a two-phase equilibrium model that partly explains insulator/ insulator contact charging. In this model, a vapor of ions within a gas is in equilibrium with a submonolayer of ions of the same species that have been adsorbed on the surface of an insulator. The surface is modeled as having localized states, each with a certain energy of adsorption for an ion. In an earlier version of the model described in the first paper, the ions do not interact with each other. Using the grand canonical ensemble, the chemical potentials of both vapor and absorbed phases are derived and equated to determine the vapor pressure. If a charge is assigned to the vapor particles (in particular, if single ionization is assumed), then the surface charge density associated with adsorbed ions can be calculated as a function of pressure. In a later version of the model presented in the second paper, the submodel of the vapor phase is extended to include electrostatic interactions between vapor ions and adsorbed ones as well as the screening effect, at a given distance from the surface, of ions closer to the surface. Theoretical values of this model closely match preliminary experimental data on the discharge of insulators as a function of pressure.

Rotatingwall Technique and Centrifugal Separation

NASA Astrophysics Data System (ADS)

Anderegg, François

This chapter describes the "rotating wall" technique which enables essentially unlimited confinement time of 109-1010 charged particles in a Penning trap. The applied rotating wall electric field provides a positive torque that counteracts background drags, resulting in radial compression or steady-state confinement in near-thermal equilibrium states. The last part of the chapter discusses centrifugal separation in a rotating multi-species non-neutral plasma. Separation occurs when the centrifugal energy is larger than the mixing due to thermal energy.

Kinetic neoclassical calculations of impurity radiation profiles

DOE PAGES

Stotler, D. P.; Battaglia, D. J.; Hager, R.; ...

2016-12-30

Modifications of the drift-kinetic transport code XGC0 to include the transport, ionization, and recombination of individual charge states, as well as the associated radiation, are described. The code is first applied to a simulation of an NSTX H-mode discharge with carbon impurity to demonstrate the approach to coronal equilibrium. The effects of neoclassical phenomena on the radiated power profile are examined sequentially through the activation of individual physics modules in the code. Orbit squeezing and the neoclassical inward pinch result in increased radiation for temperatures above a few hundred eV and changes to the ratios of charge state emissions atmore » a given electron temperature. As a result, analogous simulations with a neon impurity yield qualitatively similar results.« less

Steady-State Ion Beam Modeling with MICHELLE

NASA Astrophysics Data System (ADS)

Petillo, John

2003-10-01

There is a need to efficiently model ion beam physics for ion implantation, chemical vapor deposition, and ion thrusters. Common to all is the need for three-dimensional (3D) simulation of volumetric ion sources, ion acceleration, and optics, with the ability to model charge exchange of the ion beam with a background neutral gas. The two pieces of physics stand out as significant are the modeling of the volumetric source and charge exchange. In the MICHELLE code, the method for modeling the plasma sheath in ion sources assumes that the electron distribution function is a Maxwellian function of electrostatic potential over electron temperature. Charge exchange is the process by which a neutral background gas with a "fast" charged particle streaming through exchanges its electron with the charged particle. An efficient method for capturing this is essential, and the model presented is based on semi-empirical collision cross section functions. This appears to be the first steady-state 3D algorithm of its type to contain multiple generations of charge exchange, work with multiple species and multiple charge state beam/source particles simultaneously, take into account the self-consistent space charge effects, and track the subsequent fast neutral particles. The solution used by MICHELLE is to combine finite element analysis with particle-in-cell (PIC) methods. The basic physics model is based on the equilibrium steady-state application of the electrostatic particle-in-cell (PIC) approximation employing a conformal computational mesh. The foundation stems from the same basic model introduced in codes such as EGUN. Here, Poisson's equation is used to self-consistently include the effects of space charge on the fields, and the relativistic Lorentz equation is used to integrate the particle trajectories through those fields. The presentation will consider the complexity of modeling ion thrusters.

Sodium dopants in helium clusters: Structure, equilibrium and submersion kinetics

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

Calvo, F.

Alkali impurities bind to helium nanodroplets very differently depending on their size and charge state, large neutral or charged dopants being wetted by the droplet whereas small neutral impurities prefer to reside aside. Using various computational modeling tools such as quantum Monte Carlo and path-integral molecular dynamics simulations, we have revisited some aspects of the physical chemistry of helium droplets interacting with sodium impurities, including the onset of snowball formation in presence of many-body polarization forces, the transition from non-wetted to wetted behavior in larger sodium clusters, and the kinetics of submersion of small dopants after sudden ionization.

Charge-transfer modified embedded atom method dynamic charge potential for Li-Co-O system

NASA Astrophysics Data System (ADS)

Kong, Fantai; Longo, Roberto C.; Liang, Chaoping; Nie, Yifan; Zheng, Yongping; Zhang, Chenxi; Cho, Kyeongjae

2017-11-01

To overcome the limitation of conventional fixed charge potential methods for the study of Li-ion battery cathode materials, a dynamic charge potential method, charge-transfer modified embedded atom method (CT-MEAM), has been developed and applied to the Li-Co-O ternary system. The accuracy of the potential has been tested and validated by reproducing a variety of structural and electrochemical properties of LiCoO2. A detailed analysis on the local charge distribution confirmed the capability of this potential for dynamic charge modeling. The transferability of the potential is also demonstrated by its reliability in describing Li-rich Li2CoO2 and Li-deficient LiCo2O4 compounds, including their phase stability, equilibrium volume, charge states and cathode voltages. These results demonstrate that the CT-MEAM dynamic charge potential could help to overcome the challenge of modeling complex ternary transition metal oxides. This work can promote molecular dynamics studies of Li ion cathode materials and other important transition metal oxides systems that involve complex electrochemical and catalytic reactions.

Charge-transfer modified embedded atom method dynamic charge potential for Li-Co-O system.

PubMed

Kong, Fantai; Longo, Roberto C; Liang, Chaoping; Nie, Yifan; Zheng, Yongping; Zhang, Chenxi; Cho, Kyeongjae

2017-11-29

To overcome the limitation of conventional fixed charge potential methods for the study of Li-ion battery cathode materials, a dynamic charge potential method, charge-transfer modified embedded atom method (CT-MEAM), has been developed and applied to the Li-Co-O ternary system. The accuracy of the potential has been tested and validated by reproducing a variety of structural and electrochemical properties of LiCoO 2 . A detailed analysis on the local charge distribution confirmed the capability of this potential for dynamic charge modeling. The transferability of the potential is also demonstrated by its reliability in describing Li-rich Li 2 CoO 2 and Li-deficient LiCo 2 O 4 compounds, including their phase stability, equilibrium volume, charge states and cathode voltages. These results demonstrate that the CT-MEAM dynamic charge potential could help to overcome the challenge of modeling complex ternary transition metal oxides. This work can promote molecular dynamics studies of Li ion cathode materials and other important transition metal oxides systems that involve complex electrochemical and catalytic reactions.

Charge dynamics of 57Fe probe atoms in La2Li0.5Cu0.5O4

NASA Astrophysics Data System (ADS)

Presniakov, I. A.; Sobolev, A. V.; Rusakov, V. S.; Moskvin, A. S.; Baranov, A. V.

2018-06-01

The objective of this study is to characterize the electronic state and local surrounding of 57Fe Mössbauer probe atoms within iron-doped layered perovskite La2Li0.5Cu0.5O4 containing transition metal in unusual formal oxidation states "+3". An approach based on the qualitative energy diagrams analysis and the calculations within the cluster configuration interaction method have been developed. It was shown that a large amount of charge is transferred via Cu-O bonds from the O: 2p bands to the Cu: 3d orbitals and the ground state is dominated by the d9L configuration ("Cu2+-O-" state). The dominant d9L ground state for the (CuO6) sublattice induces in the environment of the 57Fe probe cations a charge transfer Fe3+ + O-(L) → Fe4+ + O2-, which transforms "Fe3+" into "Fe4+" state. The experimental spectra in the entire temperature range 77-300 K were described with the use of the stochastic two-level model based on the assumption of dynamic equilibrium between two Fe3+↔Fe4+ valence states related to the iron atom in the [Fe(1)O4]4- center. The relaxation frequencies and activation energies of the corresponding charge fluctuations were estimated based on Mössbauer data. The results are discussed assuming a temperature-induced change in the electronic state of the [CuO4]5- clusters in the layered perovskite.

Rate Dependency During Relaxation of Superelastic Orthodontic NiTi Alloys After Hydrogen Charging

NASA Astrophysics Data System (ADS)

Elkhal Letaief, Wissem; Hassine, Tarek; Gamaoun, Fehmi

2016-03-01

The relaxation behavior under tensile loading of a superelastic NiTi alloy was investigated after hydrogen charging with respect to aging from one to 77 days in air at room temperature. The specimens were immersed for 3 h in a 0.9 % NaCl aqueous solution and then relaxed with an imposed strain of 4.8 %—which results in half of the martensite transformation—for different strain rates of 10-4, 10-3, and 5 × 10-3 s-1. For the non-charged specimens, the relaxed stress at the beginning exhibited a temporary dependence on the strain rates and then reached the same equilibrium stress after 2.5 h. After hydrogen charging, this equilibrium stress did not vary for the as-charged specimen. Nevertheless, the greater the aging period is the greater the equilibrium stress is. This behavior can be attributed to the diffusion of hydrogen into the entire specimen, which hinders the relaxation mechanism of the martensite bands.

Effect of the size of charged spherical macroparticles on their electrostatic interaction in an equilibrium plasma

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

Filippov, A. V., E-mail: fav@triniti.ru; Derbenev, I. N.

The effect of the size of two charged spherical macroparticles on their electrostatic interaction in an equilibrium plasma is analyzed within the linearized Poisson–Botzmann model. It is established that, under the interaction of two charged dielectric macroparticles in an equilibrium plasma, the forces acting on each particle turn out to be generally unequal. The forces become equal only in the case of conducting macroparticles or in the case of dielectric macroparticles of the same size and charge. They also turn out to be equal when the surface potentials of the macroparticles remain constant under the variation of interparticle distances. Formulasmore » are proposed that allow one to calculate the interaction force with a high degree of accuracy under the condition that the radii of macroparticles are much less than the screening length, which is usually satisfied in experiments with dusty plasmas.« less

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.

Non-equilibrium dynamics in disordered materials: Ab initio molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Ohmura, Satoshi; Nagaya, Kiyonobu; Shimojo, Fuyuki; Yao, Makoto

2015-08-01

The dynamic properties of liquid B2O3 under pressure and highly-charged bromophenol molecule are studied by using molecular dynamics (MD) simulations based on density functional theory (DFT). Diffusion properties of covalent liquids under high pressure are very interesting in the sense that they show unexpected pressure dependence. It is found from our simulation that the magnitude relation of diffusion coefficients for boron and oxygen in liquid B2O3 shows the anomalous pressure dependence. The simulation clarified the microscopic origin of the anomalous diffusion properties. Our simulation also reveals the dissociation mechanism in the coulomb explosion of the highly-charged bromophenol molecule. When the charge state n is 6, hydrogen atom in the hydroxyl group dissociates at times shorter than 20 fs while all hydrogen atoms dissociate when n is 8. After the hydrogen dissociation, the carbon ring breaks at about 100 fs. There is also a difference on the mechanism of the ring breaking depending on charge states, in which the ring breaks with expanding (n = 6) or shrink (n = 8).

Interpreting equilibrium-conductivity and conductivity-relaxation measurements to establish thermodynamic and transport properties for multiple charged defect conducting ceramics.

PubMed

Zhu, Huayang; Ricote, Sandrine; Coors, W Grover; Kee, Robert J

2015-01-01

A model-based interpretation of measured equilibrium conductivity and conductivity relaxation is developed to establish thermodynamic, transport, and kinetics parameters for multiple charged defect conducting (MCDC) ceramic materials. The present study focuses on 10% yttrium-doped barium zirconate (BZY10). In principle, using the Nernst-Einstein relationship, equilibrium conductivity measurements are sufficient to establish thermodynamic and transport properties. However, in practice it is difficult to establish unique sets of properties using equilibrium conductivity alone. Combining equilibrium and conductivity-relaxation measurements serves to significantly improve the quantitative fidelity of the derived material properties. The models are developed using a Nernst-Planck-Poisson (NPP) formulation, which enables the quantitative representation of conductivity relaxations caused by very large changes in oxygen partial pressure.

Variational study of fermionic and bosonic systems with non-Gaussian states: Theory and applications

NASA Astrophysics Data System (ADS)

Shi, Tao; Demler, Eugene; Ignacio Cirac, J.

2018-03-01

We present a new variational method for investigating the ground state and out of equilibrium dynamics of quantum many-body bosonic and fermionic systems. Our approach is based on constructing variational wavefunctions which extend Gaussian states by including generalized canonical transformations between the fields. The key advantage of such states compared to simple Gaussian states is presence of non-factorizable correlations and the possibility of describing states with strong entanglement between particles. In contrast to the commonly used canonical transformations, such as the polaron or Lang-Firsov transformations, we allow parameters of the transformations to be time dependent, which extends their regions of applicability. We derive equations of motion for the parameters characterizing the states both in real and imaginary time using the differential structure of the variational manifold. The ground state can be found by following the imaginary time evolution until it converges to a steady state. Collective excitations in the system can be obtained by linearizing the real-time equations of motion in the vicinity of the imaginary time steady-state solution. Our formalism allows us not only to determine the energy spectrum of quasiparticles and their lifetime, but to obtain the complete spectral functions and to explore far out of equilibrium dynamics such as coherent evolution following a quantum quench. We illustrate and benchmark this framework with several examples: a single polaron in the Holstein and Su-Schrieffer-Heeger models, non-equilibrium dynamics in the spin-boson and Kondo models, the superconducting to charge density wave phase transitions in the Holstein model.

Energetics and Self-Assembly of Amphipathic Peptide Pores in Lipid Membranes

PubMed Central

Zemel, Assaf; Fattal, Deborah R.; Ben-Shaul, Avinoam

2003-01-01

We present a theoretical study of the energetics, equilibrium size, and size distribution of membrane pores composed of electrically charged amphipathic peptides. The peptides are modeled as cylinders (mimicking α-helices) carrying different amounts of charge, with the charge being uniformly distributed over a hydrophilic face, defined by the angle subtended by polar amino acid residues. The free energy of a pore of a given radius, R, and a given number of peptides, s, is expressed as a sum of the peptides' electrostatic charging energy (calculated using Poisson-Boltzmann theory), and the lipid-perturbation energy associated with the formation of a membrane rim (which we model as being semitoroidal) in the gap between neighboring peptides. A simple phenomenological model is used to calculate the membrane perturbation energy. The balance between the opposing forces (namely, the radial free energy derivatives) associated with the electrostatic free energy that favors large R, and the membrane perturbation term that favors small R, dictates the equilibrium properties of the pore. Systematic calculations are reported for circular pores composed of various numbers of peptides, carrying different amounts of charge (1–6 elementary, positive charges) and characterized by different polar angles. We find that the optimal R's, for all (except, possibly, very weakly) charged peptides conform to the “toroidal” pore model, whereby a membrane rim larger than ∼1 nm intervenes between neighboring peptides. Only weakly charged peptides are likely to form “barrel-stave” pores where the peptides essentially touch one another. Treating pore formation as a two-dimensional self-assembly phenomenon, a simple statistical thermodynamic model is formulated and used to calculate pore size distributions. We find that the average pore size and size polydispersity increase with peptide charge and with the amphipathic polar angle. We also argue that the transition of peptides from the adsorbed to the inserted (membrane pore) state is cooperative and thus occurs rather abruptly upon a change in ambient conditions. PMID:12668433

Statistical mechanics of light elements at high pressure. VI - Liquid-state calculations with Thomas-Fermi-Dirac theory

NASA Technical Reports Server (NTRS)

Macfarlane, J. J.

1984-01-01

A model free energy is developed for hydrogen-helium mixtures based on solid-state Thomas-Fermi-Dirac calculations at pressures relevant to the interiors of giant planets. Using a model potential similar to that for a two-component plasma, effective charges for the nuclei (which are in general smaller than the actual charges because of screening effects) are parameterized, being constrained by calculations at a number of densities, compositions, and lattice structures. These model potentials are then used to compute the equilibrium properties of H-He fluids using a charged hard-sphere model. The results find critical temperatures of about 0 K, 500 K, and 1500 K, for pressures of 10, 100, and 1000 Mbar, respectively. These phase separation temperatures are considerably lower (approximately 6,000-10,000 K) than those found from calculations using free electron perturbation theory, and suggest that H-He solutions should be stable against phase separation in the metallic zones of Jupiter and Saturn.

Analytical Model for Gyro-Phase Drift Arising from Abrupt Inhomogeneity

NASA Technical Reports Server (NTRS)

Walker, Jeffrey J.; Koepke, M. E.; Zimmerman, M. I.; Farrell, W. M.; Demidov, V. I.

2013-01-01

If a magnetized-orbit-charged grain encounters any abrupt inhomogeneity in plasma conditions during a gyro-orbit, such that the resulting in-situ equilibrium charge is significantly different between these regions (q(sub1)/q(sub 2) approximately 2, where q(sub 1) is the in-situ equilibrium charge on one side of the inhomogeneity, q(sub 2) is the in-situ equilibrium charge on the other side, and q(sub1) less than q(sub 2) less than 0), then the capacitive effects of charging and discharging of the dust grain can result in a modification to the orbit-averaged grain trajectory, i.e. gyro-phase drift. The special case of q(sub 1)/q(sub 2) is notioned for the purpose of illustrating the utility of the method. An analytical expression is derived for the grain velocity, assuming a capacitor approximation to the OML charging model. For cases in which a strong electric field suddenly appears in the wake or at the space-plasma-to-crater interface from solar wind and/or ultraviolet illumination and in which a magnetic field permeates an asteroid, comet, or moon, this model could contribute to the interpretation of the distribution of fields and particles.

Total Charge Movement per Channel

PubMed Central

Sigg, Daniel; Bezanilla, Francisco

1997-01-01

One measure of the voltage dependence of ion channel conductance is the amount of gating charge that moves during activation and vice versa. The limiting slope method, introduced by Almers (Almers, W. 1978. Rev. Physiol. Biochem. Pharmacol. 82:96–190), exploits the relationship of charge movement and voltage sensitivity, yielding a lower limit to the range of single channel gating charge displacement. In practice, the technique is plagued by low experimental resolution due to the requirement that the logarithmic voltage sensitivity of activation be measured at very low probabilities of opening. In addition, the linear sequential models to which the original theory was restricted needed to be expanded to accommodate the complexity of mechanisms available for the activation of channels. In this communication, we refine the theory by developing a relationship between the mean activation charge displacement (a measure of the voltage sensitivity of activation) and the gating charge displacement (the integral of gating current). We demonstrate that recording the equilibrium gating charge displacement as an adjunct to the limiting slope technique greatly improves accuracy under conditions where the plots of mean activation charge displacement and gross gating charge displacement versus voltage can be superimposed. We explore this relationship for a wide variety of channel models, which include those having a continuous density of states, nonsequential activation pathways, and subconductance states. We introduce new criteria for the appropriate use of the limiting slope procedure and provide a practical example of the theory applied to low resolution simulation data. PMID:8997663

A Simple Global View of Fuel Burnup

NASA Astrophysics Data System (ADS)

Sekimoto, Hiroshi

2017-01-01

Reactor physics and fuel burnup are discussed in order to obtain a simple global view of the effects of nuclear reactor characteristics to fuel cycle system performance. It may provide some idea of free thinking and overall vision, though it is still a small part of nuclear energy system. At the beginning of this lecture, governing equations for nuclear reactors are presented. Since the set of these equations is so big and complicated, it is simplified by imposing some extreme conditions and the nuclear equilibrium equation is derived. Some features of future nuclear equilibrium state are obtained by solving this equation. The contribution of a nucleus charged into reactor core to the system performance indexes such as criticality is worth for understanding the importance of each nuclide. It is called nuclide importance and can be evaluated by using the equations adjoint to the nuclear equilibrium equation. Examples of some importances and their application to criticalily search problem are presented.

Ultrafast terahertz control of extreme tunnel currents through single atoms on a silicon surface

NASA Astrophysics Data System (ADS)

Jelic, Vedran; Iwaszczuk, Krzysztof; Nguyen, Peter H.; Rathje, Christopher; Hornig, Graham J.; Sharum, Haille M.; Hoffman, James R.; Freeman, Mark R.; Hegmann, Frank A.

2017-06-01

Ultrafast control of current on the atomic scale is essential for future innovations in nanoelectronics. Extremely localized transient electric fields on the nanoscale can be achieved by coupling picosecond duration terahertz pulses to metallic nanostructures. Here, we demonstrate terahertz scanning tunnelling microscopy (THz-STM) in ultrahigh vacuum as a new platform for exploring ultrafast non-equilibrium tunnelling dynamics with atomic precision. Extreme terahertz-pulse-driven tunnel currents up to 107 times larger than steady-state currents in conventional STM are used to image individual atoms on a silicon surface with 0.3 nm spatial resolution. At terahertz frequencies, the metallic-like Si(111)-(7 × 7) surface is unable to screen the electric field from the bulk, resulting in a terahertz tunnel conductance that is fundamentally different than that of the steady state. Ultrafast terahertz-induced band bending and non-equilibrium charging of surface states opens new conduction pathways to the bulk, enabling extreme transient tunnel currents to flow between the tip and sample.

Progress in understanding heavy-ion stopping

NASA Astrophysics Data System (ADS)

Sigmund, P.; Schinner, A.

2016-09-01

We report some highlights of our work with heavy-ion stopping in the energy range where Bethe stopping theory breaks down. Main tools are our binary stopping theory (PASS code), the reciprocity principle, and Paul's data base. Comparisons are made between PASS and three alternative theoretical schemes (CasP, HISTOP and SLPA). In addition to equilibrium stopping we discuss frozen-charge stopping, deviations from linear velocity dependence below the Bragg peak, application of the reciprocity principle in low-velocity stopping, modeling of equilibrium charges, and the significance of the so-called effective charge.

Practical thermodynamic quantities for aqueous vanadium- and iron-based flow batteries

DOE PAGES

Hudak, Nicholas S.

2013-12-31

A simple method for experimentally determining thermodynamic quantities for flow battery cell reactions is presented. Equilibrium cell potentials, temperature derivatives of cell potential (d E/d T), Gibbs free energies, and entropies are reported here for all-vanadium, iron–vanadium, and iron–chromium flow cells with state-of-the-art solution compositions. Proof is given that formal potentials and formal temperature coefficients can be used with modified forms of the Nernst Equation to quantify the thermodynamics of flow cell reactions as a function of state-of-charge. Such empirical quantities can be used in thermo-electrochemical models of flow batteries at the cell or system level. In most cases, themore » thermodynamic quantities measured here are significantly different from standard values reported and used previously in the literature. The data reported here are also useful in the selection of operating temperatures for flow battery systems. Because higher temperatures correspond to lower equilibrium cell potentials for the battery chemistries studied here, it can be beneficial to charge a cell at higher temperature and discharge at lower temperature. As a result, proof-of-concept of improved voltage efficiency with the use of such non-isothermal cycling is given for the all-vanadium redox flow battery, and the effect is shown to be more pronounced at lower current densities.« less

Universality of nonthermal behavior in spinor Bose condensates

NASA Astrophysics Data System (ADS)

Patil, Yogesh Sharad; Cheung, Hil F. H.; Shaffer, Airlia; Chen, Huiyao Y.; Vengalattore, Mukund

2016-05-01

Spinor Bose condensates exhibit a rich phase diagram with varied magnetic ordering and topological defects because of the close competition between their spin and charge dependent interactions. Quenching such a spinor condensate into a ferromagnetic state realizes robust non-equilibrium and prethermalized states whose macroscopic behavior differs from thermodynamic predictions. In previous work, we have identified the microscopic origin of prethermalization in Rubidium spinor gases as being the disparate energy scales of the phonon and magnon excitations in this gas. This identification of the microscopic origin enables us to broaden the scope of our studies to address fundamental questions regarding the equilibration of isolated quantum systems. We will discuss our recent results that suggest the universality of this coarsening behavior and evidence that this system can be mapped on to a non-thermal fixed point studied in high energy field theories. This work is supported by the ARO MURI on non-equilibrium dynamics.

Integrated fusion simulation with self-consistent core-pedestal coupling

DOE PAGES

Meneghini, O.; Snyder, P. B.; Smith, S. P.; ...

2016-04-20

In this study, accurate prediction of fusion performance in present and future tokamaks requires taking into account the strong interplay between core transport, pedestal structure, current profile and plasma equilibrium. An integrated modeling workflow capable of calculating the steady-state self- consistent solution to this strongly-coupled problem has been developed. The workflow leverages state-of-the-art components for collisional and turbulent core transport, equilibrium and pedestal stability. Validation against DIII-D discharges shows that the workflow is capable of robustly pre- dicting the kinetic profiles (electron and ion temperature and electron density) from the axis to the separatrix in good agreement with the experiments.more » An example application is presented, showing self-consistent optimization for the fusion performance of the 15 MA D-T ITER baseline scenario as functions of the pedestal density and ion effective charge Z eff.« less

Homogeneous quantum electrodynamic turbulence

NASA Technical Reports Server (NTRS)

Shebalin, John V.

1992-01-01

The electromagnetic field equations and Dirac equations for oppositely charged wave functions are numerically time-integrated using a spatial Fourier method. The numerical approach used, a spectral transform technique, is based on a continuum representation of physical space. The coupled classical field equations contain a dimensionless parameter which sets the strength of the nonlinear interaction (as the parameter increases, interaction volume decreases). For a parameter value of unity, highly nonlinear behavior in the time-evolution of an individual wave function, analogous to ideal fluid turbulence, is observed. In the truncated Fourier representation which is numerically implemented here, the quantum turbulence is homogeneous but anisotropic and manifests itself in the nonlinear evolution of equilibrium modal spatial spectra for the probability density of each particle and also for the electromagnetic energy density. The results show that nonlinearly interacting fermionic wave functions quickly approach a multi-mode, dynamic equilibrium state, and that this state can be determined by numerical means.

Electronic and transport properties of Cobalt-based valence tautomeric molecules and polymers

NASA Astrophysics Data System (ADS)

Chen, Yifeng; Calzolari, Arrigo; Buongiorno Nardelli, Marco

2011-03-01

The advancement of molecular spintronics requires further understandings of the fundamental electronic structures and transport properties of prototypical spintronics molecules and polymers. Here we present a density functional based theoretical study of the electronic structures of Cobalt-based valence tautomeric molecules Co III (SQ)(Cat)L Co II (SQ)2 L and their polymers, where SQ refers to the semiquinone ligand, and Cat the catecholate ligand, while L is a redox innocent backbone ligand. The conversion from low-spin Co III ground state to high-spin Co II excited state is realized by imposing an on-site potential U on the Co atom and elongating the Co-N bond. Transport properties are subsequently calculated by extracting electronic Wannier functions from these systems and computing the charge transport in the ballistic regime using a Non-Equilibrium Green's Function (NEGF) approach. Our transport results show distinct charge transport properties between low-spin ground state and high-spin excited state, hence suggesting potential spintronics devices from these molecules and polymers such as spin valves.

Entanglement evolution across a conformal interface

NASA Astrophysics Data System (ADS)

Wen, Xueda; Wang, Yuxuan; Ryu, Shinsei

2018-05-01

For two-dimensional conformal field theories (CFTs) in the ground state, it is known that a conformal interface along the entanglement cut can suppress the entanglement entropy from to , where L is the length of the subsystem A, and is the effective central charge which depends on the transmission property of the conformal interface. In this work, by making use of conformal mappings, we show that a conformal interface has the same effect on entanglement evolution in non-equilibrium cases, including global, local and certain inhomogeneous quantum quenches. I.e. a conformal interface suppresses the time evolution of entanglement entropy by effectively replacing the central charge c with , where is exactly the same as that in the ground state case. We confirm this conclusion by a numerical study on a critical fermion chain. Furthermore, based on the quasi-particle picture, we conjecture that this conclusion holds for an arbitrary quantum quench in CFTs, as long as the initial state can be described by a regularized conformal boundary state.

Coulomb energy of uniformly charged spheroidal shell systems.

PubMed

Jadhao, Vikram; Yao, Zhenwei; Thomas, Creighton K; de la Cruz, Monica Olvera

2015-03-01

We provide exact expressions for the electrostatic energy of uniformly charged prolate and oblate spheroidal shells. We find that uniformly charged prolate spheroids of eccentricity greater than 0.9 have lower Coulomb energy than a sphere of the same area. For the volume-constrained case, we find that a sphere has the highest Coulomb energy among all spheroidal shells. Further, we derive the change in the Coulomb energy of a uniformly charged shell due to small, area-conserving perturbations on the spherical shape. Our perturbation calculations show that buckling-type deformations on a sphere can lower the Coulomb energy. Finally, we consider the possibility of counterion condensation on the spheroidal shell surface. We employ a Manning-Oosawa two-state model approximation to evaluate the renormalized charge and analyze the behavior of the equilibrium free energy as a function of the shell's aspect ratio for both area-constrained and volume-constrained cases. Counterion condensation is seen to favor the formation of spheroidal structures over a sphere of equal area for high values of shell volume fractions.

Equilibrium charge distribution on a finite straight one-dimensional wire

NASA Astrophysics Data System (ADS)

Batle, Josep; Ciftja, Orion; Abdalla, Soliman; Elhoseny, Mohamed; Alkhambashi, Majid; Farouk, Ahmed

2017-09-01

The electrostatic properties of uniformly charged regular bodies are prominently discussed on college-level electromagnetism courses. However, one of the most basic problems of electrostatics that deals with how a continuous charge distribution reaches equilibrium is rarely mentioned at this level. In this work we revisit the problem of equilibrium charge distribution on a straight one-dimensional (1D) wire with finite length. The majority of existing treatments in the literature deal with the 1D wire as a limiting case of a higher-dimensional structure that can be treated analytically for a Coulomb interaction potential between point charges. Surprisingly, different models (for instance, an ellipsoid or a cylinder model) may lead to different results, thus there is even some ambiguity on whether the problem is well-posed. In this work we adopt a different approach where we do not start with any higher-dimensional body that reduces to a 1D wire in the appropriate limit. Instead, our starting point is the obvious one, a finite straight 1D wire that contains charge. However, the new tweak in the model is the assumption that point charges interact with each other via a non-Coulomb power-law interaction potential. This potential is well-behaved, allows exact analytical results and approaches the standard Coulomb interaction potential as a limit. The results originating from this approach suggest that the equilibrium charge distribution for a finite straight 1D wire is a uniform charge density when the power-law interaction potential approaches the Coulomb interaction potential as a suitable limit. We contrast such a finding to results obtained using a different regularised logarithmic interaction potential which allows exact treatment in 1D. The present self-contained material may be of interest to instructors teaching electromagnetism as well as students who will discover that simple-looking problems may sometimes pose important scientific challenges.

Intramolecular, Exciplex-Mediated, Proton-Coupled, Charge-Transfer Processes in N,N-Dimethyl-3-(1-pyrenyl)propan-1-ammonium Cations: Influence of Anion, Solvent Polarity, and Temperature.

PubMed

Safko, Trevor M; Faleiros, Marcelo M; Atvars, Teresa D Z; Weiss, Richard G

2016-06-16

An intramolecular exciplex-mediated, proton-coupled, charge-transfer (PCCT) process has been investigated for a series of N,N-dimethyl-3-(1-pyrenyl)propan-1-ammonium cations with different anions (PyS) in solvents of low to intermediate polarity over a wide temperature range. Solvent mediates both the equilibrium between conformations of the cation that place the pyrenyl and ammonium groups in proximity (conformation C) or far from each other (conformation O) and the ability of the ammonium group to transfer a proton adiabatically in the PyS excited singlet state. Thus, exciplex emission, concurrent with the PCCT process, was observed only in hydrogen-bond accepting solvents of relatively low polarity (tetrahydrofuran, ethyl acetate, and 1,4-dioxane) and not in dichloromethane. From the exciplex emission and other spectroscopic and thermodynamic data, the acidity of the ammonium group in conformation C of the excited singlet state of PyS (pKa*) has been estimated to be ca. -3.4 in tetrahydrofuran. The ratios between the intensities of emission from the exciplex and the locally excited state (IEx/ILE) appear to be much more dependent on the nature of the anion than are the rates of exciplex formation and decay, although the excited state data do not provide a quantitative measure of the anion effect on the C-O equilibrium. The activation energies associated with exciplex formation in THF are calculated to be 0.08 to 0.15 eV lower than for the neutral amine, N,N-dimethyl-3-(1-pyrenyl)propan-1-amine. Decay of the exciplexes formed from the deprotonation of PyS is hypothesized to occur through charge-recombination processes. To our knowledge, this is the first example in which photoacidity and intramolecular exciplex formation (i.e., a PCCT reaction) are coupled.

Charged drop dynamics experiment using an electrostatic-acoustic hybrid system

NASA Technical Reports Server (NTRS)

Rhim, W. K.; Chung, S. K.; Trinh, E. H.; Elleman, D. D.

1987-01-01

The design and the performance of an electrostatic-acoustic hybrid system and its application to a charge drop rotation experiment are presented. This system can levitate a charged drop electrostatically and induce drop rotation or oscillation by imposing an acoustic torque or an oscillating acoustic pressure. Using this system, the equilibrium shapes and stability of a rotating charged drop were experimentally investigated. A 3 mm size water drop was rotated as a rigid body and its gyrostatic equilibrium shapes were observed. Families of axisymmetric shapes, two-lobed shapes, and eventual fissioning have been observed. With the assumption of 'effective surface tension' in which the surface charge simply modified the surface tension of neutral liquid, the results agree exceptionally well with the Brown and Scriven's (1980) prediction for uncharged drops.

Teaching Chemical Equilibrium with the Jigsaw Technique

NASA Astrophysics Data System (ADS)

Doymus, Kemal

2008-03-01

This study investigates the effect of cooperative learning (jigsaw) versus individual learning methods on students’ understanding of chemical equilibrium in a first-year general chemistry course. This study was carried out in two different classes in the department of primary science education during the 2005-2006 academic year. One of the classes was randomly assigned as the non-jigsaw group (control) and other as the jigsaw group (cooperative). Students participating in the jigsaw group were divided into four “home groups” since the topic chemical equilibrium is divided into four subtopics (Modules A, B, C and D). Each of these home groups contained four students. The groups were as follows: (1) Home Group A (HGA), representin g the equilibrium state and quantitative aspects of equilibrium (Module A), (2) Home Group B (HGB), representing the equilibrium constant and relationships involving equilibrium constants (Module B), (3) Home Group C (HGC), representing Altering Equilibrium Conditions: Le Chatelier’s principle (Module C), and (4) Home Group D (HGD), representing calculations with equilibrium constants (Module D). The home groups then broke apart, like pieces of a jigsaw puzzle, and the students moved into jigsaw groups consisting of members from the other home groups who were assigned the same portion of the material. The jigsaw groups were then in charge of teaching their specific subtopic to the rest of the students in their learning group. The main data collection tool was a Chemical Equilibrium Achievement Test (CEAT), which was applied to both the jigsaw and non-jigsaw groups The results indicated that the jigsaw group was more successful than the non-jigsaw group (individual learning method).

Properties of the low-lying electronic states of phenanthrene: Exact PPP results

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

Chakrabarti, A.; Ramasesha, S.

1996-10-05

The authors report properties of the exact low-lying states of phenanthrene, its anion and dianion within the Pariser-Parr-Pople (PPP) model. The experimentally known singlet states of the neutral molecule are well reproduced by the model. The intensities for one and two photon absorption to various single states are also in good agreement with experiment. From the bond orders of these states, the authors predict the equilibrium geometries. The relaxation energies of these states, computed from charge-charge correlations and bond orders, are presented. The authors also present results of ring current calculations in the singlet ground state of phenanthrene. The authorsmore » have also reported energies, spin densities, bond orders, and relaxation energies of several triplet states and compared then with experiments as well as with other calculations, where available. The fine structure constants D and E, computed in the lowest triplet state, compare well with those obtained from experiments. These properties are also presented for the anions and the dianions. The PPP model in these cases predicts a low-energy (< 1 eV) dipole excitation. 31 refs., 4 figs., 9 tabs.« less

Non-equilibrium Transport in Carbon based Adsorbate Systems

NASA Astrophysics Data System (ADS)

Fürst, Joachim; Brandbyge, Mads; Stokbro, Kurt; Jauho, Antti-Pekka

2007-03-01

We have used the Atomistix Tool Kit(ATK) and TranSIESTA[1] packages to investigate adsorption of iron atoms on a graphene sheet. The technique of both codes is based on density functional theory using local basis sets[2], and non-equilibrium Green's functions (NEGF) to calculate the charge distribution under external bias. Spin dependent electronic structure calculations are performed for different iron coverages. These reveal adsorption site dependent charge transfer from iron to graphene leading to screening effects. Transport calculations show spin dependent scattering of the transmission which is analysed obtaining the transmission eigenchannels for each spin type. The phenomena of electromigration of iron in these systems at finite bias will be discussed, estimating the so-called wind force from the reflection[3]. [1] M. Brandbyge, J.-L. Mozos, P. Ordejon, J. Taylor, and K. Stokbro. Physical Review B (Condensed Matter and Materials Physics), 65(16):165401/11-7, 2002. [2] Jose M. Soler, Emilio Artacho, Julian D. Gale, Alberto Garcia, Javier Junquera, Pablo Ordejon, and Daniel Sanchez-Portal. Journal of Physics Condensed Matter, 14(11):2745-2779, 2002. [3] Sorbello. Theory of electromigration. Solid State Physics, 1997.

Electromagnetic pulse-driven spin-dependent currents in semiconductor quantum rings.

PubMed

Zhu, Zhen-Gang; Berakdar, Jamal

2009-04-08

We investigate the non-equilibrium charge and spin-dependent currents in a quantum ring with a Rashba spin-orbit interaction (SOI) driven by two asymmetric picosecond electromagnetic pulses. The equilibrium persistent charge and persistent spin-dependent currents are investigated as well. It is shown that the dynamical charge and the dynamical spin-dependent currents vary smoothly with a static external magnetic flux and the SOI provides a SU(2) effective flux that changes the phases of the dynamic charge and the dynamic spin-dependent currents. The period of the oscillation of the total charge current with the delay time between the pulses is larger in a quantum ring with a larger radius. The parameters of the pulse fields control to a certain extent the total charge and the total spin-dependent currents. The calculations are applicable to nanometre rings fabricated in heterojunctions of III-V and II-VI semiconductors containing several hundreds of electrons.

Electrostatic charge on a dust size distribution in a plasma. [in interplanetary space

NASA Technical Reports Server (NTRS)

Houpis, Harry L. F.; Whipple, Elden C., Jr.

1987-01-01

The capacitance of a grain immersed in a steady state plasma containing a size distribution of dust particles is studied. The grain charge is determined by assuming the equilibrium potential has been obtained by a simple balance of electron and ion collection currents. It is shown that the validity of the analytical treatment given here for the linearized Poisson equation is confined to a certain region of space. Within this region and starting at very small plasma Debye length lambda(D), the capacitance at first exhibits a monotonic increase with increasing lambda(D). The capacitance eventually reaches a maximum, followed by a monotonic decrease. The charge density of the dust in the plasma is found to be only a function of the lambda(D); there is no significant dependence on the interparticle spacing.

In situ study of LaY2Ni9 compound as Ni MH negative-electrode material

NASA Astrophysics Data System (ADS)

Latroche, M.; Isnard, O.

2008-03-01

The behavior of a Ni-MH (metal hydride) negative composite electrode made of LaY2Ni9 active material has been studied dynamically using in situ neutron diffraction during a complete charge-discharge electrochemical cycle. From the analysis of the collected diffraction patterns, the phase identity, phase amount variations and cell volume evolutions have been determined as a function of the electrochemical state of (dis)charge. The active material shows a typical two-phase behavior with equilibrium between a hydrogen-poor α phase and a hydrogen-rich β one. The lower electrochemical reversible capacity as compared to solid-gas properties has been interpreted in terms of hydrogen gas evolving during charge and kinetic limitation due to slow β to α transformation during discharge, which hinders high discharge rates.

Charged Substrate and Product Together Contribute Like a Nonreactive Species to the Overall Electrostatic Steering in Diffusion-Reaction Processes.

PubMed

Xu, Jingjie; Xie, Yan; Lu, Benzhuo; Zhang, Linbo

2016-08-25

The Debye-Hückel limiting law is used to study the binding kinetics of substrate-enzyme system as well as to estimate the reaction rate of a electrostatically steered diffusion-controlled reaction process. It is based on a linearized Poisson-Boltzmann model and known for its accurate predictions in dilute solutions. However, the substrate and product particles are in nonequilibrium states and are possibly charged, and their contributions to the total electrostatic field cannot be explicitly studied in the Poisson-Boltzmann model. Hence the influences of substrate and product on reaction rate coefficient were not known. In this work, we consider all the charged species, including the charged substrate, product, and mobile salt ions in a Poisson-Nernst-Planck model, and then compare the results with previous work. The results indicate that both the charged substrate and product can significantly influence the reaction rate coefficient with different behaviors under different setups of computational conditions. It is interesting to find that when substrate and product are both considered, under an overall neutral boundary condition for all the bulk charged species, the computed reaction rate kinetics recovers a similar Debye-Hückel limiting law again. This phenomenon implies that the charged product counteracts the influence of charged substrate on reaction rate coefficient. Our analysis discloses the fact that the total charge concentration of substrate and product, though in a nonequilibrium state individually, obeys an equilibrium Boltzmann distribution, and therefore contributes as a normal charged ion species to ionic strength. This explains why the Debye-Hückel limiting law still works in a considerable range of conditions even though the effects of charged substrate and product particles are not specifically and explicitly considered in the theory.

Measurements of ultrafine particles carrying different number of charges in on- and near-freeway environments

NASA Astrophysics Data System (ADS)

Lee, Eon S.; Xu, Bin; Zhu, Yifang

2012-12-01

This paper presents measurements of electrical charges on ultrafine particles (UFPs) of different electrical mobility diameters (30, 50, 80, and 100 nm) in on- and near-freeway environments. Using a tandem Differential Mobility Analyzer (DMA) system, we first examined the fraction of UFPs carrying different number of charges on two distinctive freeways: a gasoline-vehicle dominated freeway (I-405) and a heavy-duty diesel truck dominated freeway (I-710). The fractions of UFPs of a given size carrying one or more charges were significantly higher on the freeways than in the background. The background UFPs only carried up to two charges but freeway UFPs could have up to three charges. The total fraction of charged particles was higher on the I-710 than I-405 across the studied electrical mobility diameters. Near the I-405 freeway, we observed a strong decay of charged particles on the downwind side of the freeway. We also found fractional decay of the charged particles was faster than total particle number concentrations, but slower than total ion concentrations downwind from the freeway I-405. Among charged particles, the highest decay rate was observed for particles carrying three charges. Near the I-710 freeway, we found strong net positive charges on nucleation mode particles, suggesting that UFPs were not at steady-state charge equilibrium near freeways.

Mutational analysis of cysteine 328 and cysteine 368 at the interface of Plasmodium falciparum adenylosuccinate synthetase.

PubMed

Mehrotra, Sonali; B Ningappa, Mylarappa; Raman, Jayalakshmi; Anand, Ranjith P; Balaram, Hemalatha

2012-04-01

Plasmodium falciparum adenylosuccinate synthetase, a homodimeric enzyme, contains 10 cysteine residues per subunit. Among these, Cys250, Cys328 and Cys368 lie at the dimer interface and are not conserved across organisms. PfAdSS has a positively charged interface with the crystal structure showing additional electron density around Cys328 and Cys368. Biochemical characterization of site directed mutants followed by equilibrium unfolding studies permits elucidation of the role of interface cysteines and positively charged interface in dimer stability. Mutation of interface cysteines, Cys328 and Cys368 to serine, perturbed the monomer-dimer equilibrium in the protein with a small population of monomer being evident in the double mutant. Introduction of negative charge in the form of C328D mutation resulted in stabilization of protein dimer as evident by size exclusion chromatography at high ionic strength buffer and equilibrium unfolding in the presence of urea. These observations suggest that cysteines at the dimer interface of PfAdSS may indeed be charged and exist as thiolate anion. Copyright © 2012 Elsevier B.V. All rights reserved.

Profiles of equilibrium constants for self-association of aromatic molecules

NASA Astrophysics Data System (ADS)

Beshnova, Daria A.; Lantushenko, Anastasia O.; Davies, David B.; Evstigneev, Maxim P.

2009-04-01

Analysis of the noncovalent, noncooperative self-association of identical aromatic molecules assumes that the equilibrium self-association constants are either independent of the number of molecules (the EK-model) or change progressively with increasing aggregation (the AK-model). The dependence of the self-association constant on the number of molecules in the aggregate (i.e., the profile of the equilibrium constant) was empirically derived in the AK-model but, in order to provide some physical understanding of the profile, it is proposed that the sources for attenuation of the equilibrium constant are the loss of translational and rotational degrees of freedom, the ordering of molecules in the aggregates and the electrostatic contribution (for charged units). Expressions are derived for the profiles of the equilibrium constants for both neutral and charged molecules. Although the EK-model has been widely used in the analysis of experimental data, it is shown in this work that the derived equilibrium constant, KEK, depends on the concentration range used and hence, on the experimental method employed. The relationship has also been demonstrated between the equilibrium constant KEK and the real dimerization constant, KD, which shows that the value of KEK is always lower than KD.

Enhanced flashover strength in polyethylene nanodielectrics by secondary electron emission modification

NASA Astrophysics Data System (ADS)

Wang, Weiwang; Li, Shengtao; Min, Daomin

2016-04-01

This work studies the correlation between secondary electron emission (SEE) characteristics and impulse surface flashover in polyethylene nanodielectrics both theoretically and experimentally, and illustrates the enhancement of flashover voltage in low-density polyethylene (LDPE) through incorporating Al2O3 nanoparticles. SEE characteristics play key roles in surface charging and gas desorption during surface flashover. This work demonstrates that the presence of Al2O3 nanoparticles decreases the SEE coefficient of LDPE and enhances the impact energy at the equilibrium state of surface charging. These changes can be explained by the increase of surface roughness and of surface ionization energy, and the strong interaction between nanoparticles and the polymer dielectric matrix. The surface charge and flashover voltage are calculated according to the secondary electron emission avalanche (SEEA) model, which reveals that the positive surface charges are reduced near the cathode triple point, while the presence of more nanoparticles in high loading samples enhances the gas desorption. Consequently, the surface flashover performance of LDPE/Al2O3 nanodielectrics is improved.

Applications of finite-size scaling for atomic and non-equilibrium systems

NASA Astrophysics Data System (ADS)

Antillon, Edwin A.

We apply the theory of Finite-size scaling (FSS) to an atomic and a non-equilibrium system in order to extract critical parameters. In atomic systems, we look at the energy dependence on the binding charge near threshold between bound and free states, where we seek the critical nuclear charge for stability. We use different ab initio methods, such as Hartree-Fock, Density Functional Theory, and exact formulations implemented numerically with the finite-element method (FEM). Using Finite-size scaling formalism, where in this case the size of the system is related to the number of elements used in the basis expansion of the wavefunction, we predict critical parameters in the large basis limit. Results prove to be in good agreement with previous Slater-basis set calculations and demonstrate that this combined approach provides a promising first-principles approach to describe quantum phase transitions for materials and extended systems. In the second part we look at non-equilibrium one-dimensional model known as the raise and peel model describing a growing surface which grows locally and has non-local desorption. For a specific values of adsorption ( ua) and desorption (ud) the model shows interesting features. At ua = ud, the model is described by a conformal field theory (with conformal charge c = 0) and its stationary probability can be mapped to the ground state of a quantum chain and can also be related a two dimensional statistical model. For ua ≥ ud, the model shows a scale invariant phase in the avalanche distribution. In this work we study the surface dynamics by looking at avalanche distributions using FSS formalism and explore the effect of changing the boundary conditions of the model. The model shows the same universality for the cases with and with our the wall for an odd number of tiles removed, but we find a new exponent in the presence of a wall for an even number of avalanches released. We provide new conjecture for the probability distribution of avalanches with a wall obtained by using exact diagonalization of small lattices and Monte-Carlo simulations.

Ion Current Rectification, Limiting and Overlimiting Conductances in Nanopores

PubMed Central

van Oeffelen, Liesbeth; Van Roy, Willem; Idrissi, Hosni; Charlier, Daniel; Lagae, Liesbet; Borghs, Gustaaf

2015-01-01

Previous reports on Poisson-Nernst-Planck (PNP) simulations of solid-state nanopores have focused on steady state behaviour under simplified boundary conditions. These are Neumann boundary conditions for the voltage at the pore walls, and in some cases also Donnan equilibrium boundary conditions for concentrations and voltages at both entrances of the nanopore. In this paper, we report time-dependent and steady state PNP simulations under less restrictive boundary conditions, including Neumann boundary conditions applied throughout the membrane relatively far away from the nanopore. We simulated ion currents through cylindrical and conical nanopores with several surface charge configurations, studying the spatial and temporal dependence of the currents contributed by each ion species. This revealed that, due to slow co-diffusion of oppositely charged ions, steady state is generally not reached in simulations or in practice. Furthermore, it is shown that ion concentration polarization is responsible for the observed limiting conductances and ion current rectification in nanopores with asymmetric surface charges or shapes. Hence, after more than a decade of collective research attempting to understand the nature of ion current rectification in solid-state nanopores, a relatively intuitive model is retrieved. Moreover, we measured and simulated current-voltage characteristics of rectifying silicon nitride nanopores presenting overlimiting conductances. The similarity between measurement and simulation shows that overlimiting conductances can result from the increased conductance of the electric double-layer at the membrane surface at the depletion side due to voltage-induced polarization charges. The MATLAB source code of the simulation software is available via the website http://micr.vub.ac.be. PMID:25978328

Competing nucleation pathways in a mixture of oppositely charged colloids: out-of-equilibrium nucleation revisited.

PubMed

Peters, Baron

2009-12-28

Recent simulations of crystal nucleation from a compressed liquid of oppositely charged colloids show that the natural Brownian dynamics results in nuclei of a charge-disordered FCC (DFCC) solid whereas artificially accelerated dynamics with charge swap moves result in charge-ordered nuclei of a CsCl phase. These results were interpreted as a breakdown of the quasiequilibrium assumption for precritical nuclei. We use structure-specific nucleus size coordinates for the CsCl and DFCC structures and equilibrium based sampling methods to understand the dynamical effects on structure selectivity in this system. Nonequilibrium effects observed in previous simulations emerge from a diffusion tensor that dramatically changes when charge swap moves are used. Without the charge swap moves diffusion is strongly anisotropic with very slow motion along the charge-ordered CsCl axis and faster motion along the DFCC axis. Kramers-Langer-Berezhkovskii-Szabo theory predicts that under the realistic dynamics, the diffusion anisotropy shifts the current toward the DFCC axis. The diffusion tensor also varies with location on the free energy landscape. A numerical calculation of the current field with a diffusion tensor that depends on the location in the free energy landscape exacerbates the extent to which the current is skewed toward DFCC structures. Our analysis confirms that quasiequilibrium theories based on equilibrium properties can explain the nonequilibrium behavior of this system. Our analysis also shows that using a structure-specific nucleus size coordinate for each possible nucleation product can provide mechanistic insight on selectivity and competition between nucleation pathways.

Competing nucleation pathways in a mixture of oppositely charged colloids: Out-of-equilibrium nucleation revisited

NASA Astrophysics Data System (ADS)

Peters, Baron

2009-12-01

Recent simulations of crystal nucleation from a compressed liquid of oppositely charged colloids show that the natural Brownian dynamics results in nuclei of a charge-disordered FCC (DFCC) solid whereas artificially accelerated dynamics with charge swap moves result in charge-ordered nuclei of a CsCl phase. These results were interpreted as a breakdown of the quasiequilibrium assumption for precritical nuclei. We use structure-specific nucleus size coordinates for the CsCl and DFCC structures and equilibrium based sampling methods to understand the dynamical effects on structure selectivity in this system. Nonequilibrium effects observed in previous simulations emerge from a diffusion tensor that dramatically changes when charge swap moves are used. Without the charge swap moves diffusion is strongly anisotropic with very slow motion along the charge-ordered CsCl axis and faster motion along the DFCC axis. Kramers-Langer-Berezhkovskii-Szabo theory predicts that under the realistic dynamics, the diffusion anisotropy shifts the current toward the DFCC axis. The diffusion tensor also varies with location on the free energy landscape. A numerical calculation of the current field with a diffusion tensor that depends on the location in the free energy landscape exacerbates the extent to which the current is skewed toward DFCC structures. Our analysis confirms that quasiequilibrium theories based on equilibrium properties can explain the nonequilibrium behavior of this system. Our analysis also shows that using a structure-specific nucleus size coordinate for each possible nucleation product can provide mechanistic insight on selectivity and competition between nucleation pathways.

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.

Experimental apparatus for overlapping a ground-state cooled ion with ultracold atoms

NASA Astrophysics Data System (ADS)

Meir, Ziv; Sikorsky, Tomas; Ben-shlomi, Ruti; Akerman, Nitzan; Pinkas, Meirav; Dallal, Yehonatan; Ozeri, Roee

2018-03-01

Experimental realizations of charged ions and neutral atoms in overlapping traps are gaining increasing interest due to their wide research application ranging from chemistry at the quantum level to quantum simulations of solid state systems. In this paper, we describe our experimental system in which we overlap a single ground-state cooled ion trapped in a linear Paul trap with a cloud of ultracold atoms such that both constituents are in the ?K regime. Excess micromotion (EMM) currently limits atom-ion interaction energy to the mK energy scale and above. We demonstrate spectroscopy methods and compensation techniques which characterize and reduce the ion's parasitic EMM energy to the ?K regime even for ion crystals of several ions. We further give a substantial review on the non-equilibrium dynamics which governs atom-ion systems. The non-equilibrium dynamics is manifested by a power law distribution of the ion's energy. We also give an overview on the coherent and non-coherent thermometry tools which can be used to characterize the ion's energy distribution after single to many atom-ion collisions.

Theoretical calculation of reorganization energy for electron self-exchange reaction by constrained density functional theory and constrained equilibrium thermodynamics.

PubMed

Ren, Hai-Sheng; Ming, Mei-Jun; Ma, Jian-Yi; Li, Xiang-Yuan

2013-08-22

Within the framework of constrained density functional theory (CDFT), the diabatic or charge localized states of electron transfer (ET) have been constructed. Based on the diabatic states, inner reorganization energy λin has been directly calculated. For solvent reorganization energy λs, a novel and reasonable nonequilibrium solvation model is established by introducing a constrained equilibrium manipulation, and a new expression of λs has been formulated. It is found that λs is actually the cost of maintaining the residual polarization, which equilibrates with the extra electric field. On the basis of diabatic states constructed by CDFT, a numerical algorithm using the new formulations with the dielectric polarizable continuum model (D-PCM) has been implemented. As typical test cases, self-exchange ET reactions between tetracyanoethylene (TCNE) and tetrathiafulvalene (TTF) and their corresponding ionic radicals in acetonitrile are investigated. The calculated reorganization energies λ are 7293 cm(-1) for TCNE/TCNE(-) and 5939 cm(-1) for TTF/TTF(+) reactions, agreeing well with available experimental results of 7250 cm(-1) and 5810 cm(-1), respectively.

Turbulent Equilibria for Charged Particles in Space

NASA Astrophysics Data System (ADS)

Yoon, Peter

2017-04-01

The solar wind electron distribution function is apparently composed of several components including non-thermal tail population. The electron distribution that contains energetic tail feature is well fitted with the kappa distribution function. The solar wind protons also possess quasi power-law tail distribution function that is well fitted with an inverse power law model. The present paper discusses the latest theoretical development regarding the dynamical steady-state solution of electrons and Langmuir turbulence that are in turbulent equilibrium. According to such a theory, the Maxwellian and kappa distribution functions for the electrons emerge as the only two possible solution that satisfy the steady-state weak turbulence plasma kinetic equation. For the proton inverse power-law tail problem, a similar turbulent equilibrium solution can be conceived of, but instead of high-frequency Langmuir fluctuation, the theory involves low-frequency kinetic Alfvenic turbulence. The steady-state solution of the self-consistent proton kinetic equation and wave kinetic equation for Alfvenic waves can be found in order to obtain a self-consistent solution for the inverse power law tail distribution function.

Metal-organic complexes in geochemical processes: temperature dependence of the standard thermodynamic properties of aqueous complexes between metal cations and dicarboxylate ligands

NASA Astrophysics Data System (ADS)

Prapaipong, Panjai; Shock, Everett L.; Koretsky, Carla M.

1999-10-01

By combining results from regression and correlation methods, standard state thermodynamic properties for aqueous complexes between metal cations and divalent organic acid ligands (oxalate, malonate, succinate, glutarate, and adipate) are evaluated and applied to geochemical processes. Regression of experimental standard-state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state yields standard partial molal entropies (S¯°) of aqueous metal-organic complexes, which allow determination of thermodynamic properties of the complexes at elevated temperatures. In cases where S¯° is not available from either regression or calorimetric measurement, the values of S¯° can be estimated from a linear correlation between standard partial molal entropies of association (ΔS¯°r) and standard partial molal entropies of aqueous cations (S¯°M). The correlation is independent of cation charge, which makes it possible to predict S¯° for complexes between divalent organic acids and numerous metal cations. Similarly, correlations between standard Gibbs free energies of association of metal-organic complexes (ΔḠ°r) and Gibbs free energies of formation (ΔḠ°f) for divalent metal cations allow estimates of standard-state equilibrium constants where experimental data are not available. These correlations are found to be a function of ligand structure and cation charge. Predicted equilibrium constants for dicarboxylate complexes of numerous cations were included with those for inorganic and other organic complexes to study the effects of dicarboxylate complexes on the speciation of metals and organic acids in oil-field brines. Relatively low concentrations of oxalic and malonic acids affect the speciation of cations more than similar concentrations of succinic, glutaric, and adipic acids. However, the extent to which metal-dicarboxylate complexes contribute to the speciation of dissolved metals depends on the type of dicarboxylic acid ligand; relative concentration of inorganic, mono-, and dicarboxylate ligands; and the type of metal cation. As an example, in the same solution, dicarboxylic acids have a greater influence on the speciation of Fe+2 and Mg+2 than on the speciation of Zn+2 and Mn+2.

Solution equilibrium behind the room-temperature synthesis of nanocrystalline titanium dioxide.

PubMed

Seisenbaeva, Gulaim A; Daniel, Geoffrey; Nedelec, Jean-Marie; Kessler, Vadim G

2013-04-21

Formation of nanocrystalline and monodisperse TiO2 from a water soluble and stable precursor, ammonium oxo-lactato-titanate, (NH4)8Ti4O4(Lactate)8·4H2O, often referred to as TiBALDH or TALH, is demonstrated to be due to a coordination equilibrium. This compound, individual in the solid state, exists in solution in equilibrium with ammonium tris-lactato-titanate, (NH4)2Ti(Lactate)3 and uniform crystalline TiO2 nanoparticles (anatase) stabilized by surface-capping with lactate ligands. This equilibrium can be shifted towards nano-TiO2via application of a less polar solvent like methanol or ethanol, dilution of the solution, introduction of salts or raising the temperature, and reverted on addition of polar and strongly solvating media such as dimethyl sulfoxide, according to NMR. Aggregation and precipitation of the particles were followed by DLS and could be achieved by a decrease in their surface charge by adsorption of strongly hydrogen-bonding cations, e.g. in solutions of ammonia, ethanolamine or amino acid arginine or by addition of ethanol. The observed equilibrium may be involved in formation of nano-titania on the surface of plant roots exerting chelating organic carboxylate ligands and thus potentially influencing plant interactions.

{P}{T}-symmetric interpretation of the electromagnetic self-force

NASA Astrophysics Data System (ADS)

Bender, Carl M.; Gianfreda, Mariagiovanna

2015-08-01

In 1980 Englert examined the classic problem of the electromagnetic self-force on an oscillating charged particle. His approach, which was based on an earlier idea of Bateman, was to introduce a time-reversed (charge-conjugate) particle and to show that the two-particle system is Hamiltonian. Unfortunately, Englert’s model did not solve the problem of runaway modes, and the corresponding quantum theory had ghost states. It is shown here that Englert’s Hamiltonian is {P}{T} symmetric, and that the problems with his model arise because the {P}{T} symmetry is broken at both the classical and the quantum level. However, by allowing the charged particles to interact and by adjusting the coupling parameters to put the model into an unbroken {P}{T}-symmetric region, one eliminates the classical nonrelativistic runaway modes and obtains a corresponding nonrelativistic quantum system that is in equilibrium and ghost free.

Study of charged stellar structures in f(R, T) gravity

NASA Astrophysics Data System (ADS)

Sharif, M.; Siddiqa, Aisha

2017-12-01

This paper explores charged stellar structures whose pressure and density are related through polytropic equation of state ( p=ωρ^{σ}; ω is polytropic constant, p is pressure, ρ denotes density and σ is polytropic exponent) in the scenario of f(R,T) gravity (where R is the Ricci scalar and T is the trace of energy-momentum tensor). The Einstein-Maxwell field equations are solved together with the hydrostatic equilibrium equation for f(R,T)=R+2λ T where λ is the coupling constant, also called model parameter. We discuss different features of such configurations (like pressure, mass and charge) using graphical behavior for two values of σ. It is found that the effects of model parameter λ on different quantities remain the same for both cases. The energy conditions are satisfied and stellar configurations are stable in each case.

Modulation of terrestrial ion escape flux composition /by low-altitude acceleration and charge exchange chemistry/

NASA Technical Reports Server (NTRS)

Moore, T. E.

1980-01-01

Motivated by recent observations of highly variable hot plasma composition in the magnetosphere, control of the ionospheric escape flux composition by low-altitude particle dynamics and ion chemistry has been investigated for an e(-), H(+), O(+) ionosphere. It is found that the fraction of the steady state escape flux which is O(+) can be controlled very sensitively by the occurrence of parallel or transverse ion acceleration at altitudes below the altitude where the neutral oxygen density falls rapidly below the neutral hydrogen density and the ionospheric source of O(+) tends to be rapidly converted by charge exchange to H(+). The acceleration is required both to overcome the gravitational confinement of O(+) and to violate charge exchange equilibrium so that the neutral hydrogen atmosphere appears 'optically' thin to escaping O(+). Constraints are placed on the acceleration processes, and it is shown that O(+) escape is facilitated by observed ionospheric responses to magnetic activity.

Oligomeric ferrocene rings

NASA Astrophysics Data System (ADS)

Inkpen, Michael S.; Scheerer, Stefan; Linseis, Michael; White, Andrew J. P.; Winter, Rainer F.; Albrecht, Tim; Long, Nicholas J.

2016-09-01

Cyclic oligomers comprising strongly interacting redox-active monomer units represent an unknown, yet highly desirable class of nanoscale materials. Here we describe the synthesis and properties of the first family of molecules belonging to this compound category—differently sized rings comprising only 1,1‧-disubstituted ferrocene units (cyclo[n], n = 5-7, 9). Due to the close proximity and connectivity of centres (covalent Cp-Cp linkages; Cp = cyclopentadienyl) solution voltammograms exhibit well-resolved, separated 1e- waves. Theoretical interrogations into correlations based on ring size and charge state are facilitated using values of the equilibrium potentials of these transitions, as well as their relative spacing. As the interaction free energies between the redox centres scale linearly with overall ring charge and in conjunction with fast intramolecular electron transfer (˜107 s-1), these molecules can be considered as uniformly charged nanorings (diameter ˜1-2 nm).

The Thermal Equilibrium Solution of a Generic Bipolar Quantum Hydrodynamic Model

NASA Astrophysics Data System (ADS)

Unterreiter, Andreas

The thermal equilibrium state of a bipolar, isothermic quantum fluid confined to a bounded domain ,d = 1,2 or d = 3 is entirely described by the particle densities n, p, minimizing the energy where G1,2 are strictly convex real valued functions, . It is shown that this variational problem has a unique minimizer in and some regularity results are proven. The semi-classical limit is carried out recovering the minimizer of the limiting functional. The subsequent zero space charge limit leads to extensions of the classical boundary conditions. Due to the lack of regularity the asymptotics can not be settled on Sobolev embedding arguments. The limit is carried out by means of a compactness-by-convexity principle.

Non-equilibrium Green's functions method: Non-trivial and disordered leads

NASA Astrophysics Data System (ADS)

He, Yu; Wang, Yu; Klimeck, Gerhard; Kubis, Tillmann

2014-11-01

The non-equilibrium Green's function algorithm requires contact self-energies to model charge injection and extraction. All existing approaches assume infinitely periodic leads attached to a possibly quite complex device. This contradicts today's realistic devices in which contacts are spatially inhomogeneous, chemically disordered, and impacting the overall device characteristics. This work extends the complex absorbing potentials method for arbitrary, ideal, or non-ideal leads in atomistic tight binding representation. The algorithm is demonstrated on a Si nanowire with periodic leads, a graphene nanoribbon with trumpet shape leads, and devices with leads of randomly alloyed Si0.5Ge0.5. It is found that alloy randomness in the leads can reduce the predicted ON-state current of Si0.5Ge0.5 transistors by 45% compared to conventional lead methods.

Non local-thermodynamical-equilibrium effects in the simulation of laser-produced plasmas

NASA Astrophysics Data System (ADS)

Klapisch, M.; Bar-Shalom, A.; Oreg, J.; Colombant, D.

1998-05-01

Local thermodynamic equilibrium (LTE) breaks down in directly or indirectly driven laser plasmas because of sharp gradients, energy deposition, etc. For modeling non-LTE effects in hydrodynamical simulations, Busquet's model [Phys. Fluids B 5, 4191 (1993)] is very convenient and efficient. It uses off-line generated LTE opacities and equation of states via an effective, radiation-dependent ionization temperature Tz. An overview of the model is given. The results are compared with an elaborate collisional radiative model based on superconfigurations. The agreements for average charge Z* and opacities are surprisingly good, even more so when the plasma is immersed in a radiation field. Some remaining discrepancy at low density is attributed to dielectronic recombination. Improvement appears possible, especially for emissivities, because the concept of ionization temperature seems to be validated.

Are two plasma equilibrium states possible when the emission coefficient exceeds unity?

NASA Astrophysics Data System (ADS)

Campanell, M. D.; Umansky, M. V.

2017-05-01

Two floating sheath solutions with strong electron emission in planar geometry have been proposed, a "space-charge limited" (SCL) sheath and an "inverse" sheath. SCL and inverse models contain different assumptions about conditions outside the sheath (e.g., the velocity of ions entering the sheath). So it is not yet clear whether both sheaths are possible in practice, or only one. Here we treat the global presheath-sheath problem for a plasma produced volumetrically between two planar walls. We show that all equilibrium requirements (a) floating condition, (b) plasma shielding, and (c) presheath force balance, can indeed be satisfied in two different ways when the emission coefficient γ > 1. There is one solution with SCL sheaths and one with inverse sheaths, each with sharply different presheath distributions. As we show for the first time in 1D-1V simulations, a SCL and inverse equilibrium are both possible in plasmas with the same upstream properties (e.g., same N and Te). However, maintaining a true SCL equilibrium requires no ionization or charge exchange collisions in the sheath, or else cold ion accumulation in the SCL's "dip" forces a transition to the inverse. This suggests that only a monotonic inverse type sheath potential should exist at any plasma-facing surface with strong emission, whether be a divertor plate, emissive probe, dust grain, Hall thruster channel wall, sunlit object in space, etc. Nevertheless, SCL sheaths might still be possible if the ions in the dip can escape. Our simulations demonstrate ways in which SCL and inverse regimes might be distinguished experimentally based on large-scale presheath effects, without having to probe inside the sheath.

Are two plasma equilibrium states possible when the emission coefficient exceeds unity?

DOE PAGES

Campanell, Michael D.; Umansky, M. V.

2017-02-28

Two floating sheath solutions with strong electron emission in planar geometry have been proposed, a “space-charge limited” (SCL) sheath and an “inverse” sheath. SCL and inverse models contain different assumptions about conditions outside the sheath (e.g., the velocity of ions entering the sheath). So it is not yet clear whether both sheaths are possible in practice, or only one. Here we treat the global presheath-sheath problem for a plasma produced volumetrically between two planar walls. We show that all equilibrium requirements (a) floating condition, (b) plasma shielding, and (c) presheath force balance, can indeed be satisfied in two different waysmore » when the emission coefficient γ > 1. There is one solution with SCL sheaths and one with inverse sheaths, each with sharply different presheath distributions. As we show for the first time in 1D-1V simulations, a SCL and inverse equilibrium are both possible in plasmas with the same upstream properties (e.g., same N and Te). However, maintaining a true SCL equilibrium requires no ionization or charge exchange collisions in the sheath, or else cold ion accumulation in the SCL's “dip” forces a transition to the inverse. This suggests that only a monotonic inverse type sheath potential should exist at any plasma-facing surface with strong emission, whether be a divertor plate, emissive probe, dust grain, Hall thruster channel wall, sunlit object in space, etc. Nevertheless, SCL sheaths might still be possible if the ions in the dip can escape. Finally, our simulations demonstrate ways in which SCL and inverse regimes might be distinguished experimentally based on large-scale presheath effects, without having to probe inside the sheath.« less

Mixed polyanion glass cathodes: Glass-state conversion reactions

DOE PAGES

Kercher, Andrew K.; Kolopus, James A.; Carroll, Kyler; ...

2015-11-10

Mixed polyanion (MP) glasses can undergo glass-state conversion (GSC) reactions to provide an alternate class of high-capacity cathode materials. GSC reactions have been demonstrated in phosphate/vanadate glasses with Ag, Co, Cu, Fe, and Ni cations. These MP glasses provided high capacity and good high power performance, but suffer from moderate voltages, large voltage hysteresis, and significant capacity fade with cycling. Details of the GSC reaction have been revealed by x-ray absorption spectroscopy, electron microscopy, and energy dispersive x-ray spectroscopy of ex situ cathodes at key states of charge. Using the Open Quantum Materials Database (OQMD), a computational thermodynamic model hasmore » been developed to predict the near-equilibrium voltages of glass-state conversion reactions in MP glasses.« less

Non-equilibrium steady states in the Klein-Gordon theory

NASA Astrophysics Data System (ADS)

Doyon, Benjamin; Lucas, Andrew; Schalm, Koenraad; Bhaseen, M. J.

2015-03-01

We construct non-equilibrium steady states in the Klein-Gordon theory in arbitrary space dimension d following a local quench. We consider the approach where two independently thermalized semi-infinite systems, with temperatures {{T}L} and {{T}R}, are connected along a d-1-dimensional hypersurface. A current-carrying steady state, described by thermally distributed modes with temperatures {{T}L} and {{T}R} for left and right-moving modes, respectively, emerges at late times. The non-equilibrium density matrix is the exponential of a non-local conserved charge. We obtain exact results for the average energy current and the complete distribution of energy current fluctuations. The latter shows that the long-time energy transfer can be described by a continuum of independent Poisson processes, for which we provide the exact weights. We further describe the full time evolution of local observables following the quench. Averages of generic local observables, including the stress-energy tensor, approach the steady state with a power-law in time, where the exponent depends on the initial conditions at the connection hypersurface. We describe boundary conditions and special operators for which the steady state is reached instantaneously on the connection hypersurface. A semiclassical analysis of freely propagating modes yields the average energy current at large distances and late times. We conclude by comparing and contrasting our findings with results for interacting theories and provide an estimate for the timescale governing the crossover to hydrodynamics. As a modification of our Klein-Gordon analysis we also include exact results for free Dirac fermions.

Dissecting the dynamic conformations of the metamorphic protein lymphotactin.

PubMed

Harvey, Sophie R; Porrini, Massimiliano; Konijnenberg, Albert; Clarke, David J; Tyler, Robert C; Langridge-Smith, Patrick R R; MacPhee, Cait E; Volkman, Brian F; Barran, Perdita E

2014-10-30

A mass spectrometer provides an ideal laboratory to probe the structure and stability of isolated protein ions. Interrogation of each discrete mass/charge-separated species enables the determination of the intrinsic stability of a protein fold, gaining snapshots of unfolding pathways. In solution, the metamorphic protein lymphotactin (Ltn) exists in equilibrium between two distinct conformations, a monomeric (Ltn10) and a dimeric (Ltn40) fold. Here, we use electron capture dissociation (ECD) and drift tube ion mobility-mass spectrometry (DT IM-MS) to analyze both forms and use molecular dynamics (MD) to consider how the solution fold alters in a solvent-free environment. DT IM-MS reveals significant conformational flexibility for the monomer, while the dimer appears more conformationally restricted. These findings are supported by MD calculations, which reveal how salt bridges stabilize the conformers in vacuo. Following ECD experiments, a distinctive fragmentation pattern is obtained for both the monomer and dimer. Monomer fragmentation becomes more pronounced with increasing charge state especially in the disordered regions and C-terminal α-helix in the solution fold. Lower levels of fragmentation are seen in the β-sheet regions and in regions that contain salt bridges, identified by MD simulations. The lowest charge state of the dimer for which we obtain ECD data ([D+9H](9+)) exhibits extensive fragmentation with no relationship to the solution fold and has a smaller collision cross section (CCS) than charge states 10-13+, suggesting a "collapsed" encounter complex. Other charge states of the dimer, as for the monomer, are resistant to fragmentation in regions of β-sheets in the solution fold. This study provides evidence for preservation and loss of global fold and secondary structural elements, providing a tantalizing glimpse into the power of the emerging field of native top-down mass spectrometry.

Points of Equilibrium in Electrostatic Fields.

ERIC Educational Resources Information Center

Rogers, Peter J.

1979-01-01

Discusses the electric field line pattern for four equal charges of the same sign placed at the corners of a square. The electric field intensity and the point of equilibrium are interpreted, taking into account three dimensions. (HM)

Solution equilibrium behind the room-temperature synthesis of nanocrystalline titanium dioxide

NASA Astrophysics Data System (ADS)

Seisenbaeva, Gulaim A.; Daniel, Geoffrey; Nedelec, Jean-Marie; Kessler, Vadim G.

2013-03-01

Formation of nanocrystalline and monodisperse TiO2 from a water soluble and stable precursor, ammonium oxo-lactato-titanate, (NH4)8Ti4O4(Lactate)8.4H2O, often referred to as TiBALDH or TALH, is demonstrated to be due to a coordination equilibrium. This compound, individual in the solid state, exists in solution in equilibrium with ammonium tris-lactato-titanate, (NH4)2Ti(Lactate)3 and uniform crystalline TiO2 nanoparticles (anatase) stabilized by surface-capping with lactate ligands. This equilibrium can be shifted towards nano-TiO2via application of a less polar solvent like methanol or ethanol, dilution of the solution, introduction of salts or raising the temperature, and reverted on addition of polar and strongly solvating media such as dimethyl sulfoxide, according to NMR. Aggregation and precipitation of the particles were followed by DLS and could be achieved by a decrease in their surface charge by adsorption of strongly hydrogen-bonding cations, e.g. in solutions of ammonia, ethanolamine or amino acid arginine or by addition of ethanol. The observed equilibrium may be involved in formation of nano-titania on the surface of plant roots exerting chelating organic carboxylate ligands and thus potentially influencing plant interactions.Formation of nanocrystalline and monodisperse TiO2 from a water soluble and stable precursor, ammonium oxo-lactato-titanate, (NH4)8Ti4O4(Lactate)8.4H2O, often referred to as TiBALDH or TALH, is demonstrated to be due to a coordination equilibrium. This compound, individual in the solid state, exists in solution in equilibrium with ammonium tris-lactato-titanate, (NH4)2Ti(Lactate)3 and uniform crystalline TiO2 nanoparticles (anatase) stabilized by surface-capping with lactate ligands. This equilibrium can be shifted towards nano-TiO2via application of a less polar solvent like methanol or ethanol, dilution of the solution, introduction of salts or raising the temperature, and reverted on addition of polar and strongly solvating media such as dimethyl sulfoxide, according to NMR. Aggregation and precipitation of the particles were followed by DLS and could be achieved by a decrease in their surface charge by adsorption of strongly hydrogen-bonding cations, e.g. in solutions of ammonia, ethanolamine or amino acid arginine or by addition of ethanol. The observed equilibrium may be involved in formation of nano-titania on the surface of plant roots exerting chelating organic carboxylate ligands and thus potentially influencing plant interactions. Electronic supplementary information (ESI) available: Crystallographic data in cif and table format, detailed description of hydrogen bonding in (NH4)2[Ti(l-Lactate)3].3H2O, additional TEM images, DLS data on particle size in solutions and NanoSight data on particle size distribution, photos of produced TiO2 colloids, details of NMR experiments and a real-time movie demonstrating the equilibrium leading to TiO2 formation and re-dissolution in pH-neutral ammonium lactate solutions. CCDC 915222. For ESI and crystallographic data in CIF or other electronic format. see DOI: 10.1039/c3nr34068f

Ion-ion interactions in the denatured state contribute to the stabilization of CutA1 proteins.

PubMed

Yutani, Katsuhide; Matsuura, Yoshinori; Naitow, Hisashi; Joti, Yasumasa

2018-05-16

In order to elucidate features of the denatured state ensembles that exist in equilibrium with the native state under physiological conditions, we performed 1.4-μs molecular dynamics (MD) simulations at 400 K and 450 K using the monomer subunits of three CutA1 mutants from Escherichia coli: an SH-free mutant (Ec0SH) with denaturation temperature (T d ) = 85.6 °C, a hydrophobic mutant (Ec0VV) with T d  = 113.3 °C, and an ionic mutant (Ec0VV_6) with T d  = 136.8 °C. The occupancy of salt bridges by the six substituted charged residues in Ec0VV_6 was 140.1% at 300 K and 89.5% at 450 K, indicating that even in the denatured state, salt bridge occupancy was high, approximately 60% of that at 300 K. From these results, we can infer that proteins from hyperthermophiles with a high ratio of charged residues are stabilized by a decrease in conformational entropy due to ion-ion interactions in the denatured state. The mechanism must be comparable to the stabilization conferred by disulfide bonds within a protein. This suggests that introduction of charged residues, to promote formation of salt bridges in the denatured state, would be a simple way to rationally design stability-enhanced mutants.

Mechanistic Studies of Metal-Oxo Cubane Catalysts for Lightweight Solar Fuels Storage

DTIC Science & Technology

2013-03-01

in the Co2+ and Co3+ states has allowed us to undertake detailed studies of the Co2+|Co3+ self-exchange kinetics, which is a critical factor in the...film thickness, indicating this indicates that the kinetic profile of catalyst films is not influenced by barriers to charge and/or mass transport... mass transport limitations through solution. A 60 mV/decade Tafel slope indicates that there exists a one-electron pre- equilibrium, prior to a

Magnetofluid dynamics in curved spacetime

NASA Astrophysics Data System (ADS)

Bhattacharjee, Chinmoy; Das, Rupam; Mahajan, S. M.

2015-03-01

A grand unified field Mμ ν is constructed from Maxwell's field tensor and an appropriately modified flow field, both nonminimally coupled to gravity, to analyze the dynamics of hot charged fluids in curved background space-time. With a suitable 3 +1 decomposition, this new formalism of the hot fluid is then applied to investigate the vortical dynamics of the system. Finally, the equilibrium state for plasma with nonminimal coupling through Ricci scalar R to gravity is investigated to derive a double Beltrami equation in curved space-time.

A novel multiphysic model for simulation of swelling equilibrium of ionized thermal-stimulus responsive hydrogels

NASA Astrophysics Data System (ADS)

Li, Hua; Wang, Xiaogui; Yan, Guoping; Lam, K. Y.; Cheng, Sixue; Zou, Tao; Zhuo, Renxi

2005-03-01

In this paper, a novel multiphysic mathematical model is developed for simulation of swelling equilibrium of ionized temperature sensitive hydrogels with the volume phase transition, and it is termed the multi-effect-coupling thermal-stimulus (MECtherm) model. This model consists of the steady-state Nernst-Planck equation, Poisson equation and swelling equilibrium governing equation based on the Flory's mean field theory, in which two types of polymer-solvent interaction parameters, as the functions of temperature and polymer-network volume fraction, are specified with or without consideration of the hydrogen bond interaction. In order to examine the MECtherm model consisting of nonlinear partial differential equations, a meshless Hermite-Cloud method is used for numerical solution of one-dimensional swelling equilibrium of thermal-stimulus responsive hydrogels immersed in a bathing solution. The computed results are in very good agreements with experimental data for the variation of volume swelling ratio with temperature. The influences of the salt concentration and initial fixed-charge density are discussed in detail on the variations of volume swelling ratio of hydrogels, mobile ion concentrations and electric potential of both interior hydrogels and exterior bathing solution.

Quantum thermodynamics of nanoscale steady states far from equilibrium

NASA Astrophysics Data System (ADS)

Taniguchi, Nobuhiko

2018-04-01

We develop an exact quantum thermodynamic description for a noninteracting nanoscale steady state that couples strongly with multiple reservoirs. We demonstrate that there exists a steady-state extension of the thermodynamic function that correctly accounts for the multiterminal Landauer-Büttiker formula of quantum transport of charge, energy, or heat via the nonequilibrium thermodynamic relations. Its explicit form is obtained for a single bosonic or fermionic level in the wide-band limit, and corresponding thermodynamic forces (affinities) are identified. Nonlinear generalization of the Onsager reciprocity relations are derived. We suggest that the steady-state thermodynamic function is also capable of characterizing the heat current fluctuations of the critical transport where the thermal fluctuations dominate. Also, the suggested nonequilibrium steady-state thermodynamic relations seemingly persist for a spin-degenerate single level with local interaction.

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.

The Gibbs Variational Method in Thermodynamics of Equilibrium Plasma: 1. General Conditions of Equilibrium and Stability for One-Component Charged Gas

DTIC Science & Technology

2018-04-01

systems containing ionized gases. 2. Gibbs Method in the Integral Form As per the Gibbs general methodology , based on the concept of heterogeneous...ARL-TR-8348 ● APR 2018 US Army Research Laboratory The Gibbs Variational Method in Thermodynamics of Equilibrium Plasma: 1...ARL-TR-8348 ● APR 2018 US Army Research Laboratory The Gibbs Variational Method in Thermodynamics of Equilibrium Plasma: 1. General

Discharge, Relaxation, and Charge Model for the Lithium Trivanadate Electrode: Reactions, Phase Change, and Transport

DOE PAGES

Brady, Nicholas W.; Zhang, Qing; Knehr, K. W.; ...

2016-10-26

The electrochemical behavior of lithium trivanadate (LiV 3O 8) during lithiation, delithiation, and voltage recovery experiments is simulated using a crystal-scale model that accounts for solid-state diffusion, charge-transfer kinetics, and phase transformations. The kinetic expression for phase change was modeled using an approach inspired by the Avrami formulation for nucleation and growth. Numerical results indicate that the solid-state diffusion coefficient of lithium in LiV 3O 8 is ~ 10 -13 cm 2 s -1 and the equilibrium compositions in the two phase region (~2.5 V) are Li 2.5V 3O 8:Li 4V 3O 8. Agreement between the simulated and experimental resultsmore » is excellent. Relative to the lithiation curves, the experimental delithiation curves show significantly less overpotential and at low levels of lithiation (end of charge). Simulations are only able to capture this result by assuming that the solid-state mass-transfer resistance is less during delithiation. The proposed rationale for this difference is that the (100) face is inactive during lithiation, but active during delithiation. Finally, by assuming non-instantaneous phase-change kinetics, estimates are made for the overpotential due to imperfect phase change (supersaturation).« less

Role of the Charge-Transfer State in Reduced Langevin Recombination in Organic Solar Cells: A Theoretical Study

PubMed Central

2015-01-01

Reduced Langevin recombination has been observed in organic solar cells (OSCs) for many years, but its origin is still unclear. A recent work by Burke et al. (Adv. Energy Mater.2015, 5, 1500123-1) was inspired by this reduced Langevin recombination, and they proposed an equilibrium model of charge-transfer (CT) states that correlates the open-circuit voltage of OSCs with experimentally available device parameters. In this work, we extend Burke et al.’s CT model further and for the first time directly correlate the reduced Langevin recombination with the energetic and dynamic behavior of the CT state. Recombination through CT states leads in a straightforward manner to a decrease in the Langevin reduction factor with increasing temperature, without explicit consideration of the temperature dependence of the mobility. To verify the correlation between the CT states and reduced Langevin recombination, we incorporated this CT model and the reduced Langevin model into drift-diffusion simulations of a bilayer OSC. The simulations not only successfully reproduced realistic current–voltage (J–V) characteristics of the bilayer OSC, but also demonstrate that the two models consistently lead to same value of the apparent Langevin reduction factor. PMID:26640611

Equilibrium configurations of a charged fluid around a Kerr black hole

NASA Astrophysics Data System (ADS)

Trova, Audrey; Schroven, Kris; Hackmann, Eva; Karas, Vladimír; Kovář, Jiří; Slaný, Petr

2018-05-01

Equilibrium configurations of electrically charged perfect fluid surrounding a central rotating black hole endowed with a test electric charge and embedded in a large-scale asymptotically uniform magnetic field are presented. Following our previous studies considering the central black hole to be nonrotating, we show that in the rotating case conditions for the configurations existence change according to the spin of the black hole. We focus our attention on the charged fluid in rigid rotation, which can form toroidal configurations centered in the equatorial plane or the ones hovering above the black hole, along the symmetry axis. We conclude that a nonzero value of spin changes the existence conditions and the morphology of the solutions significantly. In the case of fast rotation, the morphology of the structures is close to an oblate shape.

Conformational flexibility of arginine-82 as source for the heterogeneous and pH-dependent kinetics of the primary proton transfer step in the bacteriorhodopsin photocycle: An electrostatic model

NASA Astrophysics Data System (ADS)

Scharnagl, Christina; Fischer, Sighart F.

1996-11-01

We use equilibrium thermodynamic concepts to relate protein conformational and protonation substates and their pH-dependent population to kinetic schemes for the rise of the M intermediate in the photocycle of bacteriorhodopsin. Conformational flexibility of arginine R82 is described by a two-state model. The analysis accounts for the electrostatic coupling between its orientation and hydrogen ion titration and presents a structural basis for the linkage between the protonation states of the primary proton acceptor, aspartate D85, and the extracellular release group, glutamate E204. We find that the charge state of D85 is a significant determinant for the orientation of R82. The molecular model predicts the following: the primary proton transfer to D85 can be described by a kinetic scheme with two heterogeneous substates. They control the event with different activation parameters due to the reorientation of R82 away from the chromophore binding site. Their population depends on the external pH and the proton exchange equilibrium between the membrane buried residues and the bulk aqueous solvent. Proton transfer in the physiologic pH range is strongly activated and followed by the reorientation of R82 which shifts the equilibrium toward complete transfer. In the alkaline pH region a different mechanism operates, which involves the increased population of a substate with already reoriented R82 as a consequence of the deprotonation of E204, leading to accelerated proton transfer. Assuming full proton exchange equilibrium with the bulk water on the millisecond time scale leads to an increased population of substates which are non-productive for proton transfer.

Photoinduced intramolecular charge transfer (ICT) reaction in trans-methyl p-(dimethylamino) cinnamate: A combined fluorescence measurement and quantum chemical calculations

NASA Astrophysics Data System (ADS)

Chakraborty, Amrita; Kar, Samiran; Guchhait, Nikhil

2006-01-01

The photophysical behaviour of trans-methyl p-(dimethylamino) cinnamate ( t-MDMAC) donor-acceptor system has been investigated by steady-state absorption and emission spectroscopy and quantum chemical calculations. The molecule t-MDMAC shows an emission from the locally excited state in non-polar solvents. In addition to weak local emission, a strong solvent dependent red shifted fluorescence in polar aprotic solvents is attributed to highly polar intramolecular charge transfer state. However, the formation of hydrogen-bonded clusters with polar protic solvents has been suggested from a linear correlation between the observed red shifted fluorescence band maxima with hydrogen bonding parameters ( α). Calculations by ab initio and density functional theory show that the lone pair electron at nitrogen center is out of plane of the benzene ring in the global minimum ground state structure. In the gas phase, a potential energy surface along the twist coordinate at the donor (-NMe 2) and acceptor (-CH = CHCOOMe) sites shows stabilization of S 1 state and destabilization S 2 and S 0 states. A similar potential energy calculation along the twist coordinate in acetonitrile solvent using non-equilibrium polarized continuum model also shows more stabilization of S 1 state relative to other states and supports solvent dependent red shifted emission properties. In all types of calculations it is found that the nitrogen lone pair is delocalized over the benzene ring in the global minimum ground state and is localized on the nitrogen centre at the 90° twisted configuration. The S 1 energy state stabilization along the twist coordinate at the donor site and localized nitrogen lone pair at the perpendicular configuration support well the observed dual fluorescence in terms of proposed twisted intramolecular charge transfer (TICT) model.

A theoretical DFT study on the structural parameters and azide-tetrazole equilibrium in substituted azidothiazole systems.

PubMed

Abu-Eittah, Rafie H; El-Kelany, Khaled E

2012-12-01

Azido-tetrazole equilibrium is sensitive to: substitution, solvent, temperature and phase. In this work, the effects of the type and position of substitution on the thiazole ring of azidothiazoles on its structural parameters and on the azido-tetrazole equilibrium have been theoretically investigated using the density functional procedures at the B3LYP/6-311G(∗∗) level of theory. This study includes the investigation of the equilibrium geometry, the transformation of the trans-conformer to the cis one then the ring closure to the tetrazole isomer. The transition states of the two steps were located, confirmed and the structural parameters were calculated. In all the steps of calculations, geometry optimization was considered. The results obtained indicate that substitution by: -NO(2) and -CN group shifts the equilibrium to the azide side and in some cases the tetrazole isomer is not obtained. On the other hand, substitution by: -NH(2) and -OH groups shifts the equilibrium to the tetrazole side and in some cases the azide isomer is not obtained and if formed changes spontaneously to the tetrazole isomer. The decisive parameters which determine the position of the equilibrium are: charge density on atoms N3 and N8, rearrangement of bond length and bond angles during the process of cyclization and variation of dipole moment as a result of cyclization. Results of this work indicate that substitution on C5 is more efficient than substitution on C4 of the thiazole ring. Copyright © 2012 Elsevier B.V. All rights reserved.

Non-equilibrium Green's functions method: Non-trivial and disordered leads

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

He, Yu, E-mail: heyuyhe@gmail.com; Wang, Yu; Klimeck, Gerhard

2014-11-24

The non-equilibrium Green's function algorithm requires contact self-energies to model charge injection and extraction. All existing approaches assume infinitely periodic leads attached to a possibly quite complex device. This contradicts today's realistic devices in which contacts are spatially inhomogeneous, chemically disordered, and impacting the overall device characteristics. This work extends the complex absorbing potentials method for arbitrary, ideal, or non-ideal leads in atomistic tight binding representation. The algorithm is demonstrated on a Si nanowire with periodic leads, a graphene nanoribbon with trumpet shape leads, and devices with leads of randomly alloyed Si{sub 0.5}Ge{sub 0.5}. It is found that alloy randomnessmore » in the leads can reduce the predicted ON-state current of Si{sub 0.5}Ge{sub 0.5} transistors by 45% compared to conventional lead methods.« less

Anomalous behavior of 1/f noise in graphene near the charge neutrality point

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

Takeshita, Shunpei; Tanaka, Takahiro; Arakawa, Tomonori

2016-03-07

We investigate the noise in single layer graphene devices from equilibrium to far-from equilibrium and found that the 1/f noise shows an anomalous dependence on the source-drain bias voltage (V{sub SD}). While the Hooge's relation is not the case around the charge neutrality point, we found that it is recovered at very low V{sub SD} region. We propose that the depinning of the electron-hole puddles is induced at finite V{sub SD}, which may explain this anomalous noise behavior.

Charged particle layers in the Debye limit.

PubMed

Golden, Kenneth I; Kalman, Gabor J; Kyrkos, Stamatios

2002-09-01

We develop an equivalent of the Debye-Hückel weakly coupled equilibrium theory for layered classical charged particle systems composed of one single charged species. We consider the two most important configurations, the charged particle bilayer and the infinite superlattice. The approach is based on the link provided by the classical fluctuation-dissipation theorem between the random-phase approximation response functions and the Debye equilibrium pair correlation function. Layer-layer pair correlation functions, screened and polarization potentials, static structure functions, and static response functions are calculated. The importance of the perfect screening and compressibility sum rules in determining the overall behavior of the system, especially in the r--> infinity limit, is emphasized. The similarities and differences between the quasi-two-dimensional bilayer and the quasi-three-dimensional superlattice are highlighted. An unexpected behavior that emerges from the analysis is that the screened potential, the correlations, and the screening charges carried by the individual layers exhibit a marked nonmonotonic dependence on the layer separation.

Equilibrium polyelectrolyte bundles with different multivalent counterion concentrations

NASA Astrophysics Data System (ADS)

Sayar, Mehmet; Holm, Christian

2010-09-01

We present the results of molecular-dynamics simulations on the salt concentration dependence of the formation of polyelectrolyte bundles in thermodynamic equilibrium. Extending our results on salt-free systems we investigate here deficiency or excess of trivalent counterions in solution. Our results reveal that the trivalent counterion concentration significantly alters the bundle size and size distribution. The onset of bundle formation takes place at earlier Bjerrum length values with increasing trivalent counterion concentration. For the cases of 80%, 95%, and 100% charge compensation via trivalent counterions, the net charge of the bundles decreases with increasing size. We suggest that competition among two different mechanisms, counterion condensation and merger of bundles, leads to a nonmonotonic change in line-charge density with increasing Bjerrum length. The investigated case of having an abundance of trivalent counterions by 200% prohibits such a behavior. In this case, we find that the difference in effective line-charge density of different size bundles diminishes. In fact, the system displays an isoelectric point, where all bundles become charge neutral.

Simulation of Turbulent Combustion Fields of Shock-Dispersed Aluminum Using the AMR Code

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

Kuhl, A L; Bell, J B; Beckner, V E

2006-11-02

We present a Model for simulating experiments of combustion in Shock-Dispersed-Fuel (SDF) explosions. The SDF charge consisted of a 0.5-g spherical PETN booster, surrounded by 1-g of fuel powder (flake Aluminum). Detonation of the booster charge creates a high-temperature, high-pressure source (PETN detonation products gases) that both disperses the fuel and heats it. Combustion ensues when the fuel mixes with air. The gas phase is governed by the gas-dynamic conservation laws, while the particle phase obeys the continuum mechanics laws for heterogeneous media. The two phases exchange mass, momentum and energy according to inter-phase interaction terms. The kinetics model usedmore » an empirical particle burn relation. The thermodynamic model considers the air, fuel and booster products to be of frozen composition, while the Al combustion products are assumed to be in equilibrium. The thermodynamic states were calculated by the Cheetah code; resulting state points were fit with analytic functions suitable for numerical simulations. Numerical simulations of combustion of an Aluminum SDF charge in a 6.4-liter chamber were performed. Computed pressure histories agree with measurements.« less

The change in hydrogen bond strength accompanying charge rearrangement: Implications for enzymatic catalysis

PubMed Central

Shan, Shu-ou; Herschlag, Daniel

1996-01-01

The equilibrium for formation of the intramolecular hydrogen bond (KHB) in a series of substituted salicylate monoanions was investigated as a function of ΔpKa, the difference between the pKa values of the hydrogen bond donor and acceptor, in both water and dimethyl sulfoxide. The dependence of log KHB upon ΔpKa is linear in both solvents, but is steeper in dimethyl sulfoxide (slope = 0.73) than in water (slope = 0.05). Thus, hydrogen bond strength can undergo substantially larger increases in nonaqueous media than aqueous solutions as the charge density on the donor or acceptor atom increases. These results support a general mechanism for enzymatic catalysis, in which hydrogen bonding to a substrate is strengthened as charge rearranges in going from the ground state to the transition state; the strengthening of the hydrogen bond would be greater in a nonaqueous enzymatic active site than in water, thus providing a rate enhancement for an enzymatic reaction relative to the solution reaction. We suggest that binding energy of an enzyme is used to fix the substrate in the low-dielectric active site, where the strengthening of the hydrogen bond in the course of a reaction is increased. PMID:8962076

Non-equilibrium time evolution of higher order cumulants of conserved charges and event-by-event analysis

NASA Astrophysics Data System (ADS)

Kitazawa, Masakiyo; Asakawa, Masayuki; Ono, Hirosato

2014-01-01

We investigate the time evolution of higher order cumulants of conserved charges in a volume with the diffusion master equation. Applying the result to the diffusion of non-Gaussian fluctuations in the hadronic stage of relativistic heavy ion collisions, we show that the fourth-order cumulant of net-electric charge at LHC energy is suppressed compared with the recently observed second-order cumulant at ALICE, if the higher order cumulants at hadronization are suppressed compared with their values in the hadron phase in equilibrium. The significance of the experimental information on the rapidity window dependence of various cumulants in investigating the history of the dynamical evolution of the hot medium created in relativistic heavy ion collisions is emphasized.

The physicist's companion to current fluctuations: one-dimensional bulk-driven lattice gases

NASA Astrophysics Data System (ADS)

Lazarescu, Alexandre

2015-12-01

One of the main features of statistical systems out of equilibrium is the currents they exhibit in their stationary state: microscopic currents of probability between configurations, which translate into macroscopic currents of mass, charge, etc. Understanding the general behaviour of these currents is an important step towards building a universal framework for non-equilibrium steady states akin to the Gibbs-Boltzmann distribution for equilibrium systems. In this review, we consider one-dimensional bulk-driven particle gases, and in particular the asymmetric simple exclusion process (ASEP) with open boundaries, which is one of the most popular models of one-dimensional transport. We focus, in particular, on the current of particles flowing through the system in its steady state, and on its fluctuations. We show how one can obtain the complete statistics of that current, through its large deviation function, by combining results from various methods: exact calculation of the cumulants of the current, using the integrability of the model; direct diagonalization of a biased process in the limits of very high or low current; hydrodynamic description of the model in the continuous limit using the macroscopic fluctuation theory. We give a pedagogical account of these techniques, starting with a quick introduction to the necessary mathematical tools, as well as a short overview of the existing works relating to the ASEP. We conclude by drawing the complete dynamical phase diagram of the current. We also remark on a few possible generalizations of these results.

Vibrational study and Natural Bond Orbital analysis of serotonin in monomer and dimer states by density functional theory

NASA Astrophysics Data System (ADS)

Borah, Mukunda Madhab; Devi, Th. Gomti

2018-06-01

The vibrational spectral analysis of Serotonin and its dimer were carried out using the Fourier Transform Infrared (FTIR) and Raman techniques. The equilibrium geometrical parameters, harmonic vibrational wavenumbers, Frontier orbitals, Mulliken atomic charges, Natural Bond orbitals, first order hyperpolarizability and some optimized energy parameters were computed by density functional theory with 6-31G(d,p) basis set. The detailed analysis of the vibrational spectra have been carried out by computing Potential Energy Distribution (PED, %) with the help of Vibrational Energy Distribution Analysis (VEDA) program. The second order delocalization energies E(2) confirms the occurrence of intramolecular Charge Transfer (ICT) within the molecule. The computed wavenumbers of Serotonin monomer and dimer were found in good agreement with the experimental Raman and IR values.

Phase diagram, correlation gap, and critical properties of the coulomb glass.

PubMed

Goethe, Martin; Palassini, Matteo

2009-07-24

We investigate the lattice Coulomb glass model in three dimensions via Monte Carlo simulations. No evidence for an equilibrium glass phase is found down to very low temperatures, although the correlation length increases rapidly near T = 0. A charge-ordered phase exists at low disorder. The transition to this phase is consistent with the random field Ising universality class, which shows that the interaction is effectively screened at moderate temperature. For large disorder, the single-particle density of states near the Coulomb gap satisfies the scaling relation g(epsilon, T) = T;{delta}f(|epsilon|/T) with delta = 2.01 +/- 0.05 in agreement with the prediction of Efros and Shklovskii. For decreasing disorder, a crossover to a larger effective exponent occurs due to the proximity of the charge-ordered phase.

Phase diagram, correlation gap, and critical properties of the Coulomb glass

NASA Astrophysics Data System (ADS)

Palassini, Matteo; Goethe, Martin

2009-03-01

We investigate the lattice Coulomb glass model in three dimensions via extensive Monte Carlo simulations. 1. No evidence for an equilibrium glass phase is found down to very low temperatures, contrary to mean-field predictions, although the correlation length increases rapidly near T=0. 2. The single-particle density of states near the Coulomb gap satisfies the scaling law g(e,T)=T^λf(e/T) with λ 2.2. 3. A charge-ordered phase exists at low disorder. The phase transition from the fluid to the charge ordered phase is consistent with the Random Field Ising universality class, which shows that the interaction is effectively screened at moderate temperature. Results from nonequilibrium simulations will also be briefly discussed. Reference: M.Goethe and M.Palassini, arXiv:0810.1047

Enhanced flashover strength in polyethylene nanodielectrics by secondary electron emission modification

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

Wang, Weiwang; Li, Shengtao, E-mail: sli@xjtu.edu.cn; Min, Daomin

2016-04-15

This work studies the correlation between secondary electron emission (SEE) characteristics and impulse surface flashover in polyethylene nanodielectrics both theoretically and experimentally, and illustrates the enhancement of flashover voltage in low-density polyethylene (LDPE) through incorporating Al{sub 2}O{sub 3} nanoparticles. SEE characteristics play key roles in surface charging and gas desorption during surface flashover. This work demonstrates that the presence of Al{sub 2}O{sub 3} nanoparticles decreases the SEE coefficient of LDPE and enhances the impact energy at the equilibrium state of surface charging. These changes can be explained by the increase of surface roughness and of surface ionization energy, and themore » strong interaction between nanoparticles and the polymer dielectric matrix. The surface charge and flashover voltage are calculated according to the secondary electron emission avalanche (SEEA) model, which reveals that the positive surface charges are reduced near the cathode triple point, while the presence of more nanoparticles in high loading samples enhances the gas desorption. Consequently, the surface flashover performance of LDPE/Al{sub 2}O{sub 3} nanodielectrics is improved.« less

Exactly solvable model of the two-dimensional electrical double layer.

PubMed

Samaj, L; Bajnok, Z

2005-12-01

We consider equilibrium statistical mechanics of a simplified model for the ideal conductor electrode in an interface contact with a classical semi-infinite electrolyte, modeled by the two-dimensional Coulomb gas of pointlike unit charges in the stability-against-collapse regime of reduced inverse temperatures 0< or = beta < 2. If there is a potential difference between the bulk interior of the electrolyte and the grounded electrode, the electrolyte region close to the electrode (known as the electrical double layer) carries some nonzero surface charge density. The model is mappable onto an integrable semi-infinite sine-Gordon theory with Dirichlet boundary conditions. The exact form-factor and boundary state information gained from the mapping provide asymptotic forms of the charge and number density profiles of electrolyte particles at large distances from the interface. The result for the asymptotic behavior of the induced electric potential, related to the charge density via the Poisson equation, confirms the validity of the concept of renormalized charge and the corresponding saturation hypothesis. It is documented on the nonperturbative result for the asymptotic density profile at a strictly nonzero beta that the Debye-Hückel beta-->0 limit is a delicate issue.

Transient electrokinetic transport in a finite length microchannel: currents, capacitance, and an electrical analogy.

PubMed

Mansouri, Ali; Bhattacharjee, Subir; Kostiuk, Larry W

2007-11-08

Numerical simulations with the fluid mechanics based on the unsteady Navier-Stokes equations and the Poisson-Nernst-Planck formulation of electrostatics and ion transport were used to explore the transient transport of charge through a finite length cylindrical microchannel that is driven by a pressure difference. The evolution of the transcapillary potential from a no-flow equilibrium to the steady-state-steady-flow streaming potential was analyzed by following the convection, migration, and net currents. Observations of the unsteady characteristics of the streaming current, electrical resistance, and capacitance led to an electrical analogy. This electrical analogy was made from a current source (to represent convection current), which was placed in parallel with a capacitor (to allow the accumulation of charge) and a resistor (to permit a migration current). A parametric study involving a range of geometries, fluid mechanics, electrostatics, and mass transfer states allowed predictive submodels for the current source, capacitor, and resistor to be developed based on a dimensional analysis.

Electron capture by U(91+) and U(92+) and ionization of U(90+) and U(91+)

NASA Technical Reports Server (NTRS)

Gould, H.; Greiner, D.; Lindstrom, P.; Symons, T. J. M.; Crawford, H.

1984-01-01

U(92+)/U(91+) and U(91+)/U(90+) electron-capture and ionization cross sections and equilibrium charge-state distributions are measured experimentally in mylar, Cu and Ta of varying thickness. Relativistic U(68+) ions at 437 or 962 MeV/nucleon are produced by a heavy-ion linear accelerator and synchrotron in tandem and passed through the target material into a magnetic specrometer and position-sensitive proportional counter for evaluation of charge states. The results are presented graphically and discussed. At 962 MeV/nucleon, beams containing 85 percent bare U(92+) nuclei are obtained using 150-mg/sq cm Cu or 85-mg/sq cm Ta; at 437 MeV/nucleon, 50 percent bare U(92+) nuclei are obtained with 90-mg/sq cm Cu. The techniques decribed can be applied to produce beams of bare U nuclei for acceleration to ultrarelativistic speeds or beams of few-electron U for atomic-physics experiments on quantum electrodynamics.

Time dependent charging of layer clouds in the global electric circuit

NASA Astrophysics Data System (ADS)

Zhou, Limin; Tinsley, Brian A.

2012-09-01

There is much observational data consistent with the hypothesis that the ionosphere-earth current density (Jz) in the global electric circuit, which is modulated by both solar activity and thunderstorm activity, affects atmospheric dynamics and cloud cover. One candidate mechanism involves Jz causing the accumulation of space charge on droplets and aerosol particles, that affects the rate of scavenging of the latter, notably those of Cloud Condensation Nuclei (CCN) and Ice Forming Nuclei (IFN) (Tinsley, 2008, 2010). Space charge is the difference, per unit volume, between total positive and total negative electrical charge that is on droplets, aerosol particles (including the CCN and IFN) and air ions. The cumulative effects of the scavenging in stratiform clouds and aerosol layers in an air mass over the lifetime of the aerosol particles of 1-10 days affects the concentration and size distribution of the CCN, so that in subsequent episodes of cloud formation (including deep convective clouds) there can be effects on droplet size distribution, coagulation, precipitation processes, and even storm dynamics.Because the time scales for charging for some clouds can be long compared to cloud lifetimes, the amount of charge at a given time, and its effect on scavenging, depend more on the charging rate than on the equilibrium charge that would eventually be attained. To evaluate this, a new time-dependent charging model has been developed. The results show that for typical altostratus clouds with typical droplet radii 10 μm and aerosol particles of radius of 0.04 μm, the time constant for charging in response to a change in Jz is about 800 s, which is comparable to cloud formation and dissipation timescales for some cloud situations. The charging timescale is found to be strong functions of altitude and aerosol concentration, with the time constant for droplet charging at 2 km in air with a high concentration of aerosols being about an hour, and for clouds at 10 km in clean air being about a minute. The charging timescale is also a strong function of droplet size, with the rate for 15 μm radii droplets being about 70% longer than that for 10 μm droplets, and the rate for 5 μm radii droplets being about 50% smaller. The equilibrium charges accumulated on droplets ranged from tens to hundreds of elementary charges, which is comparable to observed values, and to vary approximately directly with Jz and inversely with the ion production rate q, which is due to the Galactic Cosmic Ray (GCR) flux and depends strongly on altitude.For the case of Jz varying directly with q, which to some extent is the case during Forbush decreases of the GCR flux, the effects on the equilibrium charge tend to cancel. In one run with the model, both q and Jz were decreased by 30%. There was little change in equilibrium charge, but the timescale for charging increased by about 40%, or equivalently, the rate of charging decreased by about 40%. Thus, for exploring the hypothesis that space charge provides a link between GCR (and other inputs that modulate Jz) and changes in clouds and atmospheric dynamics, it is necessary to consider variations in the rate of charging. The present work is intended to provide illustrative examples of time dependent charging for several different types of layer clouds.

Bus-based park-and-ride system: a stochastic model on multimodal network with congestion pricing schemes

NASA Astrophysics Data System (ADS)

Liu, Zhiyuan; Meng, Qiang

2014-05-01

This paper focuses on modelling the network flow equilibrium problem on a multimodal transport network with bus-based park-and-ride (P&R) system and congestion pricing charges. The multimodal network has three travel modes: auto mode, transit mode and P&R mode. A continuously distributed value-of-time is assumed to convert toll charges and transit fares to time unit, and the users' route choice behaviour is assumed to follow the probit-based stochastic user equilibrium principle with elastic demand. These two assumptions have caused randomness to the users' generalised travel times on the multimodal network. A comprehensive network framework is first defined for the flow equilibrium problem with consideration of interactions between auto flows and transit (bus) flows. Then, a fixed-point model with unique solution is proposed for the equilibrium flows, which can be solved by a convergent cost averaging method. Finally, the proposed methodology is tested by a network example.

Nonequilibrium Kondo effect by the equilibrium numerical renormalization group method: The hybrid Anderson model subject to a finite spin bias

NASA Astrophysics Data System (ADS)

Fang, Tie-Feng; Guo, Ai-Min; Sun, Qing-Feng

2018-06-01

We investigate Kondo correlations in a quantum dot with normal and superconducting electrodes, where a spin bias voltage is applied across the device and the local interaction U is either attractive or repulsive. When the spin current is blockaded in the large-gap regime, this nonequilibrium strongly correlated problem maps into an equilibrium model solvable by the numerical renormalization group method. The Kondo spectra with characteristic splitting due to the nonequilibrium spin accumulation are thus obtained at high precision. It is shown that while the bias-induced decoherence of the spin Kondo effect is partially compensated by the superconductivity, the charge Kondo effect is enhanced out of equilibrium and undergoes an additional splitting by the superconducting proximity effect, yielding four Kondo peaks in the local spectral density. In the charge Kondo regime, we find a universal scaling of charge conductance in this hybrid device under different spin biases. The universal conductance as a function of the coupling to the superconducting lead is peaked at and hence directly measures the Kondo temperature. Our results are of direct relevance to recent experiments realizing a negative-U charge Kondo effect in hybrid oxide quantum dots [Nat. Commun. 8, 395 (2017), 10.1038/s41467-017-00495-7].

Investigation of surface charge density on solid-liquid interfaces by modulating the electrical double layer.

PubMed

Moon, Jong Kyun; Song, Myung Won; Pak, Hyuk Kyu

2015-05-20

A solid surface in contact with water or aqueous solution usually carries specific electric charges. These surface charges attract counter ions from the liquid side. Since the geometry of opposite charge distribution parallel to the solid-liquid interface is similar to that of a capacitor, it is called an electrical double layer capacitor (EDLC). Therefore, there is an electrical potential difference across an EDLC in equilibrium. When a liquid bridge is formed between two conducting plates, the system behaves as two serially connected EDLCs. In this work, we propose a new method for investigating the surface charge density on solid-liquid interfaces. By mechanically modulating the electrical double layers and simultaneously applying a dc bias voltage across the plates, an ac electric current can be generated. By measuring the voltage drop across a load resistor as a function of bias voltage, we can study the surface charge density on solid-liquid interfaces. Our experimental results agree very well with the simple equivalent electrical circuit model proposed here. Furthermore, using this method, one can determine the polarity of the adsorbed state on the solid surface depending on the material used. We expect this method to aid in the study of electrical phenomena on solid-liquid interfaces.

Quantum Chemical Study of Rare Gas/Halide Interactions as a Model for High Energy Density Material: 2. The Interaction of Hydrogen Chloride with the Rare Gas Xenon

DTIC Science & Technology

1994-11-01

the negatively charged halide, X(-), remains scparatcd from the Rgnl(+) hole. But when the (+) holes migrate to the X(-), they rapidly form the exciplex ...Xe2.(+)X(-), releasing the exciton energy as fluorescence. The gas phase equilibrium geometry for the Xe 2C1 exciplex in the 421- state is predicted...understanding of the microscopic processes involved in formation c. the exciplex , as well as the factors determining the lifetime of the separated

Thermodynamics of nickel-cadmium and nickel-hydrogen batteries

NASA Technical Reports Server (NTRS)

Macdonald, Digby D.; Challingsworth, Mark L.

1993-01-01

Thermodynamic parameters for Nickel-Cadmium (NiCad) and Nickel-Hydrogen (NiH2) batteries are calculated for temperatures ranging from 273.15K (0 C) to 373.15K (100 C). For both systems, we list equilibrium and thermoneutral voltages for the cells, and in the case of the NiH2 battery, these data are provide for hydrogen fugacities ranging from 0.01 to 100 (atm) to simulate the full discharged and charged states. The quality of the input thermodynamic data are assessed and the effect of assuming different cell reactions is analyzed.

Structural and spectroscopic (UV-Vis, IR, Raman, and NMR) characteristics of anisaldehydes that are flavoring food additives: A density functional study in comparison with experiments

NASA Astrophysics Data System (ADS)

Altun, Ahmet; Swesi, O. A. A.; Alhatab, B. S. S.

2017-01-01

The molecular structures, vibrational spectra (IR and Raman), electronic spectra (UV-Vis and DOS), and NMR spectra (13C and 1H) of p-anisaldehyde, m-anisaldehyde, and o-anisaldehyde have been studied by using the B3LYP density functional and the 6-311++G** basis set. While p-anisaldehyde has been found to contain two stable conformers at room temperature, m-anisaldehyde and o-anisaldehyde contain four stable conformers. In agreement with the calculated ground-state energetics and small transition barriers, the comparison of the experimental and calculated spectra of the anisaldehydes indicates equilibrium between all conformers at room temperature. However, the two conformers of o-anisaldehyde, in which the methoxy group lies out of the ring plane, are too rare at the equilibrium. The equilibrium conditions of the conformers of the anisaldehyde isomers have been shown readily accessible through UV-Vis and 13C NMR spectral studies but requiring very detailed vibrational analyses. The effect of the solvent has been found to red-shift the electronic absorption bands and to make the anisaldehydes more reactive and soft. Molecular electrostatic potential maps of the anisaldehydes show that their oxygen atoms are the sites for nucleophilic reactivity. Compared with the most sophisticated NBO method, ESP charges have been found mostly reliable while Mulliken charges fail badly with the present large 6-311++G** basis set. The present calculations reproduce not only the experimental spectral characteristics of the anisaldehydes but also reveal their several structural features.

Dynamics of dissipative self-assembly of particles interacting through oscillatory forces

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

Tagliazucchi, M.; Szleifer, I.

Dissipative self-assembly is the formation of ordered structures far from equilibrium, which continuously uptake energy and dissipate it into the environment. Due to its dynamical nature, dissipative self-assembly can lead to new phenomena and possibilities of self-organization that are unavailable to equilibrium systems. Understanding the dynamics of dissipative self-assembly is required in order to direct the assembly to structures of interest. In the present work, Brownian dynamics simulations and analytical theory were used to study the dynamics of self-assembly of a mixture of particles coated with weak acids and bases under continuous oscillations of the pH. The pH of themore » system modulates the charge of the particles and, therefore, the interparticle forces oscillate in time. This system produces a variety of self-assembled structures, including colloidal molecules, fibers and different types of crystalline lattices. The most important conclusions of our study are: (i) in the limit of fast oscillations, the whole dynamics (and not only those at the non-equilibrium steady state) of a system of particles interacting through time-oscillating interparticle forces can be described by an effective potential that is the time average of the time-dependent potential over one oscillation period; (ii) the oscillation period is critical to determine the order of the system. In some cases the order is favored by very fast oscillations while in others small oscillation frequencies increase the order. In the latter case, it is shown that slow oscillations remove kinetic traps and, thus, allow the system to evolve towards the most stable non-equilibrium steady state.« less

Equilibrium charge fluctuations of a charge detector and its effect on a nearby quantum dot

NASA Astrophysics Data System (ADS)

Ruiz-Tijerina, David; Vernek, Edson; Ulloa, Sergio

2014-03-01

We study the Kondo state of a spin-1/2 quantum dot (QD), in close proximity to a quantum point contact (QPC) charge detector near the conductance regime of the 0.7 anomaly. The electrostatic coupling between the QD and QPC introduces a remote gate on the QD level, which varies with the QPC gate voltage. Furthermore, models for the 0.7 anomaly [Y. Meir et al., PRL 89,196802(2002)] suggest that the QPC lodges a Kondo-screened level with charge-correlated hybridization, which may be also affected by capacitive coupling to the QD, giving rise to a competition between the two Kondo ground states. We model the QD-QPC system as two capacitively-coupled Kondo impurities, and explore the zero-bias transport of both the QD and the QPC for different local gate voltages and coupling strengths, using the numerical renormalization group and variational methods. We find that the capacitive coupling produces a remote gating effect, non-monotonic in the gate voltages, which reduces the gate voltage window for Kondo screening in either impurity, and which can also drive a quantum phase transition out of the Kondo regime. Our study is carried out for intermediate coupling strengths, and as such is highly relevant to experiments; particularly, to recent studies of decoherence effects on QDs. Supported by MWN/CIAM and NSF PIRE.

Charge movement in gating-locked HCN channels reveals weak coupling of voltage sensors and gate.

PubMed

Ryu, Sujung; Yellen, Gary

2012-11-01

HCN (hyperpolarization-activated cyclic nucleotide gated) pacemaker channels have an architecture similar to that of voltage-gated K(+) channels, but they open with the opposite voltage dependence. HCN channels use essentially the same positively charged voltage sensors and intracellular activation gates as K(+) channels, but apparently these two components are coupled differently. In this study, we examine the energetics of coupling between the voltage sensor and the pore by using cysteine mutant channels for which low concentrations of Cd(2+) ions freeze the open-closed gating machinery but still allow the sensors to move. We were able to lock mutant channels either into open or into closed states by the application of Cd(2+) and measure the effect on voltage sensor movement. Cd(2+) did not immobilize the gating charge, as expected for strict coupling, but rather it produced shifts in the voltage dependence of voltage sensor charge movement, consistent with its effect of confining transitions to either closed or open states. From the magnitude of the Cd(2+)-induced shifts, we estimate that each voltage sensor produces a roughly three- to sevenfold effect on the open-closed equilibrium, corresponding to a coupling energy of ∼1.3-2 kT per sensor. Such coupling is not only opposite in sign to the coupling in K(+) channels, but also much weaker.

Enhancement of superexchange pairing in the periodically driven Hubbard model

NASA Astrophysics Data System (ADS)

Coulthard, J. R.; Clark, S. R.; Al-Assam, S.; Cavalleri, A.; Jaksch, D.

2017-08-01

Recent experiments performed on cuprates and alkali-doped fullerides have demonstrated that key signatures of superconductivity can be induced above the equilibrium critical temperature by optical modulation. These observations in disparate physical systems may indicate a general underlying mechanism. Multiple theories have been proposed, but these either consider specific features, such as competing instabilities, or focus on conventional BCS-type superconductivity. Here we show that periodic driving can enhance electron pairing in strongly correlated systems. Focusing on the strongly repulsive limit of the doped Hubbard model, we investigate in-gap, spatially inhomogeneous, on-site modulations. We demonstrate that such modulations substantially reduce electronic hopping, while simultaneously sustaining superexchange interactions and pair hopping via driving-induced virtual charge excitations. We calculate real-time dynamics for the one-dimensional case, starting from zero- and finite-temperature initial states, and we show that enhanced singlet-pair correlations emerge quickly and robustly in the out-of-equilibrium many-body state. Our results reveal a fundamental pairing mechanism that might underpin optically induced superconductivity in some strongly correlated quantum materials.

Control of gel swelling and phase separation of weakly charged thermoreversible gels by salt addition

PubMed Central

Solis, Francisco J.; Vernon, Brent

2009-01-01

Doping of thermoreversible polymer gels with charged monomers provides a way to control phase separation and gelation conditions by coupling the properties of the gel with a tunable ionic environment. We analyze the dependence of the gelation and phase separation conditions on the amount of salt present using a mean field model of weakly charged associative polymers. The ions and co-ions present are explicitly considered at the mean field level, and we determine their concentrations in the different equilibrium phases when the system undergoes phase separation. For weak polymer charge, the entropic contributions of the ions to the free energy of the system play a central role in the determination of the location of phase equilibrium. In the simplest case, when the associative interaction responsible for gel formation is independent of the electrostatic interaction, the addition of salt changes the polymer equilibrium concentrations and indirectly changes the measurable swelling of the gel. We construct phase diagrams of these systems showing the location of the coexistence region, the gel-sol boundary and the location of the tie-lines. We determine the swelling of the gel within the co-existence region. Our main result is that the description of the effect of the salt on the properties of the weakly charged gel can be described through an extra contribution to the effective immiscibility parameter χ proportional to the square of the doping degree f2 and to the inverse square of the added salt concentration s−2. PMID:19759854

Salt Effects on Surface Structures of Polyelectrolyte Multilayers (PEMs) Investigated by Vibrational Sum Frequency Generation (SFG) Spectroscopy.

PubMed

Ge, Aimin; Matsusaki, Michiya; Qiao, Lin; Akashi, Mitsuru; Ye, Shen

2016-04-26

Sum frequency generation (SFG) vibrational spectroscopy was employed to investigate the surface structures of polyelectrolyte multilayers (PEMs) constructed by sequentially alternating adsorption of poly(diallyldimethylammonium chloride) (PDDA) and poly(styrenesulfonate) (PSS). It was found that the surface structures and surface charge density of the as-deposited PEMs of PDDA/PSS significantly depend on the concentration of sodium chloride (NaCl) present in the polyelectrolyte solutions. Furthermore, it was found that the surface structure of the as-deposited PEMs is in a metastable state and will reach the equilibrium state by diffusion of the polyelectrolyte chain after an aging process, resulting in a polyelectrolyte mixture on the PEM surfaces.

Electronic and transport properties of a molecular junction with asymmetric contacts.

PubMed

Tsai, M-H; Lu, T-H

2010-02-10

Asymmetric molecular junctions have been shown experimentally to exhibit a dual-conductance transport property with a pulse-like current-voltage characteristic, by Reed and co-workers. Using a recently developed first-principles integrated piecewise thermal equilibrium current calculation method and a gold-benzene-1-olate-4-thiolate-gold model molecular junction, this unusual transport property has been reproduced. Analysis of the electrostatics and the electronic structure reveals that the high-current state results from subtle bias induced charge transfer at the electrode-molecule contacts that raises molecular orbital energies and enhances the current-contributing molecular density of states and the probabilities of resonance tunneling of conduction electrons from one electrode to another.

On the nature of liquid junction and membrane potentials.

PubMed

Perram, John W; Stiles, Peter J

2006-09-28

Whenever a spatially inhomogeneous electrolyte, composed of ions with different mobilities, is allowed to diffuse, charge separation and an electric potential difference is created. Such potential differences across very thin membranes (e.g. biomembranes) are often interpreted using the steady state Goldman equation, which is usually derived by assuming a spatially constant electric field. Through the fundamental Poisson equation of electrostatics, this implies the absence of free charge density that must provide the source of any such field. A similarly paradoxical situation is encountered for thick membranes (e.g. in ion-selective electrodes) for which the diffusion potential is normally interpreted using the Henderson equation. Standard derivations of the Henderson equation appeal to local electroneutrality, which is also incompatible with sources of electric fields, as these require separated charges. We analyse self-consistent solutions of the Nernst-Planck-Poisson equations for a 1 : 1-univalent electrolyte to show that the Goldman and Henderson steady-state membrane potentials are artefacts of extraneous charges created in the reservoirs of electrolyte solution on either side of the membrane, due to the unphysical nature of the usual (Dirichlet) boundary conditions assumed to apply at the membrane-electrolyte interfaces. We also show, with the aid of numerical simulations, that a transient electric potential difference develops in any confined, but initially non-uniform, electrolyte solution. This potential difference ultimately decays to zero in the real steady state of the electrolyte, which corresponds to thermodynamic equilibrium. We explain the surprising fact that such transient potential differences are well described by the Henderson equation by using a computer algebra system to extend previous steady-state singular perturbation theories to the time-dependent case. Our work therefore accounts for the success of the Henderson equation in analysing experimental liquid-junction potentials.

Elucidating the Ultrafast Dynamics of Photoinduced Charge Separation in Metalloporphyrin-Fullerene Dyads Across the Electromagnetic Spectrum

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

Zhang, J.; Pápai, M.; Hirsch, A.

Metalloporphyrins are prominent building blocks in the synthetic toolbox of advanced photodriven molecular devices. When the central ion is paramagnetic, the relaxation pathways within the manifold of excited states are highly intricate so that unravelling the intramolecular energy and electron transfer processes is usually a very complex task. This fact is critically hampering the development of applications based on the enhanced coupling offered by the electronic exchange interaction. In this work, the dynamics of charge separation in a copper porphyrin-fullerene are studied with several complementary spectroscopic tools across the electromagnetic spectrum (from near infra-red to X-ray wavelengths), each of themmore » providing specific diagnostics. Correlating the various rates clearly demonstrates that the lifetime of the photoinduced charge-separated state exceeds by about 10 fold that of the isolated photoexcited CuII porphyrin. As revealed by the spectral modifications in the XANES region, this stabilization is accompanied by a transient change in covalency around the CuII center, which is induced by an enhanced interaction with the C60 moiety. This experimental finding is further confirmed by state-of-the art calculations using DFT and TD-DFT including dispersion effects that explain the electrostatic and structural origins of this interaction, as the CuIIP cation becomes ruffled and approaches closer to the fullerene in the charge-separated state. From a methodological point of view, these results exemplify the potential of multielectron excitation features in transient X-ray spectra as future diagnostics of sub-femtosecond electronic dynamics. From a practical point of view, this work is paving the way for elucidating out-of-equilibrium electron transfer events coupled to magnetic interaction processes on their intrinsic time-scales.« less

Relativity, nonextensivity, and extended power law distributions.

PubMed

Silva, R; Lima, J A S

2005-11-01

A proof of the relativistic theorem by including nonextensive effects is given. As it happens in the nonrelativistic limit, the molecular chaos hypothesis advanced by Boltzmann does not remain valid, and the second law of thermodynamics combined with a duality transformation implies that the parameter lies on the interval [0,2]. It is also proven that the collisional equilibrium states (null entropy source term) are described by the relativistic power law extension of the exponential Juttner distribution which reduces, in the nonrelativistic domain, to the Tsallis power law function. As a simple illustration of the basic approach, we derive the relativistic nonextensive equilibrium distribution for a dilute charged gas under the action of an electromagnetic field . Such results reduce to the standard ones in the extensive limit, thereby showing that the nonextensive entropic framework can be harmonized with the space-time ideas contained in the special relativity theory.

Self-amplified photo-induced gap quenching in a correlated electron material

PubMed Central

Mathias, S.; Eich, S.; Urbancic, J.; Michael, S.; Carr, A. V.; Emmerich, S.; Stange, A.; Popmintchev, T.; Rohwer, T.; Wiesenmayer, M.; Ruffing, A.; Jakobs, S.; Hellmann, S.; Matyba, P.; Chen, C.; Kipp, L.; Bauer, M.; Kapteyn, H. C.; Schneider, H. C.; Rossnagel, K.; Murnane, M. M.; Aeschlimann, M.

2016-01-01

Capturing the dynamic electronic band structure of a correlated material presents a powerful capability for uncovering the complex couplings between the electronic and structural degrees of freedom. When combined with ultrafast laser excitation, new phases of matter can result, since far-from-equilibrium excited states are instantaneously populated. Here, we elucidate a general relation between ultrafast non-equilibrium electron dynamics and the size of the characteristic energy gap in a correlated electron material. We show that carrier multiplication via impact ionization can be one of the most important processes in a gapped material, and that the speed of carrier multiplication critically depends on the size of the energy gap. In the case of the charge-density wave material 1T-TiSe2, our data indicate that carrier multiplication and gap dynamics mutually amplify each other, which explains—on a microscopic level—the extremely fast response of this material to ultrafast optical excitation. PMID:27698341

Photo-generated carriers lose energy during extraction from polymer-fullerene solar cells

PubMed Central

Melianas, Armantas; Etzold, Fabian; Savenije, Tom J.; Laquai, Frédéric; Inganäs, Olle; Kemerink, Martijn

2015-01-01

In photovoltaic devices, the photo-generated charge carriers are typically assumed to be in thermal equilibrium with the lattice. In conventional materials, this assumption is experimentally justified as carrier thermalization completes before any significant carrier transport has occurred. Here, we demonstrate by unifying time-resolved optical and electrical experiments and Monte Carlo simulations over an exceptionally wide dynamic range that in the case of organic photovoltaic devices, this assumption is invalid. As the photo-generated carriers are transported to the electrodes, a substantial amount of their energy is lost by continuous thermalization in the disorder broadened density of states. Since thermalization occurs downward in energy, carrier motion is boosted by this process, leading to a time-dependent carrier mobility as confirmed by direct experiments. We identify the time and distance scales relevant for carrier extraction and show that the photo-generated carriers are extracted from the operating device before reaching thermal equilibrium. PMID:26537357

Simple Derivation of the Maxwell Stress Tensor and Electrostrictive Effects in Crystals

ERIC Educational Resources Information Center

Juretschke, H. J.

1977-01-01

Shows that local equilibrium and energy considerations in an elastic dielectric crystal lead to a simple derivation of the Maxwell stress tensor in anisotropic dielectric solids. The resulting equilibrium stress-strain relations are applied to determine the deformations of a charged parallel plate capacitor. (MLH)

Measurements of Charging of Apollo 17 Lunar Dust Grains by Electron Impact

NASA Technical Reports Server (NTRS)

Abbas, Mian M.; Tankosic, Dragana; Spann, James F.; Dube, Michael J.

2008-01-01

It is well known since the Apollo missions that the lunar surface is covered with a thick layer of micron size dust grains with unusually high adhesive characteristics. The dust grains observed to be levitated and transported on the lunar surface are believed to have a hazardous impact on the robotic and human missions to the Moon. The observed dust phenomena are attributed to the lunar dust being charged positively during the day by UV photoelectric emissions, and negatively during the night by the solar wind electrons. The current dust charging and the levitation models, however, do not fully explain the observed phenomena, with the uncertainty of dust charging processes and the equilibrium potentials of the individual dust grains. It is well recognized that the charging properties of individual dust grains are substantially different from those determined from measurements made on bulk materials that are currently available. An experimental facility has been developed in the Dusty Plasma Laboratory at MSFC for investigating the charging and optical properties of individual micron/sub-micron size positively or negatively charged dust grains by levitating them in an electrodynamic balance in simulated space environments. In this paper, we present the laboratory measurements on charging of Apollo 17 individual lunar dust grains by a low energy electron beam. The charging rates and the equilibrium potentials produced by direct electron impact and by secondary electron emission process are discussed.

Phase-field approach to implicit solvation of biomolecules with Coulomb-field approximation

NASA Astrophysics Data System (ADS)

Zhao, Yanxiang; Kwan, Yuen-Yick; Che, Jianwei; Li, Bo; McCammon, J. Andrew

2013-07-01

A phase-field variational implicit-solvent approach is developed for the solvation of charged molecules. The starting point of such an approach is the representation of a solute-solvent interface by a phase field that takes one value in the solute region and another in the solvent region, with a smooth transition from one to the other on a small transition layer. The minimization of an effective free-energy functional of all possible phase fields determines the equilibrium conformations and free energies of an underlying molecular system. All the surface energy, the solute-solvent van der Waals interaction, and the electrostatic interaction are coupled together self-consistently through a phase field. The surface energy results from the minimization of a double-well potential and the gradient of a field. The electrostatic interaction is described by the Coulomb-field approximation. Accurate and efficient methods are designed and implemented to numerically relax an underlying charged molecular system. Applications to single ions, a two-plate system, and a two-domain protein reveal that the new theory and methods can capture capillary evaporation in hydrophobic confinement and corresponding multiple equilibrium states as found in molecular dynamics simulations. Comparisons of the phase-field and the original sharp-interface variational approaches are discussed.

Transport coefficients of a hot QCD medium and their relative significance in heavy-ion collisions

NASA Astrophysics Data System (ADS)

Mitra, Sukanya; Chandra, Vinod

2017-11-01

The main focus of this article is to obtain various transport coefficients for a hot QCD medium that is likely to be produced while colliding two heavy nuclei ultra-relativistically. The technical approach adopted here is the semiclassical transport theory. The away-from-equilibrium linearized transport equation has been set up by employing the Chapman-Enskog technique from the kinetic theory of a many-particle system with a collision term that includes the binary collisions of quarks/antiquarks and gluons. In order to include the effects of a strongly interacting, thermal medium, a quasi-particle description of a realistic hot QCD equation of state has been employed through the equilibrium modeling of the momentum distributions of gluons and quarks with nontrivial dispersion relations while extending the model for finite but small quark chemical potential. The effective coupling for strong interaction has been redefined following the charge renormalization under the scheme of the quasi-particle model. The consolidated effects on transport coefficients are seen to have a significant impact on their temperature dependence. Finally, the relative significances of momentum and heat transfer, as well as the charge diffusion processes in hot QCD, have been investigated by studying the ratios of the respective transport coefficients indicating different physical laws.

Black branes as piezoelectrics.

PubMed

Armas, Jay; Gath, Jakob; Obers, Niels A

2012-12-14

We find a realization of linear electroelasticity theory in gravitational physics by uncovering a new response coefficient of charged black branes, exhibiting their piezoelectric behavior. Taking charged dilatonic black strings as an example and using the blackfold approach we measure their elastic and piezolectric moduli. We also use our results to draw predictions about the equilibrium condition of charged dilatonic black rings in dimensions higher than six.

A probable probability distribution of a series nonequilibrium states in a simple system out of equilibrium

NASA Astrophysics Data System (ADS)

Gao, Haixia; Li, Ting; Xiao, Changming

2016-05-01

When a simple system is in its nonequilibrium state, it will shift to its equilibrium state. Obviously, in this process, there are a series of nonequilibrium states. With the assistance of Bayesian statistics and hyperensemble, a probable probability distribution of these nonequilibrium states can be determined by maximizing the hyperensemble entropy. It is known that the largest probability is the equilibrium state, and the far a nonequilibrium state is away from the equilibrium one, the smaller the probability will be, and the same conclusion can also be obtained in the multi-state space. Furthermore, if the probability stands for the relative time the corresponding nonequilibrium state can stay, then the velocity of a nonequilibrium state returning back to its equilibrium can also be determined through the reciprocal of the derivative of this probability. It tells us that the far away the state from the equilibrium is, the faster the returning velocity will be; if the system is near to its equilibrium state, the velocity will tend to be smaller and smaller, and finally tends to 0 when it gets the equilibrium state.

A general intermolecular force field based on tight-binding quantum chemical calculations

NASA Astrophysics Data System (ADS)

Grimme, Stefan; Bannwarth, Christoph; Caldeweyher, Eike; Pisarek, Jana; Hansen, Andreas

2017-10-01

A black-box type procedure is presented for the generation of a molecule-specific, intermolecular potential energy function. The method uses quantum chemical (QC) information from our recently published extended tight-binding semi-empirical scheme (GFN-xTB) and can treat non-covalently bound complexes and aggregates with almost arbitrary chemical structure. The necessary QC information consists of the equilibrium structure, Mulliken atomic charges, charge centers of localized molecular orbitals, and also of frontier orbitals and orbital energies. The molecular pair potential includes model density dependent Pauli repulsion, penetration, as well as point charge electrostatics, the newly developed D4 dispersion energy model, Drude oscillators for polarization, and a charge-transfer term. Only one element-specific and about 20 global empirical parameters are needed to cover systems with nuclear charges up to radon (Z = 86). The method is tested for standard small molecule interaction energy benchmark sets where it provides accurate intermolecular energies and equilibrium distances. Examples for structures with a few hundred atoms including charged systems demonstrate the versatility of the approach. The method is implemented in a stand-alone computer code which enables rigid-body, global minimum energy searches for molecular aggregation or alignment.

Analysis of Static Spacecraft Floating Potential at Low Earth Orbit (LEO)

NASA Technical Reports Server (NTRS)

Herr, Joel L.; Hwang, K. S.; Wu, S. T.

1995-01-01

Spacecraft floating potential is the charge on the external surfaces of orbiting spacecraft relative to the space. Charging is caused by unequal negative and positive currents to spacecraft surfaces. The charging process continues until the accelerated particles can be collected rapidly enough to balance the currents at which point the spacecraft has reached its equilibrium or floating potential. In low inclination. Low Earth Orbit (LEO), the collection of positive ion and negative electrons. in a particular direction. are typically not equal. The level of charging required for equilibrium to be established is influenced by the characteristics of the ambient plasma environment. by the spacecraft motion, and by the geometry of the spacecraft. Using the kinetic theory, a statistical approach for studying the interaction is developed. The approach used to study the spacecraft floating potential depends on which phenomena are being applied. and on the properties of the plasma. especially the density and temperature. The results from kinetic theory derivation are applied to determine the charging level and the electric potential distribution at an infinite flat plate perpendicular to a streaming plasma using finite-difference scheme.

Optical conductivity of cuprates in the pseudogap state: Yang-Rice-Zhang model and antiferromagnetic spin waves

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

Singh, Navinder; Sharma, Raman

In the underdoped regime of the cuprate phase diagram, the modified version of the Resonance Valence Bond (RVB) model by Yang, Rice and Zhang (YRZ) captures the strong electronic correlation effects very well as corroborated by the ARPES and many other experiments. However, under a non-equilibrium transport setting, YRZ says nothing about the scattering mechanisms of the charge carriers. In the present investigation we include, in a very simplified way, the scattering of charge carriers due to antiferromagnetic type spin waves (ASW). The effect of ASW excitations on conductivity has been studied by changing combined life times of the includedmore » process. It has been found that there is a qualitative change in the conductivity in the right direction. The theoretical conductivity reproduces qualitatively the experimental one.« less

Modeling quantum cascade lasers: Coupled electron and phonon transport far from equilibrium and across disparate spatial scales

DOE PAGES

Shi, Y. B.; Mei, S.; Jonasson, O.; ...

2016-12-28

Quantum cascade lasers (QCLs) are high-power coherent light sources in the midinfrared and terahertz parts of the electromagnetic spectrum. They are devices in which the electronic and lattice systems are far from equilibrium, strongly coupled to one another, and the problem bridges disparate spatial scales. Here, we present our ongoing work on the multiphysics and multiscale simulation of far-from-equilibrium transport of charge and heat in midinfrared QCLs.

Spin Polarization Transfer from a Photogenerated Radical Ion Pair to a Stable Radical Controlled by Charge Recombination.

PubMed

Horwitz, Noah E; Phelan, Brian T; Nelson, Jordan N; Mauck, Catherine M; Krzyaniak, Matthew D; Wasielewski, Michael R

2017-06-15

Photoexcitation of electron donor-acceptor molecules frequently produces radical ion pairs with well-defined initial spin-polarized states that have attracted significant interest for spintronics. Transfer of this initial spin polarization to a stable radical is predicted to depend on the rates of the radical ion pair recombination reactions, but this prediction has not been tested experimentally. In this study, a stable radical/electron donor/chromophore/electron acceptor molecule, BDPA • -mPD-ANI-NDI, where BDPA • is α,γ-bisdiphenylene-β-phenylallyl, mPD is m-phenylenediamine, ANI is 4-aminonaphthalene-1,8-dicarboximide, and NDI is naphthalene-1,4:5,8-bis(dicarboximide), was synthesized. Photoexcitation of ANI produces the triradical BDPA • -mPD +• -ANI-NDI -• in which the mPD +• -ANI-NDI -• radical ion pair is spin coupled to the BDPA • stable radical. BDPA • -mPD +• -ANI-NDI -• and its counterpart lacking the stable radical are found to exhibit spin-selective charge recombination in which the triplet radical ion pair 3 (mPD +• -ANI-NDI -• ) is in equilibrium with the 3 *NDI charge recombination product. Time-resolved EPR measurements show that this process is associated with an inversion of the sign of the polarization transferred to BDPA • over time. The polarization transfer rates are found to be strongly solvent dependent, as shifts in this equilibrium affect the spin dynamics. These results demonstrate that even small changes in electron transfer dynamics can have a large effect on the spin dynamics of photogenerated multispin systems.

Variational multiscale models for charge transport.

PubMed

Wei, Guo-Wei; Zheng, Qiong; Chen, Zhan; Xia, Kelin

2012-01-01

This work presents a few variational multiscale models for charge transport in complex physical, chemical and biological systems and engineering devices, such as fuel cells, solar cells, battery cells, nanofluidics, transistors and ion channels. An essential ingredient of the present models, introduced in an earlier paper (Bulletin of Mathematical Biology, 72, 1562-1622, 2010), is the use of differential geometry theory of surfaces as a natural means to geometrically separate the macroscopic domain from the microscopic domain, meanwhile, dynamically couple discrete and continuum descriptions. Our main strategy is to construct the total energy functional of a charge transport system to encompass the polar and nonpolar free energies of solvation, and chemical potential related energy. By using the Euler-Lagrange variation, coupled Laplace-Beltrami and Poisson-Nernst-Planck (LB-PNP) equations are derived. The solution of the LB-PNP equations leads to the minimization of the total free energy, and explicit profiles of electrostatic potential and densities of charge species. To further reduce the computational complexity, the Boltzmann distribution obtained from the Poisson-Boltzmann (PB) equation is utilized to represent the densities of certain charge species so as to avoid the computationally expensive solution of some Nernst-Planck (NP) equations. Consequently, the coupled Laplace-Beltrami and Poisson-Boltzmann-Nernst-Planck (LB-PBNP) equations are proposed for charge transport in heterogeneous systems. A major emphasis of the present formulation is the consistency between equilibrium LB-PB theory and non-equilibrium LB-PNP theory at equilibrium. Another major emphasis is the capability of the reduced LB-PBNP model to fully recover the prediction of the LB-PNP model at non-equilibrium settings. To account for the fluid impact on the charge transport, we derive coupled Laplace-Beltrami, Poisson-Nernst-Planck and Navier-Stokes equations from the variational principle for chemo-electro-fluid systems. A number of computational algorithms is developed to implement the proposed new variational multiscale models in an efficient manner. A set of ten protein molecules and a realistic ion channel, Gramicidin A, are employed to confirm the consistency and verify the capability. Extensive numerical experiment is designed to validate the proposed variational multiscale models. A good quantitative agreement between our model prediction and the experimental measurement of current-voltage curves is observed for the Gramicidin A channel transport. This paper also provides a brief review of the field.

Variational multiscale models for charge transport

PubMed Central

Wei, Guo-Wei; Zheng, Qiong; Chen, Zhan; Xia, Kelin

2012-01-01

This work presents a few variational multiscale models for charge transport in complex physical, chemical and biological systems and engineering devices, such as fuel cells, solar cells, battery cells, nanofluidics, transistors and ion channels. An essential ingredient of the present models, introduced in an earlier paper (Bulletin of Mathematical Biology, 72, 1562-1622, 2010), is the use of differential geometry theory of surfaces as a natural means to geometrically separate the macroscopic domain from the microscopic domain, meanwhile, dynamically couple discrete and continuum descriptions. Our main strategy is to construct the total energy functional of a charge transport system to encompass the polar and nonpolar free energies of solvation, and chemical potential related energy. By using the Euler-Lagrange variation, coupled Laplace-Beltrami and Poisson-Nernst-Planck (LB-PNP) equations are derived. The solution of the LB-PNP equations leads to the minimization of the total free energy, and explicit profiles of electrostatic potential and densities of charge species. To further reduce the computational complexity, the Boltzmann distribution obtained from the Poisson-Boltzmann (PB) equation is utilized to represent the densities of certain charge species so as to avoid the computationally expensive solution of some Nernst-Planck (NP) equations. Consequently, the coupled Laplace-Beltrami and Poisson-Boltzmann-Nernst-Planck (LB-PBNP) equations are proposed for charge transport in heterogeneous systems. A major emphasis of the present formulation is the consistency between equilibrium LB-PB theory and non-equilibrium LB-PNP theory at equilibrium. Another major emphasis is the capability of the reduced LB-PBNP model to fully recover the prediction of the LB-PNP model at non-equilibrium settings. To account for the fluid impact on the charge transport, we derive coupled Laplace-Beltrami, Poisson-Nernst-Planck and Navier-Stokes equations from the variational principle for chemo-electro-fluid systems. A number of computational algorithms is developed to implement the proposed new variational multiscale models in an efficient manner. A set of ten protein molecules and a realistic ion channel, Gramicidin A, are employed to confirm the consistency and verify the capability. Extensive numerical experiment is designed to validate the proposed variational multiscale models. A good quantitative agreement between our model prediction and the experimental measurement of current-voltage curves is observed for the Gramicidin A channel transport. This paper also provides a brief review of the field. PMID:23172978

Some comments on thermodynamic consistency for equilibrium mixture equations of state

DOE PAGES

Grove, John W.

2018-03-28

We investigate sufficient conditions for thermodynamic consistency for equilibrium mixtures. Such models assume that the mass fraction average of the material component equations of state, when closed by a suitable equilibrium condition, provide a composite equation of state for the mixture. Here, we show that the two common equilibrium models of component pressure/temperature equilibrium and volume/temperature equilibrium (Dalton, 1808) define thermodynamically consistent mixture equations of state and that other equilibrium conditions can be thermodynamically consistent provided appropriate values are used for the mixture specific entropy and pressure.

Systematic Approach to Calculate the Concentration of Chemical Species in Multi-Equilibrium Problems

ERIC Educational Resources Information Center

Baeza-Baeza, Juan Jose; Garcia-Alvarez-Coque, Maria Celia

2011-01-01

A general systematic approach is proposed for the numerical calculation of multi-equilibrium problems. The approach involves several steps: (i) the establishment of balances involving the chemical species in solution (e.g., mass balances, charge balance, and stoichiometric balance for the reaction products), (ii) the selection of the unknowns (the…

Out-of-equilibrium chiral magnetic effect from chiral kinetic theory

NASA Astrophysics Data System (ADS)

Huang, Anping; Jiang, Yin; Shi, Shuzhe; Liao, Jinfeng; Zhuang, Pengfei

2018-02-01

Recently there has been significant interest in the macroscopic manifestation of chiral anomaly in many-body systems of chiral fermions. A notable example is the Chiral Magnetic Effect (CME). Enthusiastic efforts have been made to search for the CME in the quark-gluon plasma created in heavy ion collisions. A crucial challenge is that the extremely strong magnetic field in such collisions may last only for a brief moment and the CME current may have to occur at so early a stage that the quark-gluon matter is still far from thermal equilibrium. This thus requires modeling of the CME in an out-of-equilibrium setting. With the recently developed theoretical tool of chiral kinetic theory, we make a first phenomenological study of the CME-induced charge separation during the pre-thermal stage in heavy ion collisions. The effect is found to be very sensitive to the time dependence of the magnetic field and also influenced by the initial quark momentum spectrum as well as the relaxation time of the system evolution toward thermal equilibrium. Within the present approach, such pre-thermal charge separation is found to be modest.

Non-equilibrium modeling of UV laser induced plasma on a copper target in the presence of Cu{sup 2+}

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

Ait Oumeziane, Amina, E-mail: a.aitoumeziane@gmail.com; Liani, Bachir; Parisse, Jean-Denis

2016-03-15

This work is a contribution to the understanding of UV laser ablation of a copper sample in the presence of Cu{sup 2+} species as well as electronic non-equilibrium in the laser induced plasma. This particular study extends a previous paper and develops a 1D hydrodynamic model to describe the behavior of the laser induced plume, including the thermal non-equilibrium between electrons and heavy particles. Incorporating the formation of doubly charged ions (Cu{sup 2+}) in such an approach has not been considered previously. We evaluate the effect of the presence of doubly ionized species on the characteristics of the plume, i.e.,more » temperature, pressure, and expansion velocity, and on the material itself by evaluating the ablation depth and plasma shielding effects. This study evaluates the effects of the doubly charged species using a non-equilibrium hydrodynamic approach which comprises a contribution to the understanding of the governing processes of the interaction of ultraviolet nanosecond laser pulses with metals and the parameter optimization depending on the intended application.« less

Gravitating Q-balls in the Affleck-Dine mechanism

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

Tamaki, Takashi; Sakai, Nobuyuki; Department of Education, Yamagata University, Yamagata 990-8560

2011-04-15

We investigate how gravity affects ''Q-balls'' with the Affleck-Dine potential V{sub AD}({phi}):=(m{sup 2}/2){phi}{sup 2} [1+Kln(({phi}/M)){sup 2}]. Contrary to the flat case, in which equilibrium solutions exist only if K<0, we find three types of gravitating solutions as follows. In the case that K<0, ordinary Q-ball solutions exist; there is an upper bound of the charge due to gravity. In the case that K=0, equilibrium solutions called (mini-)boson stars appear due to gravity; there is an upper bound of the charge, too. In the case that K>0, equilibrium solutions appear, too. In this case, these solutions are not asymptotically flat butmore » surrounded by Q-matter. These solutions might be important in considering a dark matter scenario in the Affleck-Dine mechanism.« less

Coassembly of Lysozyme and Amphiphilic Biomolecules Driven by Unimer-Aggregate Equilibrium.

PubMed

Tao, Yuanyuan; Ma, Xiaoteng; Cai, Yaqian; Liu, Li; Zhao, Hanying

2018-04-12

Synthesis and self-assembly of bioconjugates composed of proteins and synthetic molecules have been widely studied because of the potential applications in medicine, biotechnology, and nanotechnology. One of the challenging research studies in this area is to develop organic solvent-free approaches to the synthesis and self-assembly of amphiphilic bioconjugates. In this research, dialysis-assisted approach, a method based on unimer-aggregate equilibrium, was applied in the coassembly of lysozyme and conjugate of cholesterol and glutathione (Ch-GSH). In phosphate buffer solution, amphiphilic Ch-GSH conjugate self-assembles into vesicles, and the vesicle solution is dialyzed against lysozyme solution. Negatively charged Ch-GSH unimers produced in the unimer-vesicle exchange equilibrium, diffuse across the dialysis membrane and have electrostatic interaction with positively charged lysozyme, resulting in the formation of Ch-GSH-lysozyme bioconjugate. Above a critical concentration, the three-component bioconjugate molecules self-assemble into bioactive vesicles.

Electron transfer across a thermal gradient

PubMed Central

Craven, Galen T.

2016-01-01

Charge transfer is a fundamental process that underlies a multitude of phenomena in chemistry and biology. Recent advances in observing and manipulating charge and heat transport at the nanoscale, and recently developed techniques for monitoring temperature at high temporal and spatial resolution, imply the need for considering electron transfer across thermal gradients. Here, a theory is developed for the rate of electron transfer and the associated heat transport between donor–acceptor pairs located at sites of different temperatures. To this end, through application of a generalized multidimensional transition state theory, the traditional Arrhenius picture of activation energy as a single point on a free energy surface is replaced with a bithermal property that is derived from statistical weighting over all configurations where the reactant and product states are equienergetic. The flow of energy associated with the electron transfer process is also examined, leading to relations between the rate of heat exchange among the donor and acceptor sites as functions of the temperature difference and the electronic driving bias. In particular, we find that an open electron transfer channel contributes to enhanced heat transport between sites even when they are in electronic equilibrium. The presented results provide a unified theory for charge transport and the associated heat conduction between sites at different temperatures. PMID:27450086

Observations of the mean ionization states of energetic particles in the vicinity of the earth's magnetosphere

NASA Technical Reports Server (NTRS)

Ma Sung, L. S.; Gloeckler, G.; Fan, C. Y.; Hovestadt, D.

1980-01-01

The mean ionization states of 44-260 keV per charge ions observed as bursts in and near the earth's magnetosphere have been determined by using the particle data collected by the University of Maryland experiment on Imp 8. We find that during the period from October 1973 to December 1976 (1) the abundance ratio of heavy ions (Z greater than 2) to alphas ranges from 0.04 to 0.10, with a mean value of 0.08 plus or minus 0.02; (2) the energy spectra of alphas and Z greater than 2 ions in these bursts are adequately represented as exponentials in energy per charge with e-folding energies of 30-50 keV/Q; (3) the e-folding energies of both alpha particles and heavier ions are generally harder upstream from the bow shock than in the magnetotail and magnetosheath; and (4) the elemental abundances and ionization state distribution of the heavy ions are consistent with those of the corona at an equilibrium coronal temperature of 1-2 x 10 to the 6th K, which tends to support a solar wind origin for these particles.

Contact electrification of insulating materials

NASA Astrophysics Data System (ADS)

Lacks, Daniel J.; Mohan Sankaran, R.

2011-11-01

The electrostatic charge that is generated when two materials are contacted or rubbed and then separated is a well-known physical process that has been studied for more than 2500 years. Contact electrification occurs in many contexts, both natural and technological. For example, in dust storms the collisions between particles lead to electrostatic charging and in extreme cases, extraordinary lightning displays. In electrophotography, toner particles are intentionally charged to guide their deposition in well-defined patterns. Despite such a long history and so many important consequences, a fundamental understanding of the mechanism behind contact electrification remains elusive. An open question is what type of species are transferred between the surfaces to generate charge—experiments suggest various species ranging from electrons to ions to nanoscopic bits of material, and theoretical work suggests that non-equilibrium states may play an important role. Another open question is the contact electrification that occurs when two insulating materials with identical physical properties touch—since there is no apparent driving force, it is not clear why charge transfer occurs. A third open question involves granular systems—models and experiments have shown that a particle-size dependence for the charging often exists. In this review, we discuss the fundamental aspects of contact electrification and highlight recent research efforts aimed at understanding these open questions.

Calculation of the acid-base equilibrium constants at the alumina/electrolyte interface from the ph dependence of the adsorption of singly charged ions (Na+, Cl-)

NASA Astrophysics Data System (ADS)

Gololobova, E. G.; Gorichev, I. G.; Lainer, Yu. A.; Skvortsova, I. V.

2011-05-01

A procedure was proposed for the calculation of the acid-base equilibrium constants at an alumina/electrolyte interface from experimental data on the adsorption of singly charged ions (Na+, Cl-) at various pH values. The calculated constants (p K {1/0}= 4.1, p K {2/0}= 11.9, p K {3/0}= 8.3, and p K {4/0}= 7.7) are shown to agree with the values obtained from an experimental pH dependence of the electrokinetic potential and the results of potentiometric titration of Al2O3 suspensions.

Attitude stabilization of a spacecraft equipped with large electrostatic protection screens

NASA Astrophysics Data System (ADS)

Nikitin, D. Yu.; Tikhonov, A. A.

2018-05-01

A satellite with a system of three electrostatic radiation protection (ERP) screens is under consideration. The screens are constructed as electrostatically charged toroidal shields with characteristic size of order equal to 100 m. The interaction of electric charge with the Earth's magnetic field (EMF) give rise to the Lorentz torque acting upon a satellite attitude motion. As the sizes of ERP system are large, we derive the Lorentz torque taking into account the complex form of ERP screens and gradient of the EMF in the screen volume. It is assumed that the satellite center of charge coincides with the satellite mass center. The EMF is modeled by the straight magnetic dipole. In the paper we investigate the usage of Lorentz torque for passive attitude stabilization for satellite in a circular equatorial orbit. Mathematical model for attitude dynamics of a satellite equipped with ERP interacting with the EMF is derived and first integral of corresponding differential equations is constructed. The straight equilibrium position of the satellite in the orbital frame is found. Sufficient conditions for stability of satellite equilibrium position are constructed with the use of the first integral. The gravity gradient torque is taken into account. The satellite equilibrium stability domain is constructed.

Structure and stabilizing interactions of casein micelles probed by high-pressure light scattering and FTIR.

PubMed

Gebhardt, Ronald; Takeda, Naohiro; Kulozik, Ulrich; Doster, Wolfgang

2011-03-17

Caseins form heterogeneous micelles composed of three types of disordered protein chains (α, β, κ), which include protein-bound calcium phosphate particles. We probe the stability limits of the micelle by applying hydrostatic pressure. The resulting changes of the size distribution and the average molecular weight are recorded in situ with static and dynamic light scattering. Pressure induces irreversible dissociation of the micelles into monomers above a critical value depending on their size. The critical pressure increases with temperature, pH, and calcium concentration due to the interplay of hydrophobic and electrostatic interactions. The pressure transition curves are biphasic, reflecting the equilibrium of two micelle states with different stability, average size, entropy, and calcium bound. The fast process of pressure dissociation is used to probe the slow equilibrium of the two micelle states under various conditions. Binding and release of β-casein from the micelle is suggested as the molecular mechanism of stabilization associated with the two states. In situ FTIR spectroscopy covering the P-O stretching region indicates that bound calcium phosphate particles are released from serine phosphate residues at pressures above 100 MPa. The resulting imbalance of charge triggers the complete decomposition of the micelle. © 2011 American Chemical Society

Incorporation of charge transfer into the explicit polarization fragment method by grand canonical density functional theory.

PubMed

Isegawa, Miho; Gao, Jiali; Truhlar, Donald G

2011-08-28

Molecular fragmentation algorithms provide a powerful approach to extending electronic structure methods to very large systems. Here we present a method for including charge transfer between molecular fragments in the explicit polarization (X-Pol) fragment method for calculating potential energy surfaces. In the conventional X-Pol method, the total charge of each fragment is preserved, and charge transfer between fragments is not allowed. The description of charge transfer is made possible by treating each fragment as an open system with respect to the number of electrons. To achieve this, we applied Mermin's finite temperature method to the X-Pol wave function. In the application of this method to X-Pol, the fragments are open systems that partially equilibrate their number of electrons through a quasithermodynamics electron reservoir. The number of electrons in a given fragment can take a fractional value, and the electrons of each fragment obey the Fermi-Dirac distribution. The equilibrium state for the electrons is determined by electronegativity equalization with conservation of the total number of electrons. The amount of charge transfer is controlled by re-interpreting the temperature parameter in the Fermi-Dirac distribution function as a coupling strength parameter. We determined this coupling parameter so as to reproduce the charge transfer energy obtained by block localized energy decomposition analysis. We apply the new method to ten systems, and we show that it can yield reasonable approximations to potential energy profiles, to charge transfer stabilization energies, and to the direction and amount of charge transferred. © 2011 American Institute of Physics

Incorporation of charge transfer into the explicit polarization fragment method by grand canonical density functional theory

PubMed Central

Isegawa, Miho; Gao, Jiali; Truhlar, Donald G.

2011-01-01

Molecular fragmentation algorithms provide a powerful approach to extending electronic structure methods to very large systems. Here we present a method for including charge transfer between molecular fragments in the explicit polarization (X-Pol) fragment method for calculating potential energy surfaces. In the conventional X-Pol method, the total charge of each fragment is preserved, and charge transfer between fragments is not allowed. The description of charge transfer is made possible by treating each fragment as an open system with respect to the number of electrons. To achieve this, we applied Mermin's finite temperature method to the X-Pol wave function. In the application of this method to X-Pol, the fragments are open systems that partially equilibrate their number of electrons through a quasithermodynamics electron reservoir. The number of electrons in a given fragment can take a fractional value, and the electrons of each fragment obey the Fermi–Dirac distribution. The equilibrium state for the electrons is determined by electronegativity equalization with conservation of the total number of electrons. The amount of charge transfer is controlled by re-interpreting the temperature parameter in the Fermi–Dirac distribution function as a coupling strength parameter. We determined this coupling parameter so as to reproduce the charge transfer energy obtained by block localized energy decomposition analysis. We apply the new method to ten systems, and we show that it can yield reasonable approximations to potential energy profiles, to charge transfer stabilization energies, and to the direction and amount of charge transferred. PMID:21895159

One-Dimensional Brownian Motion of Charged Nanoparticles along Microtubules: A Model System for Weak Binding Interactions

PubMed Central

Minoura, Itsushi; Katayama, Eisaku; Sekimoto, Ken; Muto, Etsuko

2010-01-01

Abstract Various proteins are known to exhibit one-dimensional Brownian motion along charged rodlike polymers, such as microtubules (MTs), actin, and DNA. The electrostatic interaction between the proteins and the rodlike polymers appears to be crucial for one-dimensional Brownian motion, although the underlying mechanism has not been fully clarified. We examined the interactions of positively-charged nanoparticles composed of polyacrylamide gels with MTs. These hydrophilic nanoparticles bound to MTs and displayed one-dimensional Brownian motion in a charge-dependent manner, which indicates that nonspecific electrostatic interaction is sufficient for one-dimensional Brownian motion. The diffusion coefficient decreased exponentially with an increasing particle charge (with the exponent being 0.10 kBT per charge), whereas the duration of the interaction increased exponentially (exponent of 0.22 kBT per charge). These results can be explained semiquantitatively if one assumes that a particle repeats a cycle of binding to and movement along an MT until it finally dissociates from the MT. During the movement, a particle is still electrostatically constrained in the potential valley surrounding the MT. This entire process can be described by a three-state model analogous to the Michaelis-Menten scheme, in which the two parameters of the equilibrium constant between binding and movement, and the rate of dissociation from the MT, are derived as a function of the particle charge density. This study highlights the possibility that the weak binding interactions between proteins and rodlike polymers, e.g., MTs, are mediated by a similar, nonspecific charge-dependent mechanism. PMID:20409479

One-dimensional Brownian motion of charged nanoparticles along microtubules: a model system for weak binding interactions.

PubMed

Minoura, Itsushi; Katayama, Eisaku; Sekimoto, Ken; Muto, Etsuko

2010-04-21

Various proteins are known to exhibit one-dimensional Brownian motion along charged rodlike polymers, such as microtubules (MTs), actin, and DNA. The electrostatic interaction between the proteins and the rodlike polymers appears to be crucial for one-dimensional Brownian motion, although the underlying mechanism has not been fully clarified. We examined the interactions of positively-charged nanoparticles composed of polyacrylamide gels with MTs. These hydrophilic nanoparticles bound to MTs and displayed one-dimensional Brownian motion in a charge-dependent manner, which indicates that nonspecific electrostatic interaction is sufficient for one-dimensional Brownian motion. The diffusion coefficient decreased exponentially with an increasing particle charge (with the exponent being 0.10 kBT per charge), whereas the duration of the interaction increased exponentially (exponent of 0.22 kBT per charge). These results can be explained semiquantitatively if one assumes that a particle repeats a cycle of binding to and movement along an MT until it finally dissociates from the MT. During the movement, a particle is still electrostatically constrained in the potential valley surrounding the MT. This entire process can be described by a three-state model analogous to the Michaelis-Menten scheme, in which the two parameters of the equilibrium constant between binding and movement, and the rate of dissociation from the MT, are derived as a function of the particle charge density. This study highlights the possibility that the weak binding interactions between proteins and rodlike polymers, e.g., MTs, are mediated by a similar, nonspecific charge-dependent mechanism. Copyright 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

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

Gasenzer, Thomas; McLerran, Larry; Pawlowski, Jan M.

The real-time dynamics of topological defects and turbulent configurations of gauge fields for electric and magnetic confinement are studied numerically within a 2+1D Abelian Higgs model. It is shown that confinement is appearing in such systems equilibrating after a strong initial quench such as the overpopulation of the infrared modes. While the final equilibrium state does not support confinement, metastable vortex defect configurations appearing in the gauge field are found to be closely related to the appearance of physically observable confined electric and magnetic charges. These phenomena are seen to be intimately related to the approach of a non-thermal fixedmore » point of the far-from-equilibrium dynamical evolution, signaled by universal scaling in the gauge-invariant correlation function of the Higgs field. Even when the parameters of the Higgs action do not support condensate formation in the vacuum, during this approach, transient Higgs condensation is observed. We discuss implications of these results for the far-from-equilibrium dynamics of Yang–Mills fields and potential mechanisms of how confinement and condensation in non-Abelian gauge fields can be understood in terms of the dynamics of Higgs models. These suggest that there is an interesting new class of dynamics of strong coherent turbulent gauge fields with condensates.« less

Kinetic modeling of non-ideal explosives with CHEETAH

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

Fried, L E; Howard, W M; Souers, P C

1998-08-06

We report an implementation of the Wood-Kirkwood kinetic detonation model based on multi-species equations of state and multiple reaction rate laws. Finite rate laws are used for the slowest chemical reactions. Other reactions are given infinite rates and are kept in constant thermodynamic equilibrium. We model a wide range of ideal and non-ideal composite energetic materials. We find that we can replicate experimental detonation velocities to within a few per cent, while obtaining good agreement with estimated reaction zone lengths. The detonation velocity as a function of charge radius is also correctly reproduced.

Unifying concept of serotonin transporter-associated currents.

PubMed

Schicker, Klaus; Uzelac, Zeljko; Gesmonde, Joan; Bulling, Simon; Stockner, Thomas; Freissmuth, Michael; Boehm, Stefan; Rudnick, Gary; Sitte, Harald H; Sandtner, Walter

2012-01-02

Serotonin (5-HT) uptake by the human serotonin transporter (hSERT) is driven by ion gradients. The stoichiometry of transported 5-HT and ions is predicted to result in electroneutral charge movement. However, hSERT mediates a current when challenged with 5-HT. This discrepancy can be accounted for by an uncoupled ion flux. Here, we investigated the mechanistic basis of the uncoupled currents and its relation to the conformational cycle of hSERT. Our observations support the conclusion that the conducting state underlying the uncoupled ion flux is in equilibrium with an inward facing state of the transporter with K+ bound. We identified conditions associated with accumulation of the transporter in inward facing conformations. Manipulations that increased the abundance of inward facing states resulted in enhanced steady-state currents. We present a comprehensive kinetic model of the transport cycle, which recapitulates salient features of the recorded currents. This study provides a framework for exploring transporter-associated currents.

Unifying Concept of Serotonin Transporter-associated Currents*

PubMed Central

Schicker, Klaus; Uzelac, Zeljko; Gesmonde, Joan; Bulling, Simon; Stockner, Thomas; Freissmuth, Michael; Boehm, Stefan; Rudnick, Gary; Sitte, Harald H.; Sandtner, Walter

2012-01-01

Serotonin (5-HT) uptake by the human serotonin transporter (hSERT) is driven by ion gradients. The stoichiometry of transported 5-HT and ions is predicted to result in electroneutral charge movement. However, hSERT mediates a current when challenged with 5-HT. This discrepancy can be accounted for by an uncoupled ion flux. Here, we investigated the mechanistic basis of the uncoupled currents and its relation to the conformational cycle of hSERT. Our observations support the conclusion that the conducting state underlying the uncoupled ion flux is in equilibrium with an inward facing state of the transporter with K+ bound. We identified conditions associated with accumulation of the transporter in inward facing conformations. Manipulations that increased the abundance of inward facing states resulted in enhanced steady-state currents. We present a comprehensive kinetic model of the transport cycle, which recapitulates salient features of the recorded currents. This study provides a framework for exploring transporter-associated currents. PMID:22072712

Molecular Basis of Substrate Recognition and Degradation by Human Presequence Protease

PubMed Central

King, John V.; Liang, Wenguang G.; Scherpelz, Kathryn P.; Schilling, Alexander B.; Meredith, Stephen C.; Tang, Wei-Jen

2014-01-01

Summary Human Presequence Protease (hPreP) is an M16 metalloprotease localized in mitochondria. There, hPreP facilitates proteostasis by utilizing a ∼13,300Å3 catalytic chamber to degrade a diverse array of potentially toxic peptides, including mitochondrial presequences and amyloid-β (Aβ), the latter of which contributes to Alzheimer's disease pathogenesis. Here we report crystal structures for hPreP alone and in complex with Aβ, which show that hPreP uses size-exclusion and charge complementation for substrate recognition. These structures also reveal hPreP-specific features that permit a diverse array of peptides, with distinct distributions of charged and hydrophobic residues, to be specifically captured, cleaved, and their amyloidogenic features destroyed. SAXS analysis demonstrates that hPreP in solution exists in dynamic equilibrium between closed and open states, with the former being preferred. Furthermore, Aβ binding induces the closed state and hPreP dimerization. Together, these data reveal the molecular basis for flexible yet specific substrate recognition and degradation by hPreP. PMID:24931469

Modeling the total dust production of Enceladus from stochastic charge equilibrium and simulations

NASA Astrophysics Data System (ADS)

Meier, Patrick; Motschmann, Uwe; Schmidt, Jürgen; Spahn, Frank; Hill, Thomas W.; Dong, Yaxue; Jones, Geraint H.; Kriegel, Hendrik

2015-12-01

Negatively and positively charged nano-sized ice grains were detected in the Enceladus plume by the Cassini Plasma Spectrometer (CAPS). However, no data for uncharged grains, and thus for the total amount of dust, are available. In this paper we estimate this population of uncharged grains based on a model of stochastic charging in thermodynamic equilibrium and on the assumption of quasi-neutrality in the plasma-dust system. This estimation is improved upon by combining simulations of the dust component of the plume and simulations for the plasma environment into one self-consistent model. Calibration of this model with CAPS data provides a total dust production rate of about 12 kg s-1, including larger dust grains up to a few microns in size. We find that the fraction of charged grains dominates over that of the uncharged grains. Moreover, our model reproduces densities of both negatively and positively charged nanograins measured by Cassini CAPS. In Enceladus' plume ion densities up to ~104cm-3 are required by the self-consistent model, resulting in an electron depletion of about 50% in the plasma, because electrons are attached to the negatively charged nanograins. These ion densities correspond to effective ionization rates of about 10-7s-1, which are about two orders of magnitude higher than expected.

Weakly Interacting Symmetric and Anti-Symmetric States in the Bilayer Systems

NASA Astrophysics Data System (ADS)

Marchewka, M.; Sheregii, E. M.; Tralle, I.; Tomaka, G.; Ploch, D.

We have studied the parallel magneto-transport in DQW-structures of two different potential shapes: quasi-rectangular and quasi-triangular. The quantum beats effect was observed in Shubnikov-de Haas (SdH) oscillations for both types of the DQW structures in perpendicular magnetic filed arrangement. We developed a special scheme for the Landau levels energies calculation by means of which we carried out the necessary simulations of beating effect. In order to obtain the agreement between our experimental data and the results of simulations, we introduced two different quasi-Fermi levels which characterize symmetric and anti-symmetric states in DQWs. The existence of two different quasi Fermi-Levels simply means, that one can treat two sub-systems (charge carriers characterized by symmetric and anti-symmetric wave functions) as weakly interacting and having their own rate of establishing the equilibrium state.

Adsorption and Conformation Change of Helical Peptides on Colloidal Silica

NASA Astrophysics Data System (ADS)

Read, Michael; Zhang, Shuguang; Mayes, Anne; Burkett, Sandra

2001-03-01

Helical conformations of short peptides in solution are partly stabilized by the pattern of electrostatic charge formed by the amino acid sequence. We have studied the role of electrostatics in the adsorption and helix-coil transition of peptides on oxide surfaces. Adsorption isotherms, along with a combination of spectroscopic techniques, show that this is a reversible equilibrium process. Strong electrostatic forces between ionic side chains and charged surface sites increase the adsorbed amount, and promote a loss of helicity in the adsorbed state qualitatively different from that observed upon thermal or chemical perturbation. The electrical dipole of the peptide, arising from the amino acid side chains, serves to orient the molecules on the surface. Effects of adsorption, orientation, and conformation change on the activity of peptides in model biological reactions, as well as the relevance of this simplified system to protein adsorption, are considered.

100 Years of the Physics of Diodes

NASA Astrophysics Data System (ADS)

Luginsland, John

2013-10-01

The Child-Langmuir Law (CL), discovered 100 years ago, gives the maximum current that can be transported across a planar diode in the steady state. As a quintessential example of the impact of space-charge shielding near a charged surface, it is central to the studies of high current diodes, such as high power microwave sources, vacuum microelectronics, electron and ion sources, and high current drivers used in high-energy density physics experiments. CL remains a touchstone of fundamental sheath physics, including contemporary studies of nano-scale quantum diodes and plasmonic devices. Its solid state analog is the Mott-Gurney law, governing the maximum charge injection in solids, such as organic materials and other dielectrics, which is important to energy devices, such as solar cells and light-emitting diodes. This paper reviews the important advances in the physics of diodes since the discovery of CL, including virtual cathode formation and extension of CL to multiple dimensions, to the quantum regime, and to ultrafast processes. We will review the influence of magnetic fields, multiple species in bipolar flow, electromagnetic and time dependent effects in both short pulse and high frequency THz limits, and single electron regimes. Transitions from various emission mechanisms (thermionic, field, and photo-emission) to the space charge limited state (CL) will be addressed, especially highlighting important simulation and experimental developments in selected contemporary areas of study. This talk will stress the fundamental physical links between the physics of beams to limiting currents in other areas, such as low temperature plasmas, laser plasmas, and space propulsion. Also emphasized is the role of non-equilibrium phenomena associated with materials and plasmas in close contact. Work supported by the Air Force Office of Scientific Research.

In Situ STEM-EELS observation of nanoscale interfacial phenomena in all-solid-state batteries

DOE PAGES

Wang, Ziying; Santhanagopalan, Dhamodaran; Zhang, Wei; ...

2016-05-03

Behaviors of functional interfaces are crucial factors in the performance and safety of energy storage and conversion devices. Indeed, solid electrode–solid electrolyte interfacial impedance is now considered the main limiting factor in all-solid-state batteries rather than low ionic conductivity of the solid electrolyte. In this paper, we present a new approach to conducting in situ scanning transmission electron microscopy (STEM) coupled with electron energy loss spectroscopy (EELS) in order to uncover the unique interfacial phenomena related to lithium ion transport and its corresponding charge transfer. Our approach allowed quantitative spectroscopic characterization of a galvanostatically biased electrochemical system under in situmore » conditions. Using a LiCoO 2/LiPON/Si thin film battery, an unexpected structurally disordered interfacial layer between LiCoO 2 cathode and LiPON electrolyte was discovered to be inherent to this interface without cycling. During in situ charging, spectroscopic characterization revealed that this interfacial layer evolved to form highly oxidized Co ions species along with lithium oxide and lithium peroxide species. These findings suggest that the mechanism of interfacial impedance at the LiCoO 2/LiPON interface is caused by chemical changes rather than space charge effects. Finally, insights gained from this technique will shed light on important challenges of interfaces in all-solid-state energy storage and conversion systems and facilitate improved engineering of devices operated far from equilibrium.« less

Static structure of a pointed charged drop

NASA Astrophysics Data System (ADS)

Fernandez de La Mora, Juan

2017-11-01

The static equilibrium structure of an equipotential drop with two symmetric Taylor cones is computed by assigning a charge distribution along the z axis q (z) = ∑Bn (L2 -z2)n + 1 / 2 . Taylor's local equilibrium at the poles z = L , - L fixes two of the Bn coefficients as a function of the other, determined by minimizing stress imbalance. Just two optimally chosen terms in the Bn expansion yield imperceptible errors. Prior work has argued that an exploding drop initially carrying Rayleigh's charge qR is quasi static. Paradoxically, quasi-static predictions on the size of the progeny drops emitted during a Coulombic explosion disagree with observations. The static drop structure found here also models poorly a Coulomb explosion having an equatorial over polar length ratio (0.42) and the a drop charge exceeding those observed (0.28-0.36 and qR / 2). Our explanation for this paradox is that, while the duration tc of a Coulomb explosion is much larger than the charge relaxation time, the dynamic time scale for drop elongation is typically far longer than tc. Therefore, the pressure distribution within the exploding drop is not uniform. A similar analysis for a drop in an external field fits well the experimental shape.

Lattice-mediated magnetic order melting in TbMnO 3

DOE PAGES

Baldini, Edoardo; Kubacka, Teresa; Mallett, Benjamin P. P.; ...

2018-03-15

Recent ultrafast magnetic-sensitive measurements have revealed a delayed melting of the long-range cycloid spin order in TbMnO 3 following photoexcitation across the fundamental Mott-Hubbard gap. The microscopic mechanism behind this slow transfer of energy from the photoexcited carriers to the spin degrees of freedom is still elusive and not understood. Here, we address this problem by combining spectroscopic ellipsometry, ultrafast broadband optical spectroscopy, and ab initio calculations. Upon photoexcitation, we observe the emergence of a complex collective response, which is due to high-energy coherent optical phonons coupled to the out-of-equilibrium charge density. This response precedes the magnetic order melting andmore » is interpreted as the fingerprint of the formation of anti-Jahn-Teller polarons. We propose that the charge localization in a long-lived self-trapped state hinders the emission of magnons and other spin-flip mechanisms, causing the energy transfer from the charge to the spin system to be mediated by the reorganization of the lattice. In conclusion, we provide evidence for the coherent excitation of a phonon mode associated with the ferroelectric phase transition.« less

Do surfaces of positive electrostatic potential on different halogen derivatives in molecules attract? like attracting like!

PubMed

Varadwaj, Arpita; Varadwaj, Pradeep R; Yamashita, Koichi

2018-03-15

Coulomb's law states that like charges repel, and unlike charges attract. However, it has recently been theoretically revealed that two similarly charged conducting spheres will almost always attract each other when both are in close proximity. Using multiscale first principles calculations, we illustrate practical examples of several intermolecular complexes that are formed by the consequences of attraction between positive atomic sites of similar or dissimilar electrostatic surface potential on interacting molecules. The results of the quantum theory of atoms in molecules and symmetry adapted perturbation theory support the attraction between the positive sites, characterizing the F•••X (X = F, Cl, Br) intermolecular interactions in a series of 20 binary complexes as closed-shell type, although the molecular electrostatic surface potential approach does not (a failure!). Dispersion that has an r -6 dependence, where r is the equilibrium distance of separation, is found to be the sole driving force pushing the two positive sites to attract. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Electrohydrodynamic interactions of spherical particles under Quincke rotation

NASA Astrophysics Data System (ADS)

Das, Debasish; Saintillan, David

2012-11-01

Quincke rotation denotes the spontaneous rotation of dielectric particles immersed in a slightly dielectric liquid when subjected to a high enough DC electric field. It occurs when the charge relaxation time of the particles is greater than that of the fluid medium, causing the particles to become polarized in a direction opposite to that of the electric field and therefore giving rise to an unstable equilibrium position. When slightly perturbed, the particles start to rotate, and if the electric field exceeds a critical value the perturbations do not decay and the particle rotations reach a steady state with a constant angular velocity. We use a combination of numerical simulations and asymptotic theory to study the effect of electrohydrodynamic interactions between particles under Quincke rotation. We study the prototypical case of two equally charged spheres carrying no net charge and interacting with each other both hydrodynamically and electrically. The case of spherical particles free to roll on a horizontal grounded electrode is also described. We show that Quincke rotation results in self-propulsion of the particles in the plane of the electrode, and interactions between a pair of such ``rollers'' are analyzed.

Lattice-mediated magnetic order melting in TbMnO 3

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

Baldini, Edoardo; Kubacka, Teresa; Mallett, Benjamin P. P.

Recent ultrafast magnetic-sensitive measurements have revealed a delayed melting of the long-range cycloid spin order in TbMnO 3 following photoexcitation across the fundamental Mott-Hubbard gap. The microscopic mechanism behind this slow transfer of energy from the photoexcited carriers to the spin degrees of freedom is still elusive and not understood. Here, we address this problem by combining spectroscopic ellipsometry, ultrafast broadband optical spectroscopy, and ab initio calculations. Upon photoexcitation, we observe the emergence of a complex collective response, which is due to high-energy coherent optical phonons coupled to the out-of-equilibrium charge density. This response precedes the magnetic order melting andmore » is interpreted as the fingerprint of the formation of anti-Jahn-Teller polarons. We propose that the charge localization in a long-lived self-trapped state hinders the emission of magnons and other spin-flip mechanisms, causing the energy transfer from the charge to the spin system to be mediated by the reorganization of the lattice. In conclusion, we provide evidence for the coherent excitation of a phonon mode associated with the ferroelectric phase transition.« less

What Protein Charging (and Supercharging) Reveal about the Mechanism of Electrospray Ionization

PubMed Central

Loo, Rachel R. Ogorzalek; Lakshmanan, Rajeswari

2014-01-01

Understanding the charging mechanism of electrospray ionization is central to overcoming shortcomings such as ion suppression or limited dynamic range and explaining phenomena such as supercharging. Towards that end, we explore what accumulated observations reveal about the mechanism of electrospray. We introduce the idea of an intermediate region for electrospray ionization (and other ionization methods) to account for the facts that solution charge state distributions (CSDs) do not correlate to those observed by ESI– MS (the latter bear more charge) and that gas phase reactions can reduce, but not increase the extent of charging. This region incorporates properties, e.g., basicities, intermediate between solution and gas phase. Assuming that droplet species polarize within the high electric field leads to equations describing ion emission resembling those from the equilibrium partitioning model. The equations predict many trends successfully, including CSD shifts to higher m/z for concentrated analytes and shifts to lower m/z for sprays employing smaller emitter opening diameters. From this view, a single mechanism can be formulated to explain how reagents that promote analyte charging (“supercharging”) such as m–NBA, sulfolane, and 3–nitrobenzonitrile increase analyte charge from “denaturing” and “native” solvent systems. It is suggested that additives’ Brønsted basicities are inversely correlated to their ability to shift CSDs to lower m/z in positive ESI, as are Brønsted acidities for negative ESI. Because supercharging agents reduce an analyte's solution ionization, excess spray charge is bestowed on evaporating ions carryingfewer opposing charges. Brønsted basicity (or acidity) determines how much ESI charge is lost to the agent (unavailable to evaporating analyte). PMID:25135609

Reversible hydration and aqueous exfoliation of the acetate-intercalated layered double hydroxide of Ni and Al: Observation of an ordered interstratified phase

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

Manohara, G.V.; Vishnu Kamath, P., E-mail: vishnukamath8@hotmail.com; Milius, Wolfgang

2012-12-15

Acetate-intercalated layered double hydroxides (LDHs) of Ni and Al undergo reversible hydration in the solid state in response to the ambient humidity. The LDH with a high layer charge (0.33/formula unit) undergoes facile hydration in a single step, whereas the LDH with a lower layer charge (0.24/formula unit) exhibits an ordered interstratified intermediate, comprising the hydrated and dehydrated layers stacked alternatively. This phase, also known as the staged S-2 phase, coexists with the end members suggesting the existence of a solution-type equilibrium between the S-2 phase and the end members of the hydration cycle. These LDHs also undergo facile aqueousmore » exfoliation into 2-5 nm-thick tactoids with a radial dimension of 0.2-0.5 {mu}m. - Graphical abstract: Schematic of the hydrated, dehydrated and interstratified phases observed during the hydration-dehydration of Ni/Al-CH{sub 3}COO LDH. Highlights: Black-Right-Pointing-Pointer Ni/Al-acetate LDHs were synthesized by HPFS method by hydrolysis of acetamide. Black-Right-Pointing-Pointer Intercalated acetate ion shows reversible hydration with variation in humidity. Black-Right-Pointing-Pointer An ordered interstratified phase was observed during hydration/dehydration cycle. Black-Right-Pointing-Pointer A solution type equilibrium is observed between hydration-dehydration phases. Black-Right-Pointing-Pointer These LDHs undergo facile aqueous exfoliation.« less

The Thomas-Fermi model in the theory of systems of charged particles above the surface of liquid dielectrics

NASA Astrophysics Data System (ADS)

Lytvtnenko, D. M.; Slyusarenko, Yu. V.; Kirdin, A. I.

2012-10-01

A consistent theory of equilibrium states of same sign charges above the surface of liquid dielectric film located on solid substrate in the presence of external attracting constant electric field is proposed. The approach to the development of the theory is based on the Thomas-Fermi model generalized to the systems under consideration and on the variational principle. The using of self-consistent field model allows formulating a theory containing no adjustable constants. In the framework of the variational principle we obtain the self-consistency equations for the parameters describing the system: the distribution function of charges above the liquid dielectric surface, the electrostatic field potentials in all regions of the system and the surface profile of the liquid dielectric. The self-consistency equations are used to describe the phase transition associated with the formation of spatially periodic structures in the system of charges on liquid dielectric surface. Assuming the non-degeneracy of the gas of charges above the surface of liquid dielectric film the solutions of the self-consistency equations near the critical point are obtained. In the case of the symmetric phase we obtain the expressions for the potentials and electric fields in all regions of the studied system. The distribution of the charges above the surface of liquid dielectric film for the symmetric phase is derived. The system parameters of the phase transition to nonsymmetric phase - the states with a spatially periodic ordering are obtained. We derive the expression determining the period of two-dimensional lattice as a function of physical parameters of the problem - the temperature, the external attractive electric field, the number of electrons per unit of the flat surface area of the liquid dielectric, the density of the dielectric, its surface tension and permittivity, and the permittivity of the solid substrate. The possibility of generalizing the developed theory in the case of degenerate gas of like-charged particles above the liquid dielectric surface is discussed.

Atomic charge transfer-counter polarization effects determine infrared CH intensities of hydrocarbons: a quantum theory of atoms in molecules model.

PubMed

Silva, Arnaldo F; Richter, Wagner E; Meneses, Helen G C; Bruns, Roy E

2014-11-14

Atomic charge transfer-counter polarization effects determine most of the infrared fundamental CH intensities of simple hydrocarbons, methane, ethylene, ethane, propyne, cyclopropane and allene. The quantum theory of atoms in molecules/charge-charge flux-dipole flux model predicted the values of 30 CH intensities ranging from 0 to 123 km mol(-1) with a root mean square (rms) error of only 4.2 km mol(-1) without including a specific equilibrium atomic charge term. Sums of the contributions from terms involving charge flux and/or dipole flux averaged 20.3 km mol(-1), about ten times larger than the average charge contribution of 2.0 km mol(-1). The only notable exceptions are the CH stretching and bending intensities of acetylene and two of the propyne vibrations for hydrogens bound to sp hybridized carbon atoms. Calculations were carried out at four quantum levels, MP2/6-311++G(3d,3p), MP2/cc-pVTZ, QCISD/6-311++G(3d,3p) and QCISD/cc-pVTZ. The results calculated at the QCISD level are the most accurate among the four with root mean square errors of 4.7 and 5.0 km mol(-1) for the 6-311++G(3d,3p) and cc-pVTZ basis sets. These values are close to the estimated aggregate experimental error of the hydrocarbon intensities, 4.0 km mol(-1). The atomic charge transfer-counter polarization effect is much larger than the charge effect for the results of all four quantum levels. Charge transfer-counter polarization effects are expected to also be important in vibrations of more polar molecules for which equilibrium charge contributions can be large.

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

Filippov, A. V., E-mail: fav@triniti.ru

The interaction of two charged point macroparticles located in Wigner–Seitz cells of simple cubic (SC), body-centered cubic (BCC), or face-centered cubic (FCC) lattices in an equilibrium plasma has been studied within the Debye approximation or, more specifically, based on the linearized Poisson–Boltzmann model. The shape of the outer boundary is shown to exert a strong influence on the pattern of electrostatic interaction between the two macroparticles, which transforms from repulsion at small interparticle distances to attraction as the interparticle distance approaches half the length of the computational cell. The macroparticle pair interaction potential in an equilibrium plasma is shown tomore » be nevertheless the Debye one and purely repulsive for likely charged macroparticles.« less

Induced mitochondrial membrane potential for modeling solitonic conduction of electrotonic signals

PubMed Central

Poznanski, R. R.; Cacha, L. A.; Ali, J.; Rizvi, Z. H.; Yupapin, P.; Salleh, S. H.; Bandyopadhyay, A.

2017-01-01

A cable model that includes polarization-induced capacitive current is derived for modeling the solitonic conduction of electrotonic potentials in neuronal branchlets with microstructure containing endoplasmic membranes. A solution of the nonlinear cable equation modified for fissured intracellular medium with a source term representing charge ‘soakage’ is used to show how intracellular capacitive effects of bound electrical charges within mitochondrial membranes can influence electrotonic signals expressed as solitary waves. The elastic collision resulting from a head-on collision of two solitary waves results in localized and non-dispersing electrical solitons created by the nonlinearity of the source term. It has been shown that solitons in neurons with mitochondrial membrane and quasi-electrostatic interactions of charges held by the microstructure (i.e., charge ‘soakage’) have a slower velocity of propagation compared with solitons in neurons with microstructure, but without endoplasmic membranes. When the equilibrium potential is a small deviation from rest, the nonohmic conductance acts as a leaky channel and the solitons are small compared when the equilibrium potential is large and the outer mitochondrial membrane acts as an amplifier, boosting the amplitude of the endogenously generated solitons. These findings demonstrate a functional role of quasi-electrostatic interactions of bound electrical charges held by microstructure for sustaining solitons with robust self-regulation in their amplitude through changes in the mitochondrial membrane equilibrium potential. The implication of our results indicate that a phenomenological description of ionic current can be successfully modeled with displacement current in Maxwell’s equations as a conduction process involving quasi-electrostatic interactions without the inclusion of diffusive current. This is the first study in which solitonic conduction of electrotonic potentials are generated by polarization-induced capacitive current in microstructure and nonohmic mitochondrial membrane current. PMID:28880876

Induced mitochondrial membrane potential for modeling solitonic conduction of electrotonic signals.

PubMed

Poznanski, R R; Cacha, L A; Ali, J; Rizvi, Z H; Yupapin, P; Salleh, S H; Bandyopadhyay, A

2017-01-01

A cable model that includes polarization-induced capacitive current is derived for modeling the solitonic conduction of electrotonic potentials in neuronal branchlets with microstructure containing endoplasmic membranes. A solution of the nonlinear cable equation modified for fissured intracellular medium with a source term representing charge 'soakage' is used to show how intracellular capacitive effects of bound electrical charges within mitochondrial membranes can influence electrotonic signals expressed as solitary waves. The elastic collision resulting from a head-on collision of two solitary waves results in localized and non-dispersing electrical solitons created by the nonlinearity of the source term. It has been shown that solitons in neurons with mitochondrial membrane and quasi-electrostatic interactions of charges held by the microstructure (i.e., charge 'soakage') have a slower velocity of propagation compared with solitons in neurons with microstructure, but without endoplasmic membranes. When the equilibrium potential is a small deviation from rest, the nonohmic conductance acts as a leaky channel and the solitons are small compared when the equilibrium potential is large and the outer mitochondrial membrane acts as an amplifier, boosting the amplitude of the endogenously generated solitons. These findings demonstrate a functional role of quasi-electrostatic interactions of bound electrical charges held by microstructure for sustaining solitons with robust self-regulation in their amplitude through changes in the mitochondrial membrane equilibrium potential. The implication of our results indicate that a phenomenological description of ionic current can be successfully modeled with displacement current in Maxwell's equations as a conduction process involving quasi-electrostatic interactions without the inclusion of diffusive current. This is the first study in which solitonic conduction of electrotonic potentials are generated by polarization-induced capacitive current in microstructure and nonohmic mitochondrial membrane current.

Donnan membrane speciation of Al, Fe, trace metals and REEs in coastal lowland acid sulfate soil-impacted drainage waters.

PubMed

Jones, Adele M; Xue, Youjia; Kinsela, Andrew S; Wilcken, Klaus M; Collins, Richard N

2016-03-15

Donnan dialysis has been applied to forty filtered drainage waters collected from five coastal lowland acid sulfate soil (CLASS) catchments across north-eastern NSW, Australia. Despite having average pH values<3.9, 78 and 58% of Al and total Fe, respectively, were present as neutral or negatively-charged species. Complementary isotope dilution experiments with (55)Fe and (26)Al demonstrated that only soluble (i.e. no colloidal) species were present. Trivalent rare earth elements (REEs) were also mainly present (>70%) as negatively-charged complexes. In contrast, the speciation of the divalent trace metals Co, Mn, Ni and Zn was dominated by positively-charged complexes and was strongly correlated with the alkaline earth metals Ca and Mg. Thermodynamic equilibrium speciation calculations indicated that natural organic matter (NOM) complexes dominated Fe(III) speciation in agreement with that obtained by Donnan dialysis. In the case of Fe(II), however, the free cation was predicted to dominate under thermodynamic equilibrium, whilst our results indicated that Fe(II) was mainly present as neutral or negatively-charged complexes (most likely with sulfate). For all other divalent metals thermodynamic equilibrium speciation calculations agreed well with the Donnan dialysis results. The proportion of Al and REEs predicted to be negatively-charged was also grossly underestimated, relative to the experimental results, highlighting possible inaccuracies in the stability constants developed for these trivalent Me(SO4)2(-) and/or Me-NOM complexes and difficulties in modeling complex environmental samples. These results will help improve metal mobility and toxicity models developed for CLASS-affected environments, and also demonstrate that Australian CLASS environments can discharge REEs at concentrations an order of magnitude greater than previously reported. Copyright © 2015 Elsevier B.V. All rights reserved.

Applicability of Donnan equilibrium theory at nanochannel-reservoir interfaces.

PubMed

Tian, Huanhuan; Zhang, Li; Wang, Moran

2015-08-15

Understanding ionic transport in nanochannels has attracted broad attention from various areas in energy and environmental fields. In most pervious research, Donnan equilibrium has been applied widely to nanofluidic systems to obtain ionic concentration and electrical potential at channel-reservoir interfaces; however, as well known that Donnan equilibrium is derived from classical thermodynamic theories with equilibrium assumptions. Therefore the applicability of the Donnan equilibrium may be questionable when the transport at nanochannel-reservoir interface is strongly non-equilibrium. In this work, the Poisson-Nernst-Planck model for ion transport is numerically solved to obtain the exact distributions of ionic concentration and electrical potential. The numerical results are quantitatively compared with the Donnan equilibrium predictions. The applicability of Donnan equilibrium is therefore justified by changing channel length, reservoir ionic concentration, surface charge density and channel height. The results indicate that the Donnan equilibrium is not applicable for short nanochannels, large concentration difference and wide openings. A non-dimensional parameter, Q factor, is proposed to measure the non-equilibrium extent and the relation between Q and the working conditions is studied in detail. Copyright © 2015 Elsevier Inc. All rights reserved.

Measuring the charge density of a tapered optical fiber using trapped microparticles.

PubMed

Kamitani, Kazuhiko; Muranaka, Takuya; Takashima, Hideaki; Fujiwara, Masazumi; Tanaka, Utako; Takeuchi, Shigeki; Urabe, Shinji

2016-03-07

We report the measurements of charge density of tapered optical fibers using charged particles confined in a linear Paul trap at ambient pressure. A tapered optical fiber is placed across the trap axis at a right angle, and polystyrene microparticles are trapped along the trap axis. The distance between the equilibrium position of a positively charged particle and the tapered fiber is used to estimate the amount of charge per unit length of the fiber without knowing the amount of charge of the trapped particle. The charge per unit length of a tapered fiber with a diameter of 1.6 μm was measured to be 2-1+3×10 -11 C/m.

Do goethite surfaces really control the transport and retention of multi-walled carbon nanotubes in chemically heterogeneous porous media?

USDA-ARS?s Scientific Manuscript database

Transport and retention behavior of multiwalled carbon nanotubes (MWCNTs) was studied in mixtures of negatively charged quartz sand (QS) and positively charged goethite-coated sand (GQS) to assess the role of chemical heterogeneity. The linear equilibrium sorption model provided a good description o...

A Better Criterion for the Discharging Time in an RC Circuit

ERIC Educational Resources Information Center

Lima, Fabio M. S.

2015-01-01

When all parts of an electric circuit are at the same potential, no electric current flows and it is said to be in "equilibrium." Otherwise, a current will flow from the higher potential parts to the lower ones, as when we make contact between the plates of a charged capacitor. The resulting discharging process towards equilibrium is a…

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

Grove, John W.

We investigate sufficient conditions for thermodynamic consistency for equilibrium mixtures. Such models assume that the mass fraction average of the material component equations of state, when closed by a suitable equilibrium condition, provide a composite equation of state for the mixture. Here, we show that the two common equilibrium models of component pressure/temperature equilibrium and volume/temperature equilibrium (Dalton, 1808) define thermodynamically consistent mixture equations of state and that other equilibrium conditions can be thermodynamically consistent provided appropriate values are used for the mixture specific entropy and pressure.

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

Self-amplified photo-induced gap quenching in a correlated electron material

DOE PAGES

Mathias, S.; Eich, S.; Urbancic, J.; ...

2016-10-04

Capturing the dynamic electronic band structure of a correlated material presents a powerful capability for uncovering the complex couplings between the electronic and structural degrees of freedom. When combined with ultrafast laser excitation, new phases of matter can result, since far-from-equilibrium excited states are instantaneously populated. Here, we elucidate a general relation between ultrafast non-equilibrium electron dynamics and the size of the characteristic energy gap in a correlated electron material. Here, we show that carrier multiplication via impact ionization can be one of the most important processes in a gapped material, and that the speed of carrier multiplication critically dependsmore » on the size of the energy gap. In the case of the charge-density wave material 1T-TiSe 2, our data indicate that carrier multiplication and gap dynamics mutually amplify each other, which explains—on a microscopic level—the extremely fast response of this material to ultrafast optical excitation.« less

Conformation-driven quantum interference effects mediated by through-space conjugation in self-assembled monolayers

NASA Astrophysics Data System (ADS)

Carlotti, Marco; Kovalchuk, Andrii; Wächter, Tobias; Qiu, Xinkai; Zharnikov, Michael; Chiechi, Ryan C.

2016-12-01

Tunnelling currents through tunnelling junctions comprising molecules with cross-conjugation are markedly lower than for their linearly conjugated analogues. This effect has been shown experimentally and theoretically to arise from destructive quantum interference, which is understood to be an intrinsic, electronic property of molecules. Here we show experimental evidence of conformation-driven interference effects by examining through-space conjugation in which π-conjugated fragments are arranged face-on or edge-on in sufficiently close proximity to interact through space. Observing these effects in the latter requires trapping molecules in a non-equilibrium conformation closely resembling the X-ray crystal structure, which we accomplish using self-assembled monolayers to construct bottom-up, large-area tunnelling junctions. In contrast, interference effects are completely absent in zero-bias simulations on the equilibrium, gas-phase conformation, establishing through-space conjugation as both of fundamental interest and as a potential tool for tuning tunnelling charge-transport in large-area, solid-state molecular-electronic devices.

Raman enhancement on ultra-clean graphene quantum dots produced by quasi-equilibrium plasma-enhanced chemical vapor deposition.

PubMed

Liu, Donghua; Chen, Xiaosong; Hu, Yibin; Sun, Tai; Song, Zhibo; Zheng, Yujie; Cao, Yongbin; Cai, Zhi; Cao, Min; Peng, Lan; Huang, Yuli; Du, Lei; Yang, Wuli; Chen, Gang; Wei, Dapeng; Wee, Andrew Thye Shen; Wei, Dacheng

2018-01-15

Graphene is regarded as a potential surface-enhanced Raman spectroscopy (SERS) substrate. However, the application of graphene quantum dots (GQDs) has had limited success due to material quality. Here, we develop a quasi-equilibrium plasma-enhanced chemical vapor deposition method to produce high-quality ultra-clean GQDs with sizes down to 2 nm directly on SiO 2 /Si, which are used as SERS substrates. The enhancement factor, which depends on the GQD size, is higher than conventional graphene sheets with sensitivity down to 1 × 10 -9  mol L -1 rhodamine. This is attributed to the high-quality GQDs with atomically clean surfaces and large number of edges, as well as the enhanced charge transfer between molecules and GQDs with appropriate diameters due to the existence of Van Hove singularities in the electronic density of states. This work demonstrates a sensitive SERS substrate, and is valuable for applications of GQDs in graphene-based photonics and optoelectronics.

Potential-specific structure at the hematite-electrolyte interface

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

McBriarty, Martin E.; Stubbs, Joanne; Eng, Peter

The atomic-scale structure of interfaces between metal oxides and aqueous electrolytes controls their catalytic, geochemical, and corrosion behavior. Measurements that probe these interfaces in situ provide important details of ion and solvent arrangements, but atomically precise structural models do not exist for common oxide-electrolyte interfaces far from equilibrium. Using a novel cell, we measured the structure of the hematite (a-Fe 2O 3) (110more » $$\\bar{2}$$)-electrolyte interface under controlled electrochemical bias using synchrotron crystal truncation rod X ray scattering. At increasingly cathodic potentials, charge-compensating protonation of surface oxygen groups increases the coverage of specifically bound water while adjacent water layers displace outwardly and became disordered. Returning to open circuit potential leaves the surface in a persistent metastable protonation state. The flux of current and ions at applied potential is thus regulated by a unique interfacial electrolyte environment, suggesting that electrical double layer models should be adapted to the dynamically changing interfacial structure far from equilibrium.« less

Jeans instability of a dusty plasma with dust charge variations

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

Hakimi Pajouh, H., E-mail: hakimi@alzahra.ac.ir; Afshari, N.

2015-09-15

The effect of the dust charge variations on the stability of a self-gravitating dusty plasma has been theoretically investigated. The dispersion relation for the dust-acoustic waves in a self-gravitating dusty plasma is obtained. It is shown that the dust charge variations have significant effects. It increases the growth rate of instability and the instability cutoff wavenumbers. It is found that by increasing the value of the ions temperature and the absolute value of the equilibrium dust charge, the cutoff wavenumber decreases and the stability region is extended.

The effects of a decompression on seismic parameter profiles in a gas-charged magma

NASA Astrophysics Data System (ADS)

Sturton, Susan; Neuberg, Jürgen

2003-11-01

Seismic velocities in a gas-charged magma vary with depth and time. Relationships between pressure, density, exsolved gas content, and seismic velocity are derived and used in conjunction with expressions describing diffusive bubble growth to find a series of velocity profiles which depend on time. An equilibrium solution is obtained by considering a column of magma in which the gas distribution corresponds to the magmastatic pressure profile with depth. Decompression events of various sizes are simulated, and the resulting disequilibrium between the gas pressure and magmastatic pressure leads to bubble growth and therefore to a change of seismic velocity and density with time. Bubble growth stops when the system reaches a new equilibrium. The corresponding volume increase is accommodated by accelerating the magma column upwards and an extrusion of lava. A timescale for the system to return to equilibrium can be obtained. The effect of changes in magma viscosity and bubble number density is examined.

Sedimentation dynamics and equilibrium profiles in multicomponent mixtures of colloidal particles.

PubMed

Spruijt, E; Biesheuvel, P M

2014-02-19

In this paper we give a general theoretical framework that describes the sedimentation of multicomponent mixtures of particles with sizes ranging from molecules to macroscopic bodies. Both equilibrium sedimentation profiles and the dynamic process of settling, or its converse, creaming, are modeled. Equilibrium profiles are found to be in perfect agreement with experiments. Our model reconciles two apparently contradicting points of view about buoyancy, thereby resolving a long-lived paradox about the correct choice of the buoyant density. On the one hand, the buoyancy force follows necessarily from the suspension density, as it relates to the hydrostatic pressure gradient. On the other hand, sedimentation profiles of colloidal suspensions can be calculated directly using the fluid density as apparent buoyant density in colloidal systems in sedimentation-diffusion equilibrium (SDE) as a result of balancing gravitational and thermodynamic forces. Surprisingly, this balance also holds in multicomponent mixtures. This analysis resolves the ongoing debate of the correct choice of buoyant density (fluid or suspension): both approaches can be used in their own domain. We present calculations of equilibrium sedimentation profiles and dynamic sedimentation that show the consequences of these insights. In bidisperse mixtures of colloids, particles with a lower mass density than the homogeneous suspension will first cream and then settle, whereas particles with a suspension-matched mass density form transient, bimodal particle distributions during sedimentation, which disappear when equilibrium is reached. In all these cases, the centers of the distributions of the particles with the lowest mass density of the two, regardless of their actual mass, will be located in equilibrium above the so-called isopycnic point, a natural consequence of their hard-sphere interactions. We include these interactions using the Boublik-Mansoori-Carnahan-Starling-Leland (BMCSL) equation of state. Finally, we demonstrate that our model is not limited to hard spheres, by extending it to charged spherical particles, and to dumbbells, trimers and short chains of connected beads.

Strong Deformation of the Thick Electric Double Layer around a Charged Particle during Sedimentation or Electrophoresis.

PubMed

Khair, Aditya S

2018-01-23

The deformation of the electric double layer around a charged colloidal particle during sedimentation or electrophoresis in a binary, symmetric electrolyte is studied. The surface potential of the particle is assumed to be small compared to the thermal voltage scale. Additionally, the Debye length is assumed to be large compared to the particle size. These assumptions enable a linearization of the electrokinetic equations. The particle appears as a point charge in this thick-double-layer limit; the distribution of charge in the diffuse cloud surrounding it is determined by a balance of advection due to the particle motion, Brownian diffusion of ions, and electrostatic screening of the particle by the cloud. The ability of advection to deform the charge cloud from its equilibrium state is parametrized by a Péclet number, Pe. For weak advection (Pe ≪ 1), the cloud is only slightly deformed. In contrast, the cloud can be completely stripped from the particle at Pe ≫ 1; consequently, electrokinetic effects on the particle motion vanish in this regime. Therefore, in sedimentation the drag limits to Stokes' law for an uncharged particle as Pe → ∞. Likewise, the particle velocity for electrophoresis approaches Huckel's result. The strongly deformed cloud at large Pe is predicted to generate a concomitant increase in the sedimentation field in a dilute settling suspension.

Exciton center-of-mass localization and dielectric environment effect in monolayer WS2

NASA Astrophysics Data System (ADS)

Hichri, Aïda; Ben Amara, Imen; Ayari, Sabrine; Jaziri, Sihem

2017-06-01

The ultrathin transition metal dichalcogenides (TMDs) have emerged as promising materials for various applications using two dimensional semiconductors. They have attracted increasing attention due to their unique optical properties originate from neutral and charged excitons. In this paper, we study the strong localization of exciton center-of-mass motion within random potential fluctuations caused by the monolayer defects. Here, we report negatively charged exciton formation in monolayer TMDs, notably tungsten disulfide WS2. Our theory is based on an effective mass model of neutral and charged excitons, parameterized by ab-initio calculations. Taking into the account the strong correlation between the monolayer WS2 and the surrounding dielectric environment, our theoretical results are in good agreement with one-photon photoluminescence (PL) and reflectivity measurements. We also show that the exciton state with p-symmetry, experimentally observed by two-photon PL emission, is energetically below the 2s-state. We use the equilibrium mass action law, to quantify the relative weight of exciton and trion PL. We show that exciton and trion emission can be tuned and controlled by external parameters like temperature, pumping, and injection electrons. Finally, in comparison with experimental measurements, we show that exciton emission in monolayer tungsten dichalcogenides is substantially reduced. This feature suggests that free exciton can be trapped in disordered potential wells to form a localized exciton and therefore offers a route toward novel optical properties.

Investigation of charge injection and transport behavior in multilayer structure consisted of ferromagnetic metal and organic polymer under external fields

NASA Astrophysics Data System (ADS)

Zhao, Hua; Meng, Wei-Feng

2017-10-01

In this paper a five layer organic electronic device with alternately placed ferromagnetic metals and organic polymers: ferromagnetic metal/organic layer/ferromagnetic metal/organic layer/ferromagnetic metal, which is injected a spin-polarized electron from outsides, is studied theoretically using one-dimensional tight binding model Hamiltonian. We calculated equilibrium state behavior after an electron with spin is injected into the organic layer of this structure, charge density distribution and spin polarization density distribution of this injected spin-polarized electron, and mainly studied possible transport behavior of the injected spin polarized electron in this multilayer structure under different external electric fields. We analyze the physical process of the injected electron in this multilayer system. It is found by our calculation that the injected spin polarized electron exists as an electron-polaron state with spin polarization in the organic layer and it can pass through the middle ferromagnetic layer from the right-hand organic layer to the left-hand organic layer by the action of increasing external electric fields, which indicates that this structure may be used as a possible spin-polarized charge electronic device and also may provide a theoretical base for the organic electronic devices and it is also found that in the boundaries between the ferromagnetic layer and the organic layer there exist induced interface local dipoles due to the external electric fields.

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.

Revealing the Coulomb interaction strength in a cuprate superconductor

DOE PAGES

Yang, S. -L.; Sobota, J. A.; He, Y.; ...

2017-12-08

Here, we study optimally doped Bi 2 Sr 2 Ca 0.92 Y 0.08 Cu 2 O 8 + δ (Bi2212) using angle-resolved two-photon photoemission spectroscopy. Three spectral features are resolved near 1.5, 2.7, and 3.6 eV above the Fermi level. By tuning the photon energy, we determine that the 2.7-eV feature arises predominantly from unoccupied states. The 1.5- and 3.6-eV features reflect unoccupied states whose spectral intensities are strongly modulated by the corresponding occupied states. These unoccupied states are thus consistent with the prediction from a cluster perturbation theory based on the single-band Hubbard model. Through this comparison, amore » Coulomb interaction strength U of 2.7 eV is extracted. Our study complements equilibrium photoemission spectroscopy and provides a direct spectroscopic measurement of the unoccupied states in cuprates. The determined Coulomb U indicates that the charge-transfer gap of optimally doped Bi2212 is 1.1 eV.« less

Model-based analysis of coupled equilibrium-kinetic processes: indirect kinetic studies of thermodynamic parameters using the dynamic data.

PubMed

Emami, Fereshteh; Maeder, Marcel; Abdollahi, Hamid

2015-05-07

Thermodynamic studies of equilibrium chemical reactions linked with kinetic procedures are mostly impossible by traditional approaches. In this work, the new concept of generalized kinetic study of thermodynamic parameters is introduced for dynamic data. The examples of equilibria intertwined with kinetic chemical mechanisms include molecular charge transfer complex formation reactions, pH-dependent degradation of chemical compounds and tautomerization kinetics in micellar solutions. Model-based global analysis with the possibility of calculating and embedding the equilibrium and kinetic parameters into the fitting algorithm has allowed the complete analysis of the complex reaction mechanisms. After the fitting process, the optimal equilibrium and kinetic parameters together with an estimate of their standard deviations have been obtained. This work opens up a promising new avenue for obtaining equilibrium constants through the kinetic data analysis for the kinetic reactions that involve equilibrium processes.

Accelerating Multiagent Reinforcement Learning by Equilibrium Transfer.

PubMed

Hu, Yujing; Gao, Yang; An, Bo

2015-07-01

An important approach in multiagent reinforcement learning (MARL) is equilibrium-based MARL, which adopts equilibrium solution concepts in game theory and requires agents to play equilibrium strategies at each state. However, most existing equilibrium-based MARL algorithms cannot scale due to a large number of computationally expensive equilibrium computations (e.g., computing Nash equilibria is PPAD-hard) during learning. For the first time, this paper finds that during the learning process of equilibrium-based MARL, the one-shot games corresponding to each state's successive visits often have the same or similar equilibria (for some states more than 90% of games corresponding to successive visits have similar equilibria). Inspired by this observation, this paper proposes to use equilibrium transfer to accelerate equilibrium-based MARL. The key idea of equilibrium transfer is to reuse previously computed equilibria when each agent has a small incentive to deviate. By introducing transfer loss and transfer condition, a novel framework called equilibrium transfer-based MARL is proposed. We prove that although equilibrium transfer brings transfer loss, equilibrium-based MARL algorithms can still converge to an equilibrium policy under certain assumptions. Experimental results in widely used benchmarks (e.g., grid world game, soccer game, and wall game) show that the proposed framework: 1) not only significantly accelerates equilibrium-based MARL (up to 96.7% reduction in learning time), but also achieves higher average rewards than algorithms without equilibrium transfer and 2) scales significantly better than algorithms without equilibrium transfer when the state/action space grows and the number of agents increases.

A Theory for Rapid Charging Events on the International Space Station

NASA Technical Reports Server (NTRS)

Ferguson, Dale C.; Craven, Paul D.; Minow, Joseph I.; Wright, Kenneth H., Jr.

2009-01-01

The Floating Potential Measurement Unit (FPMU) has detected high negative amplitude rapid charging events (RCEs) on the International Space Station (ISS) at the morning terminator. These events are larger and more rapid than the ISS morning charging events first seen by the Floating Potential Probe (FPP) on ISS in 2001. In this paper, we describe a theory for the RCEs that further elucidates the nature of spacecraft charging in low Earth orbit (LEO) in a non-equilibrium situation. The model accounts for all essential aspects of the newly discovered phenomenon, and is amenable to testing on-orbit. Predictions of the model for the amplitude of the ISS RCEs for the full set of ISS solar arrays and for the coming solar cycle are given, and the results of modeling by the Environments WorkBench (EWB) are compared to the observed events to show that the phenomenon can be explained by solar array driven charging. The situation is unique because the coverglasses have not yet reached equilibrium with the surrounding plasma during the RCEs. Finally, a prescription for further use of the ISS for investigating fundamental plasma physics in LEO is given. Already, plasma and charging monitoring instruments on ISS have taught us much about spacecraft interactions with the dense LEO plasma, and we expect they will continue to yield more valuable science when the Japanese Experiment Module (JEM) is in place.

Complex fluids with mobile charge-regulating macro-ions

NASA Astrophysics Data System (ADS)

Markovich, Tomer; Andelman, David; Podgornik, Rudi

2017-10-01

We generalize the concept of charge regulation of ionic solutions, and apply it to complex fluids with mobile macro-ions having internal non-electrostatic degrees of freedom. The suggested framework provides a convenient tool for investigating systems where mobile macro-ions can self-regulate their charge (e.g., proteins). We show that even within a simplified charge-regulation model, the charge dissociation equilibrium results in different and notable properties. Consequences of the charge regulation include a positional dependence of the effective charge of the macro-ions, a non-monotonic dependence of the effective Debye screening length on the concentration of the monovalent salt, a modification of the electric double-layer structure, and buffering by the macro-ions of the background electrolyte.

Theory of extrinsic and intrinsic heterojunctions in thermal equilibrium

NASA Technical Reports Server (NTRS)

Von Ross, O.

1980-01-01

A careful analysis of an abrupt heterojunction consisting of two distinct semiconductors either intrinsic or extrinsic is presented. The calculations apply to a one-dimensional, nondegenerate structure. Taking into account all appropriate boundary conditions, it is shown that the intrinsic Fermi level shows a discontinuity at the interface between the two materials which leads to a discontinuity of the valence band edge equal to the difference in the band gap energies of the two materials. The conduction band edge stays continuous however. This result is independent of possible charged interface states and in sharp contrast to the Anderson model. The reasons for this discrepancy are discussed.

On the origin of electrical conductivity in the bio-electronic material melanin

NASA Astrophysics Data System (ADS)

Bernardus Mostert, A.; Powell, Ben J.; Gentle, Ian R.; Meredith, Paul

2012-02-01

The skin pigment melanin is one of a few bio-macromolecules that display electrical and photo-conductivity in the solid-state. A model for melanin charge transport based on amorphous semiconductivity has been widely accepted for 40 years. In this letter, we show that a central pillar in support of this hypothesis, namely experimental agreement with a hydrated dielectric model, is an artefact related to measurement geometry and non-equilibrium behaviour. Our results cast significant doubt on the validity of the amorphous semiconductor model and are a reminder of the difficulties of electrical measurements on low conductivity, disordered organic materials.

Nonequilibrium restoration of duality symmetry in the vicinity of the superconductor-to-insulator transition

NASA Astrophysics Data System (ADS)

Tamir, I.; Doron, A.; Levinson, T.; Gorniaczyk, F.; Tewari, G. C.; Shahar, D.

2017-09-01

The magnetic field driven superconductor-to-insulator transition in thin films is theoretically understood in terms of the notion of vortex-charge duality symmetry. The manifestation of such symmetry is the exchange of roles of current and voltage between the superconductor and the insulator. While experimental evidence obtained from amorphous indium oxide films supported such duality symmetry, it is shown to be broken, counterintuitively, at low temperatures where the insulating phase exhibits discontinuous current-voltage characteristics. Here, we demonstrate that it is possible to effectively restore duality symmetry by driving the system beyond the discontinuity into its high current, far from equilibrium, state.

NMR Crystallography of a Carbanionic Intermediate in Tryptophan Synthase: Chemical Structure, Tautomerization, and Reaction Specificity.

PubMed

Caulkins, Bethany G; Young, Robert P; Kudla, Ryan A; Yang, Chen; Bittbauer, Thomas J; Bastin, Baback; Hilario, Eduardo; Fan, Li; Marsella, Michael J; Dunn, Michael F; Mueller, Leonard J

2016-11-23

Carbanionic intermediates play a central role in the catalytic transformations of amino acids performed by pyridoxal-5'-phosphate (PLP)-dependent enzymes. Here, we make use of NMR crystallography-the synergistic combination of solid-state nuclear magnetic resonance, X-ray crystallography, and computational chemistry-to interrogate a carbanionic/quinonoid intermediate analogue in the β-subunit active site of the PLP-requiring enzyme tryptophan synthase. The solid-state NMR chemical shifts of the PLP pyridine ring nitrogen and additional sites, coupled with first-principles computational models, allow a detailed model of protonation states for ionizable groups on the cofactor, substrates, and nearby catalytic residues to be established. Most significantly, we find that a deprotonated pyridine nitrogen on PLP precludes formation of a true quinonoid species and that there is an equilibrium between the phenolic and protonated Schiff base tautomeric forms of this intermediate. Natural bond orbital analysis indicates that the latter builds up negative charge at the substrate C α and positive charge at C4' of the cofactor, consistent with its role as the catalytic tautomer. These findings support the hypothesis that the specificity for β-elimination/replacement versus transamination is dictated in part by the protonation states of ionizable groups on PLP and the reacting substrates and underscore the essential role that NMR crystallography can play in characterizing both chemical structure and dynamics within functioning enzyme active sites.

NMR Crystallography of a Carbanionic Intermediate in Tryptophan Synthase: Chemical Structure, Tautomerization, and Reaction Specificity

PubMed Central

2016-01-01

Carbanionic intermediates play a central role in the catalytic transformations of amino acids performed by pyridoxal-5′-phosphate (PLP)-dependent enzymes. Here, we make use of NMR crystallography—the synergistic combination of solid-state nuclear magnetic resonance, X-ray crystallography, and computational chemistry—to interrogate a carbanionic/quinonoid intermediate analogue in the β-subunit active site of the PLP-requiring enzyme tryptophan synthase. The solid-state NMR chemical shifts of the PLP pyridine ring nitrogen and additional sites, coupled with first-principles computational models, allow a detailed model of protonation states for ionizable groups on the cofactor, substrates, and nearby catalytic residues to be established. Most significantly, we find that a deprotonated pyridine nitrogen on PLP precludes formation of a true quinonoid species and that there is an equilibrium between the phenolic and protonated Schiff base tautomeric forms of this intermediate. Natural bond orbital analysis indicates that the latter builds up negative charge at the substrate Cα and positive charge at C4′ of the cofactor, consistent with its role as the catalytic tautomer. These findings support the hypothesis that the specificity for β-elimination/replacement versus transamination is dictated in part by the protonation states of ionizable groups on PLP and the reacting substrates and underscore the essential role that NMR crystallography can play in characterizing both chemical structure and dynamics within functioning enzyme active sites. PMID:27779384

Charge deposition dependence of electron transmission through PET nanocapillaries and a tapered glass microcapillary

NASA Astrophysics Data System (ADS)

Tanis, J. A.; Keerthisinghe, D.; Wickramarachchi, S. J.; Ikeda, T.; Stolterfoht, N.

2018-05-01

Charge deposition dependences of electron transmission through insulating PET nanocapillaries and a tapered glass microcapillary are reported and differences with HCI transmission are noted. Investigations were conducted for electrons with incident energies 500-1000 eV, corresponding to energies per charge similar to those used for HCI studies, incident on (1) an array of PET nanocapillaries (density ∼5 × 108/cm2) with diameters 100 nm in a foil of thickness 12 μm, and (2) on a tapered glass microcapillary with inlet/outlet diameters of 800/100 μm and a length of ∼35 mm. The transmission was measured for incident electrons at small sample tilt angles ranging from 0° to 5° with respect to the beam direction. For most angles, including those near zero degrees, there was an initial quiet period during which essentially no transmission was observed, followed by large rises in the transmission during relatively short periods of charge deposition before equilibrium of the transmission was reached. The resulting equilibrium was stable, blocked or had frequent oscillations depending on the incident energy and the capillary used. Observations for both capillaries show that a negative charge patch is needed to guide incident electrons through the capillaries similar to the manner in which HCIs are guided through capillaries.

Interactions of NO{sub 2}{sup {minus}} and SO{sub 3}{sup 2{minus}} with organic triplets. Charge transfer versus energy transfer: The role of reorganization energy in triplet-anion interactions and spectroscopic methods for its evaluation

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

Loeff, I.; Treinin, A.; Linschitz, H.

1992-06-25

Charge-transfer (CT) and energy-transfer (NT) interactions of simple anions with organic triplets are reviewed and discussed in connection with new quenching rate constant (K{sub q}) and radical yield measurements for SO{sub 3}{sup 2{minus}} and No{sub 2}{sup {minus}}. In the latter case both processes may occur at high organic triplet energies. Reorganization energies for one-electron oxidations are obtained for several anions, using data on charge-transfer-to-solvent (CTTS) spectra and photoelectron emission thresholds, which like the kinetic parameters of Marcus-Hush theory, also reflect Franck-Condon strains. The results, combined with thermodynamic free energies, give vertical redox potentials which correlate better than do equilibrium potentialsmore » with quenching rates. The theoretical basis for correlation between k{sub q} and Hv{sub CTTS} is discussed in the framework of Marcus rate theory. Assigning the total reorganization energy in the CT quenching reaction to the small anion component of the D-A pair gives reasonable agreement with data on quenching of dye triplets but too slow rates for aryl carbonyl triplets where exciplex formation may possibly occur. The optical reorganization energy for NO{sub 2}{sup {minus}} leads to values of the thermal self-exchange rate agreeing with those computed from the Marcus-Hush cross-relations, which also neglect bonding effects. The mechanism of NO{sub 2}{sup {minus}} interaction with triplets is discussed in detail, including indirect kinetic evidence for quenching of a short-lived exciplex by NO{sub 2}{sup {minus}} without radical formation. The possibility of reduction by triplet NO{sub 2}{sup {minus}} formed by initial NT from the organic triplet is also considered. Finally, a scheme is presented involving an equilibrium between CT and NT states and relating the free energy difference between these states to radical yields. 54 refs., 8 figs., 3 tabs.« less

Ionization equilibrium at the transition from valence-band to acceptor-band migration of holes in boron-doped diamond

NASA Astrophysics Data System (ADS)

Poklonski, N. A.; Vyrko, S. A.; Poklonskaya, O. N.; Kovalev, A. I.; Zabrodskii, A. G.

2016-06-01

A quasi-classical model of ionization equilibrium in the p-type diamond between hydrogen-like acceptors (boron atoms which substitute carbon atoms in the crystal lattice) and holes in the valence band (v-band) is proposed. The model is applicable on the insulator side of the insulator-metal concentration phase transition (Mott transition) in p-Dia:B crystals. The densities of the spatial distributions of impurity atoms (acceptors and donors) and of holes in the crystal are considered to be Poissonian, and the fluctuations of their electrostatic potential energy are considered to be Gaussian. The model accounts for the decrease in thermal ionization energy of boron atoms with increasing concentration, as well as for electrostatic fluctuations due to the Coulomb interaction limited to two nearest point charges (impurity ions and holes). The mobility edge of holes in the v-band is assumed to be equal to the sum of the threshold energy for diffusion percolation and the exchange energy of the holes. On the basis of the virial theorem, the temperature Tj is determined, in the vicinity of which the dc band-like conductivity of holes in the v-band is approximately equal to the hopping conductivity of holes via the boron atoms. For compensation ratio (hydrogen-like donor to acceptor concentration ratio) K ≈ 0.15 and temperature Tj, the concentration of "free" holes in the v-band and their jumping (turbulent) drift mobility are calculated. Dependence of the differential energy of thermal ionization of boron atoms (at the temperature 3Tj/2) as a function of their concentration N is calculated. The estimates of the extrapolated into the temperature region close to Tj hopping drift mobility of holes hopping from the boron atoms in the charge states (0) to the boron atoms in the charge states (-1) are given. Calculations based on the model show good agreement with electrical conductivity and Hall effect measurements for p-type diamond with boron atom concentrations in the range from 3 × 1017 to 3 × 1020 cm-3, i.e., up to the Mott transition. The model uses no fitting parameters.

Kinetic and spectral descriptions of autoionization phenomena associated with atomic processes in plasmas

NASA Astrophysics Data System (ADS)

Jacobs, Verne L.

2017-06-01

This investigation has been devoted to the theoretical description and computer modeling of atomic processes giving rise to radiative emission in energetic electron and ion beam interactions and in laboratory plasmas. We are also interested in the effects of directed electron and ion collisions and of anisotropic electric and magnetic fields. In the kinetic-theory description, we treat excitation, de-excitation, ionization, and recombination in electron and ion encounters with partially ionized atomic systems, including the indirect contributions from processes involving autoionizing resonances. These fundamental collisional and electromagnetic interactions also provide particle and photon transport mechanisms. From the spectral perspective, the analysis of atomic radiative emission can reveal detailed information on the physical properties in the plasma environment, such as non-equilibrium electron and charge-state distributions as well as electric and magnetic field distributions. In this investigation, a reduced-density-matrix formulation is developed for the microscopic description of atomic electromagnetic interactions in the presence of environmental (collisional and radiative) relaxation and decoherence processes. Our central objective is a fundamental microscopic description of atomic electromagnetic processes, in which both bound-state and autoionization-resonance phenomena can be treated in a unified and self-consistent manner. The time-domain (equation-of-motion) and frequency-domain (resolvent-operator) formulations of the reduced-density-matrix approach are developed in a unified and self-consistent manner. This is necessary for our ultimate goal of a systematic and self-consistent treatment of non-equilibrium (possibly coherent) atomic-state kinetics and high-resolution (possibly overlapping) spectral-line shapes. We thereby propose the introduction of a generalized collisional-radiative atomic-state kinetics model based on a reduced-density-matrix formulation. It will become apparent that the full atomic data needs for the precise modeling of extreme non-equilibrium plasma environments extend beyond the conventional radiative-transition-probability and collisional-cross-section data sets.

Gauge turbulence, topological defect dynamics, and condensation in Higgs models

DOE PAGES

Gasenzer, Thomas; McLerran, Larry; Pawlowski, Jan M.; ...

2014-07-28

The real-time dynamics of topological defects and turbulent configurations of gauge fields for electric and magnetic confinement are studied numerically within a 2+1D Abelian Higgs model. It is shown that confinement is appearing in such systems equilibrating after a strong initial quench such as the overpopulation of the infrared modes. While the final equilibrium state does not support confinement, metastable vortex defect configurations appearing in the gauge field are found to be closely related to the appearance of physically observable confined electric and magnetic charges. These phenomena are seen to be intimately related to the approach of a non-thermal fixedmore » point of the far-from-equilibrium dynamical evolution, signaled by universal scaling in the gauge-invariant correlation function of the Higgs field. Even when the parameters of the Higgs action do not support condensate formation in the vacuum, during this approach, transient Higgs condensation is observed. We discuss implications of these results for the far-from-equilibrium dynamics of Yang–Mills fields and potential mechanisms of how confinement and condensation in non-Abelian gauge fields can be understood in terms of the dynamics of Higgs models. These suggest that there is an interesting new class of dynamics of strong coherent turbulent gauge fields with condensates.« 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.

Ion counting in supercapacitor electrodes using NMR spectroscopy.

PubMed

Griffin, John M; Forse, Alexander C; Wang, Hao; Trease, Nicole M; Taberna, Pierre-Louis; Simon, Patrice; Grey, Clare P

2014-01-01

(19)F NMR spectroscopy has been used to study the local environments of anions in supercapacitor electrodes and to quantify changes in the populations of adsorbed species during charging. In the absence of an applied potential, anionic species adsorbed within carbon micropores (in-pore) are distinguished from those in large mesopores and spaces between particles (ex-pore) by a characteristic nucleus-independent chemical shift (NICS). Adsorption experiments and two-dimensional exchange experiments confirm that anions are in dynamic equilibrium between the in- and ex-pore environments with an exchange rate in the order of tens of Hz. (19)F in situ NMR spectra recorded at different charge states reveal changes in the intensity and NICS of the in-pore resonances, which are interpreted in term of changes in the population and local environments of the adsorbed anions that arise due to the charge-storage process. A comparison of the results obtained for a range of electrolytes reveals that several factors influence the charging mechanism. For a tetraethylammonium tetrafluoroborate electrolyte, positive polarisation of the electrode is found to proceed by anion adsorption at a low concentration, whereas increased ion exchange plays a more important role for a high concentration electrolyte. In contrast, negative polarization of the electrode proceeds by cation adsorption for both concentrations. For a tetrabutylammonium tetrafluoroborate electrolyte, anion expulsion is observed in the negative charging regime; this is attributed to the reduced mobility and/or access of the larger cations inside the pores, which forces the expulsion of anions in order to build up ionic charge. Significant anion expulsion is also observed in the negative charging regime for alkali metal bis(trifluoromethane)sulfonimide electrolytes, suggesting that more subtle factors also affect the charging mechanism.

Non-equilibrium supramolecular polymerization.

PubMed

Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M

2017-09-18

Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term "non-equilibrium self-assembly" by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.

Non-equilibrium supramolecular polymerization

PubMed Central

Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J.

2017-01-01

Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term “non-equilibrium self-assembly” by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization. PMID:28349143

A Schiff base connectivity switch in sensory rhodopsin signaling

PubMed Central

Sineshchekov, Oleg A.; Sasaki, Jun; Phillips, Brian J.; Spudich, John L.

2008-01-01

Sensory rhodopsin I (SRI) in Halobacterium salinarum acts as a receptor for single-quantum attractant and two-quantum repellent phototaxis, transmitting light stimuli via its bound transducer HtrI. Signal-inverting mutations in the SRI–HtrI complex reverse the single-quantum response from attractant to repellent. Fast intramolecular charge movements reported here reveal that the unphotolyzed SRI–HtrI complex exists in two conformational states, which differ by their connection of the retinylidene Schiff base in the SRI photoactive site to inner or outer half-channels. In single-quantum photochemical reactions, the conformer with the Schiff base connected to the cytoplasmic (CP) half-channel generates an attractant signal, whereas the conformer with the Schiff base connected to the extracellular (EC) half-channel generates a repellent signal. In the wild-type complex the conformer equilibrium is poised strongly in favor of that with CP-accessible Schiff base. Signal-inverting mutations shift the equilibrium in favor of the EC-accessible Schiff base form, and suppressor mutations shift the equilibrium back toward the CP-accessible Schiff base form, restoring the wild-type phenotype. Our data show that the sign of the behavioral response directly correlates with the state of the connectivity switch, not with the direction of proton movements or changes in acceptor pKa. These findings identify a shared fundamental process in the mechanisms of transport and signaling by the rhodopsin family. Furthermore, the effects of mutations in the HtrI subunit of the complex on SRI Schiff base connectivity indicate that the two proteins are tightly coupled to form a single unit that undergoes a concerted conformational transition. PMID:18852467

A Schiff base connectivity switch in sensory rhodopsin signaling.

PubMed

Sineshchekov, Oleg A; Sasaki, Jun; Phillips, Brian J; Spudich, John L

2008-10-21

Sensory rhodopsin I (SRI) in Halobacterium salinarum acts as a receptor for single-quantum attractant and two-quantum repellent phototaxis, transmitting light stimuli via its bound transducer HtrI. Signal-inverting mutations in the SRI-HtrI complex reverse the single-quantum response from attractant to repellent. Fast intramolecular charge movements reported here reveal that the unphotolyzed SRI-HtrI complex exists in two conformational states, which differ by their connection of the retinylidene Schiff base in the SRI photoactive site to inner or outer half-channels. In single-quantum photochemical reactions, the conformer with the Schiff base connected to the cytoplasmic (CP) half-channel generates an attractant signal, whereas the conformer with the Schiff base connected to the extracellular (EC) half-channel generates a repellent signal. In the wild-type complex the conformer equilibrium is poised strongly in favor of that with CP-accessible Schiff base. Signal-inverting mutations shift the equilibrium in favor of the EC-accessible Schiff base form, and suppressor mutations shift the equilibrium back toward the CP-accessible Schiff base form, restoring the wild-type phenotype. Our data show that the sign of the behavioral response directly correlates with the state of the connectivity switch, not with the direction of proton movements or changes in acceptor pK(a). These findings identify a shared fundamental process in the mechanisms of transport and signaling by the rhodopsin family. Furthermore, the effects of mutations in the HtrI subunit of the complex on SRI Schiff base connectivity indicate that the two proteins are tightly coupled to form a single unit that undergoes a concerted conformational transition.

Modeling of equilibrium hollow objects stabilized by electrostatics.

PubMed

Mani, Ethayaraja; Groenewold, Jan; Kegel, Willem K

2011-05-18

The equilibrium size of two largely different kinds of hollow objects behave qualitatively differently with respect to certain experimental conditions. Yet, we show that they can be described within the same theoretical framework. The objects we consider are 'minivesicles' of ionic and nonionic surfactant mixtures, and shells of Keplerate-type polyoxometalates. The finite-size of the objects in both systems is manifested by electrostatic interactions. We emphasize the importance of constant charge and constant potential boundary conditions. Taking these conditions into account, indeed, leads to the experimentally observed qualitatively different behavior of the equilibrium size of the objects.

Seebeck coefficient of one electron

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

Durrani, Zahid A. K., E-mail: z.durrani@imperial.ac.uk

2014-03-07

The Seebeck coefficient of one electron, driven thermally into a semiconductor single-electron box, is investigated theoretically. With a finite temperature difference ΔT between the source and charging island, a single electron can charge the island in equilibrium, directly generating a Seebeck effect. Seebeck coefficients for small and finite ΔT are calculated and a thermally driven Coulomb staircase is predicted. Single-electron Seebeck oscillations occur with increasing ΔT, as one electron at a time charges the box. A method is proposed for experimental verification of these effects.

Unveiling the excited state energy transfer pathways in peridinin-chlorophyll a-protein by ultrafast multi-pulse transient absorption spectroscopy.

PubMed

Redeckas, Kipras; Voiciuk, Vladislava; Zigmantas, Donatas; Hiller, Roger G; Vengris, Mikas

2017-04-01

Time-resolved multi-pulse methods were applied to investigate the excited state dynamics, the interstate couplings, and the excited state energy transfer pathways between the light-harvesting pigments in peridinin-chlorophyll a-protein (PCP). The utilized pump-dump-probe techniques are based on perturbation of the regular PCP energy transfer pathway. The PCP complexes were initially excited with an ultrashort pulse, resonant to the S 0 →S 2 transition of the carotenoid peridinin. A portion of the peridinin-based emissive intramolecular charge transfer (ICT) state was then depopulated by applying an ultrashort NIR pulse that perturbed the interaction between S 1 and ICT states and the energy flow from the carotenoids to the chlorophylls. The presented data indicate that the peridinin S 1 and ICT states are spectrally distinct and coexist in an excited state equilibrium in the PCP complex. Moreover, numeric analysis of the experimental data asserts ICT→Chl-a as the main energy transfer pathway in the photoexcited PCP systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Analytical solution of the Poisson-Nernst-Planck equations for an electrochemical system close to electroneutrality

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

Pabst, M., E-mail: M.Pabst@fz-juelich.de

2014-06-14

Single charge densities and the potential are used to describe models of electrochemical systems. These quantities can be calculated by solving a system of time dependent nonlinear coupled partial differential equations, the Poisson-Nernst-Planck equations. Assuming small deviations from the electroneutral equilibrium, the linearized and decoupled equations are solved for a radial symmetric geometry, which represents the interface between a cell and a sensor device. The densities and the potential are expressed by Fourier-Bessels series. The system considered has a ratio between the Debye-length and its geometric dimension on the order of 10{sup −4} so the Fourier-Bessel series can be approximatedmore » by elementary functions. The time development of the system is characterized by two time constants, τ{sub c} and τ{sub g}. The constant τ{sub c} describes the approach to the stationary state of the total charge and the potential. τ{sub c} is several orders of magnitude smaller than the geometry-dependent constant τ{sub g}, which is on the order of 10 ms characterizing the transition to the stationary state of the single ion densities.« less

X-ray Heating and Electron Temperature of Laboratory Photoionized Plasmas

NASA Astrophysics Data System (ADS)

Mancini, Roberto; Lockard, Tom; Mayes, Daniel C.; Loisel, Guillaume; Bailey, James E.; Rochau, Gregory; Abdallah, J.; Golovkin, I.

2018-06-01

In separate experiments performed at the Z facility of Sandia National Laboratories two different samples were employed to produce and characterize photoionized plasmas. One was a gas cell filled with neon, and the other was a thin silicon layer coated with plastic. Both samples were driven by the broadband x-ray flux produced at the collapse of a wire array z-pinch implosion. Transmission spectroscopy of a narrowband portion of the x-ray flux was used to diagnose the charge state distribution, and the electron temperature was extracted from a Li-like ion level population ratio. To interpret the temperature measurement, we performed Boltzmann kinetics and radiation-hydrodynamic simulations. We found that non-equilibrium atomic physics and the coupling of the radiation flux to the atomic level population kinetics play a critical role in modeling the x-ray heating of photoionized plasmas. In spite of being driven by similar x-ray drives, differences of ionization and charged state distributions in the neon and silicon plasmas are reflected in the plasma heating and observed electron temperatures.This work was sponsored in part by DOE Office of Science Grant DE-SC0014451, and the Z Facility Fundamental Science Program of SNL.

Determination of Stark parameters by cross-calibration in a multi-element laser-induced plasma

NASA Astrophysics Data System (ADS)

Liu, Hao; Truscott, Benjamin S.; Ashfold, Michael N. R.

2016-05-01

We illustrate a Stark broadening analysis of the electron density Ne and temperature Te in a laser-induced plasma (LIP), using a model free of assumptions regarding local thermodynamic equilibrium (LTE). The method relies on Stark parameters determined also without assuming LTE, which are often unknown and unavailable in the literature. Here, we demonstrate that the necessary values can be obtained in situ by cross-calibration between the spectral lines of different charge states, and even different elements, given determinations of Ne and Te based on appropriate parameters for at least one observed transition. This approach enables essentially free choice between species on which to base the analysis, extending the range over which these properties can be measured and giving improved access to low-density plasmas out of LTE. Because of the availability of suitable tabulated values for several charge states of both Si and C, the example of a SiC LIP is taken to illustrate the consistency and accuracy of the procedure. The cross-calibrated Stark parameters are at least as reliable as values obtained by other means, offering a straightforward route to extending the literature in this area.

Non-equilibrium ionization by a periodic electron beam. II. Synthetic Si IV and O IV transition region spectra

NASA Astrophysics Data System (ADS)

Dzifčáková, Elena; Dudík, Jaroslav

2018-03-01

Context. Transition region (TR) spectra typically show the Si IV 1402.8 Å line to be enhanced by a factor of 5 or more compared to the neighboring O IV 1401.2 Å, contrary to predictions of ionization equilibrium models and the Maxwellian distribution of particle energies. Non-equilibrium effects in TR spectra are therefore expected. Aims: To investigate the combination of non-equilibrium ionization and high-energy particles, we apply the model of the periodic electron beam, represented by a κ-distribution that recurs at periods of several seconds, to plasma at chromospheric temperatures of 104 K. This simple model can approximate a burst of energy release involving accelerated particles. Methods: Instantaneous time-dependent charge states of silicon and oxygen were calculated and used to synthesize the instantaneous and period-averaged spectra of Si IV and O IV. Results: The electron beam drives the plasma out of equilibrium. At electron densities of Ne = 1010 cm-3, the plasma is out of ionization equilibrium at all times in all cases we considered, while for a higher density of Ne = 1011 cm-3, ionization equilibrium can be reached toward the end of each period, depending on the conditions. In turn, the character of the period-averaged synthetic spectra also depends on the properties of the beam. While the case of κ = 2 results in spectra with strong or even dominant O IV, higher values of κ can approximate a range of observed TR spectra. Spectra similar to typically observed spectra, with the Si IV 1402.8 Å line about a factor 5 higher than O IV 1401.2 Å, are obtained for κ = 3. An even higher value of κ = 5 results in spectra that are exclusively dominated by Si IV, with negligible O IV emission. This is a possible interpretation of the TR spectra of UV (Ellerman) bursts, although an interpretation that requires a density that is 1-3 orders of magnitude lower than for equilibrium estimates. Movies associated to Fig. A.1 are available at http://https://www.aanda.org

An allosterically regulated reversible mechanical molecular switch: A de novo protein maquette functions as a redox/ionic strength sensor coupling chemical binding energy or charge interactions to conformational change

NASA Astrophysics Data System (ADS)

Grosset, Anne Marie

2000-10-01

Switch-like structural rearrangements of subunits due to charge-interactions are common in the basic biological action of proteins that couple and transfer chemical and ionic signals, sensing and regulation, mechanical force and electrochemical free energy. A simple synthetic protein model (maquette) has been designed to better understand the engineering of natural switches. Basic thermodynamic principles define the two key elements required for biological or chemical function of a switch. First, there must be two well-defined states. In this case, the two conformational states must have an energetic difference (DeltaDeltaG°) that is spanned by the applied driving force. Second, there must be an external stimulus, which preferentially interacts with one of the two states. The external stimulus provides the driving force that shifts the equilibrium from the first state to the second state (≥10:1 shifting towards ≤1:10). The energetic difference between the states must be the same order of magnitude as the driving force. In this synthetic protein, the two conformational states correspond to parallel (syn) and antiparallel (anti) assembly of the two identical helix-ss-helix subunits that bind heme close to the di-sulfide loop region. Charge interactions between two ferric hemes bound to histidines provide a driving force on the order of 2 kcal/mol (corresponding in the syn-topology to the 75--100 mV split in the heme redox potentials, or the 25--80 times weaker binding for the second ferric heme). The tetra-alpha-helix bundle has been modified to have a DeltaG around 1.8--2.5 kcal/mol (a 50--80 fold difference in the anti/syn ratio). Therefore, oxidation and reduction of the heme, or the binding of a second charged ferric heme can reversibly switch between syn- and anti-topologies, providing a sensitive detector of redox state or heme concentration. External solution conditions (e.g. ionic composition) can act on the protein remotely from the primary internal switch action and confer a secondary level of allosteric regulation. Bifunctional ligands can link subunits to shift topology. Scanning redox potentiometry can monitor the kinetics of topological change. Point amino acid substitutions and computer repacking of the hydrophobic core can modulate both the kinetics and the energetics.

Vibrational Spectroscopy of Cation and Anion Channelrhodopsins

NASA Astrophysics Data System (ADS)

Yi, Adrian S.

Optogenetics is a technique to control and monitor cell activity with light by expression of specific microbial rhodopsins. Cation channelrhodopsins (CCRs) and anion channelrhodopsins (ACRs) have been demonstrated to activate and silence cell activity, respectively. In this dissertation, the molecular mechanisms of two channelrhodopsins are studied: a CCR from Chlamydomonas augustae (CaChR1) and an ACR from Guillardia theta (GtACR1). The recently discovered GtACR1is especially interesting, as it achieves neural silencing with 1/1000th of the light intensity compared to previous microbial rhodopsin silencing ion pumps. Static and time-resolved resonance Raman, FTIR difference, and UV-visible spectroscopies were utilized in addition to various biochemical and genetic techniques to explore the molecular mechanisms of these channelrhodopsins. In CaChR1, Glu169 and Asp299 residues are located nearby the Schiff base (SB) similar to the homologous residues Asp85 and Asp212, which exist in an ionized state in unphotolyzed bacteriorhodopsin (BR) and play a key role in proton pumping. We observe significant changes in the protonation states of the SB, Glu169, and Asp299 of CaChR1 leading up to the open-channel P2 state, where all three groups exist in a charge neutral state. This unusual charge neutrality along with the position of these groups in the CaChR1 ion channel suggests that charge neutrality plays an important role in cation gating and selectivity in these low efficiency CCRs. Significant differences exist in the photocycle and protonation/hydrogen bonding states of key residues inGtACR1compared to BR and CaChR1. Resonance Raman studies reveal that in the unphotolyzed state of GtACR1, residues Glu68, Ser97 (BR Asp85 homolog), and Asp234 (BR Asp212 homolog) located near the SB exist in charge neutral states. Furthermore, upon K formation, these residues do not change their protonation states. At room temperature, a slow decay of the red-shifted K intermediate is observed, which exists in equilibrium with the L intermediate. At 80 K, a lower thermal barrier for K → L transition is observed compared to BR and CaChR1. This effect may be due to substitution of a Met residue at position 105 for the highly conserved Leu or Ile residue.

Negative Charge Neutralization in the Loops and Turns of Outer Membrane Phospholipase A Impacts Folding Hysteresis at Neutral pH.

PubMed

McDonald, Sarah K; Fleming, Karen G

2016-11-08

Hysteresis in equilibrium protein folding titrations is an experimental barrier that must be overcome to extract meaningful thermodynamic quantities. Traditional approaches to solving this problem involve testing a spectrum of solution conditions to find ones that achieve path independence. Through this procedure, a specific pH of 3.8 was required to achieve path independence for the water-to-bilayer equilibrium folding of outer membrane protein OmpLA. We hypothesized that the neutralization of negatively charged side chains (Asp and Glu) at pH 3.8 could be the physical basis for path-independent folding at this pH. To test this idea, we engineered variants of OmpLA with Asp → Asn and Glu → Gln mutations to neutralize the negative charges within various regions of the protein and tested for reversible folding at neutral pH. Although not fully resolved, our results show that these mutations in the periplasmic turns and extracellular loops are responsible for 60% of the hysteresis in wild-type folding. Overall, our study suggests that negative charges impact the folding hysteresis in outer membrane proteins and their neutralization may aid in protein engineering applications.

Dynamic relaxation of a levitated nanoparticle from a non-equilibrium steady state.

PubMed

Gieseler, Jan; Quidant, Romain; Dellago, Christoph; Novotny, Lukas

2014-05-01

Fluctuation theorems are a generalization of thermodynamics on small scales and provide the tools to characterize the fluctuations of thermodynamic quantities in non-equilibrium nanoscale systems. They are particularly important for understanding irreversibility and the second law in fundamental chemical and biological processes that are actively driven, thus operating far from thermal equilibrium. Here, we apply the framework of fluctuation theorems to investigate the important case of a system relaxing from a non-equilibrium state towards equilibrium. Using a vacuum-trapped nanoparticle, we demonstrate experimentally the validity of a fluctuation theorem for the relative entropy change occurring during relaxation from a non-equilibrium steady state. The platform established here allows non-equilibrium fluctuation theorems to be studied experimentally for arbitrary steady states and can be extended to investigate quantum fluctuation theorems as well as systems that do not obey detailed balance.

Imaging the motion of electrons in 2D semiconductor heterostructures

NASA Astrophysics Data System (ADS)

Dani, Keshav

Technological progress since the late 20th century has centered on semiconductor devices, such as transistors, diodes, and solar cells. At the heart of these devices, is the internal motion of electrons through semiconductor materials due to applied electric fields or by the excitation of photocarriers. Imaging the motion of these electrons would provide unprecedented insight into this important phenomenon, but requires high spatial and temporal resolution. Current studies of electron dynamics in semiconductors are generally limited by the spatial resolution of optical probes, or by the temporal resolution of electronic probes. In this talk, we combine femtosecond pump-probe techniques with spectroscopic photoemission electron microscopy to image the motion of photoexcited electrons from high-energy to low-energy states in a 2D InSe/GaAs heterostructure exhibiting a type-II band alignment. At the instant of photoexcitation, energy-resolved photoelectron images reveal a highly non-equilibrium distribution of photocarriers in space and energy. Thereafter, in response to the out-of-equilibrium photocarriers, we observe the spatial redistribution of charges, thus forming internal electric fields, bending the semiconductor bands, and finally impeding further charge transfer. By assembling images taken at different time-delays, we make a movie lasting a few tens of picoseconds of the electron transfer process in the photoexcited type-II heterostructure - a fundamental phenomenon in semiconductor devices like solar cells. Quantitative analysis and theoretical modeling of spatial variations in the video provide insight into future solar cells, electron dynamics in 2D materials, and other semiconductor devices.

Imaging the motion of electrons across semiconductor heterojunctions.

PubMed

Man, Michael K L; Margiolakis, Athanasios; Deckoff-Jones, Skylar; Harada, Takaaki; Wong, E Laine; Krishna, M Bala Murali; Madéo, Julien; Winchester, Andrew; Lei, Sidong; Vajtai, Robert; Ajayan, Pulickel M; Dani, Keshav M

2017-01-01

Technological progress since the late twentieth century has centred on semiconductor devices, such as transistors, diodes and solar cells. At the heart of these devices is the internal motion of electrons through semiconductor materials due to applied electric fields or by the excitation of photocarriers. Imaging the motion of these electrons would provide unprecedented insight into this important phenomenon, but requires high spatial and temporal resolution. Current studies of electron dynamics in semiconductors are generally limited by the spatial resolution of optical probes, or by the temporal resolution of electronic probes. Here, by combining femtosecond pump-probe techniques with spectroscopic photoemission electron microscopy, we imaged the motion of photoexcited electrons from high-energy to low-energy states in a type-II 2D InSe/GaAs heterostructure. At the instant of photoexcitation, energy-resolved photoelectron images revealed a highly non-equilibrium distribution of photocarriers in space and energy. Thereafter, in response to the out-of-equilibrium photocarriers, we observed the spatial redistribution of charges, thus forming internal electric fields, bending the semiconductor bands, and finally impeding further charge transfer. By assembling images taken at different time-delays, we produced a movie lasting a few trillionths of a second of the electron-transfer process in the photoexcited type-II heterostructure-a fundamental phenomenon in semiconductor devices such as solar cells. Quantitative analysis and theoretical modelling of spatial variations in the movie provide insight into future solar cells, 2D materials and other semiconductor devices.

Imaging the motion of electrons across semiconductor heterojunctions

NASA Astrophysics Data System (ADS)

Man, Michael K. L.; Margiolakis, Athanasios; Deckoff-Jones, Skylar; Harada, Takaaki; Wong, E. Laine; Krishna, M. Bala Murali; Madéo, Julien; Winchester, Andrew; Lei, Sidong; Vajtai, Robert; Ajayan, Pulickel M.; Dani, Keshav M.

2017-01-01

Technological progress since the late twentieth century has centred on semiconductor devices, such as transistors, diodes and solar cells. At the heart of these devices is the internal motion of electrons through semiconductor materials due to applied electric fields or by the excitation of photocarriers. Imaging the motion of these electrons would provide unprecedented insight into this important phenomenon, but requires high spatial and temporal resolution. Current studies of electron dynamics in semiconductors are generally limited by the spatial resolution of optical probes, or by the temporal resolution of electronic probes. Here, by combining femtosecond pump-probe techniques with spectroscopic photoemission electron microscopy, we imaged the motion of photoexcited electrons from high-energy to low-energy states in a type-II 2D InSe/GaAs heterostructure. At the instant of photoexcitation, energy-resolved photoelectron images revealed a highly non-equilibrium distribution of photocarriers in space and energy. Thereafter, in response to the out-of-equilibrium photocarriers, we observed the spatial redistribution of charges, thus forming internal electric fields, bending the semiconductor bands, and finally impeding further charge transfer. By assembling images taken at different time-delays, we produced a movie lasting a few trillionths of a second of the electron-transfer process in the photoexcited type-II heterostructure—a fundamental phenomenon in semiconductor devices such as solar cells. Quantitative analysis and theoretical modelling of spatial variations in the movie provide insight into future solar cells, 2D materials and other semiconductor devices.

Application of surface complexation models to anion adsorption by natural materials.

PubMed

Goldberg, Sabine

2014-10-01

Various chemical models of ion adsorption are presented and discussed. Chemical models, such as surface complexation models, provide a molecular description of anion adsorption reactions using an equilibrium approach. Two such models, the constant capacitance model and the triple layer model, are described in the present study. Characteristics common to all the surface complexation models are equilibrium constant expressions, mass and charge balances, and surface activity coefficient electrostatic potential terms. Methods for determining parameter values for surface site density, capacitances, and surface complexation constants also are discussed. Spectroscopic experimental methods of establishing ion adsorption mechanisms include vibrational spectroscopy, nuclear magnetic resonance spectroscopy, electron spin resonance spectroscopy, X-ray absorption spectroscopy, and X-ray reflectivity. Experimental determinations of point of zero charge shifts and ionic strength dependence of adsorption results and molecular modeling calculations also can be used to deduce adsorption mechanisms. Applications of the surface complexation models to heterogeneous natural materials, such as soils, using the component additivity and the generalized composite approaches are described. Emphasis is on the generalized composite approach for predicting anion adsorption by soils. Continuing research is needed to develop consistent and realistic protocols for describing ion adsorption reactions on soil minerals and soils. The availability of standardized model parameter databases for use in chemical speciation-transport models is critical. Published 2014 Wiley Periodicals Inc. on behalf of SETAC. This article is a US Government work and as such, is in the public domain in the in the United States of America.

Charge density on thin straight wire, revisited

NASA Astrophysics Data System (ADS)

Jackson, J. D.

2000-09-01

The question of the equilibrium linear charge density on a charged straight conducting "wire" of finite length as its cross-sectional dimension becomes vanishingly small relative to the length is revisited in our didactic presentation. We first consider the wire as the limit of a prolate spheroidal conductor with semi-minor axis a and semi-major axis c when a/c<<1. We then treat an azimuthally symmetric straight conductor of length 2c and variable radius r(z) whose scale is defined by a parameter a. A procedure is developed to find the linear charge density λ(z) as an expansion in powers of 1/Λ, where Λ≡ln(4c2/a2), beginning with a uniform line charge density λ0. We show, for this rather general wire, that in the limit Λ>>1 the linear charge density becomes essentially uniform, but that the tiny nonuniformity (of order 1/Λ) is sufficient to produce a tangential electric field (of order Λ0) that cancels the zeroth-order field that naively seems to belie equilibrium. We specialize to a right circular cylinder and obtain the linear charge density explicitly, correct to order 1/Λ2 inclusive, and also the capacitance of a long isolated charged cylinder, a result anticipated in the published literature 37 years ago. The results for the cylinder are compared with published numerical computations. The second-order correction to the charge density is calculated numerically for a sampling of other shapes to show that the details of the distribution for finite 1/Λ vary with the shape, even though density becomes constant in the limit Λ→∞. We give a second method of finding the charge distribution on the cylinder, one that approximates the charge density by a finite polynomial in z2 and requires the solution of a coupled set of linear algebraic equations. Perhaps the most striking general observation is that the approach to uniformity as a/c→0 is extremely slow.

Analysis of gene network robustness based on saturated fixed point attractors

PubMed Central

2014-01-01

The analysis of gene network robustness to noise and mutation is important for fundamental and practical reasons. Robustness refers to the stability of the equilibrium expression state of a gene network to variations of the initial expression state and network topology. Numerical simulation of these variations is commonly used for the assessment of robustness. Since there exists a great number of possible gene network topologies and initial states, even millions of simulations may be still too small to give reliable results. When the initial and equilibrium expression states are restricted to being saturated (i.e., their elements can only take values 1 or −1 corresponding to maximum activation and maximum repression of genes), an analytical gene network robustness assessment is possible. We present this analytical treatment based on determination of the saturated fixed point attractors for sigmoidal function models. The analysis can determine (a) for a given network, which and how many saturated equilibrium states exist and which and how many saturated initial states converge to each of these saturated equilibrium states and (b) for a given saturated equilibrium state or a given pair of saturated equilibrium and initial states, which and how many gene networks, referred to as viable, share this saturated equilibrium state or the pair of saturated equilibrium and initial states. We also show that the viable networks sharing a given saturated equilibrium state must follow certain patterns. These capabilities of the analytical treatment make it possible to properly define and accurately determine robustness to noise and mutation for gene networks. Previous network research conclusions drawn from performing millions of simulations follow directly from the results of our analytical treatment. Furthermore, the analytical results provide criteria for the identification of model validity and suggest modified models of gene network dynamics. The yeast cell-cycle network is used as an illustration of the practical application of this analytical treatment. PMID:24650364

Ion-Scale Excitations in a Strongly Coupled Astrophysical Plasma with Nuclei of Heavy Elements

NASA Astrophysics Data System (ADS)

Hossen, M. R.; Ema, S. A.; Mamun, A. A.

2017-12-01

The linear and nonlinear propagation of ultrarelativistic and nonrelativistic analysis on modified ion-acoustic (MIA) waves in a strongly coupled unmagnetized collisionless relativistic space plasma system is carried out. Plasma system is assumed to contain strongly coupled nonrelativistic ion fluids, both nonrelativistic and ultrarelativistic degenerate electron and positron fluids, and positively charged static heavy elements. The restoring force is provided by the degenerate pressure of the electron and positron fluids, whereas the inertia is provided by the mass of ions. The positively charged static heavy elements participate only in maintaining the quasineutrality condition at equilibrium. The well-known reductive perturbation method is used to derive the Burgers and Korteweg-de Vries equations. Their shock and solitary wave solutions are numerically analyzed to understand the localized electrostatic disturbances. The basic characteristics of MIA shock and solitary waves are found to be significantly modified by the effects of degenerate pressures of electron, positron, and ion fluids, their number densities, and various charge state of heavy elements. The implications of our results to dense plasmas in compact astrophysical objects (e.g., nonrotating white dwarfs, neutron stars, etc.) are briefly discussed.

Dynamical behaviors of inter-out-of-equilibrium state intervals in Korean futures exchange markets

NASA Astrophysics Data System (ADS)

Lim, Gyuchang; Kim, SooYong; Kim, Kyungsik; Lee, Dong-In; Scalas, Enrico

2008-05-01

A recently discovered feature of financial markets, the two-phase phenomenon, is utilized to categorize a financial time series into two phases, namely equilibrium and out-of-equilibrium states. For out-of-equilibrium states, we analyze the time intervals at which the state is revisited. The power-law distribution of inter-out-of-equilibrium state intervals is shown and we present an analogy with discrete-time heat bath dynamics, similar to random Ising systems. In the mean-field approximation, this model reduces to a one-dimensional multiplicative process. By varying global and local model parameters, the relevance between volatilities in financial markets and the interaction strengths between agents in the Ising model are investigated and discussed.

Communications: Complete description of re-entrant phase behavior in a charge variable colloidal model system.

PubMed

Wette, Patrick; Klassen, Ina; Holland-Moritz, Dirk; Herlach, Dieter M; Schöpe, Hans Joachim; Lorenz, Nina; Reiber, Holger; Palberg, Thomas; Roth, Stephan V

2010-04-07

In titration experiments with NaOH, we have determined the full phase diagram of charged colloidal spheres in dependence on the particle density n, the particle effective charge Z(eff) and the concentration of screening electrolyte c using microscopy, light and ultrasmall angle x-ray scattering (USAXS). For sufficiently large n, the system crystallizes upon increasing Z(eff) at constant c and melts upon increasing c at only slightly altered Z(eff). In contrast to earlier work, equilibrium phase boundaries are consistent with a universal melting line prediction from computer simulation, if the elasticity effective charge is used. This charge accounts for both counterion condensation and many-body effects.

An advanced model framework for solid electrolyte intercalation batteries.

PubMed

Landstorfer, Manuel; Funken, Stefan; Jacob, Timo

2011-07-28

Recent developments of solid electrolytes, especially lithium ion conductors, led to all solid state batteries for various applications. In addition, mathematical models sprout for different electrode materials and battery types, but are missing for solid electrolyte cells. We present a mathematical model for ion flux in solid electrolytes, based on non-equilibrium thermodynamics and functional derivatives. Intercalated ion diffusion within the electrodes is further considered, allowing the computation of the ion concentration at the electrode/electrolyte interface. A generalized Frumkin-Butler-Volmer equation describes the kinetics of (de-)intercalation reactions and is here extended to non-blocking electrodes. Using this approach, numerical simulations were carried out to investigate the space charge region at the interface. Finally, discharge simulations were performed to study different limitations of an all solid state battery cell. This journal is © the Owner Societies 2011

Capillary electrophoresis investigation on equilibrium between polymer-related and surfactant-related species in aqueous polymer-surfactant solutions.

PubMed

Wu, Yefan; Chen, Miaomiao; Fang, Yun; Zhu, Meng

2017-03-17

It was inferred from aqueous solution behavior of nonionic polymers and anionic surfactants that the formation of charged polymer-bound surfactant micelle above critical aggregation concentration (cac) and the formation of free surfactant micelle beyond polymer saturation point (psp), but there was still a lack of direct experimental evidence for the considered equilibrium chemical species. Three modes of capillary electrophoresis are applied in this paper to study the complexation between nonionic polymers, polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG), and sodium dodecylbenzenesulfonate (SDBS) by successfully distinguishing the imaginary charged polymer-bound SDBS micelle from nonionic polymer and SDBS molecule. Perhaps even more important, it is the action of SDBS as both a main surfactant and a UV probe that makes the free surfactant micelle emerged in electropherogram beyond psp, and thus makes it possible for the first time to provide the equilibrium relationship of the polymer-related and the surfactant-related species in the concentration regions divided into by cac and psp. Copyright © 2017 Elsevier B.V. All rights reserved.

Numerical simulation of a non-equilibrium electrokinetic micro/nano fluidic mixer

NASA Astrophysics Data System (ADS)

Hadidi, H.; Kamali, R.

2016-03-01

In this study we numerically simulate a novel micromixer that utilizes vortex generation from the non-equilibrium electrokinetics near the micro/nanochannels interface. After mixing in combined pressure-driven and electroosmotic flows was compared with mixing in a pure pressure-driven flow, the superior mixing performance of the former was evident: for a specific case study, 90% mixing of two fluid streams for a short mixing length was achieved. The results of our numerical study were very similar to those of previously reported experiments. In this paper we explain the phenomenon occurring adjacent to the nano-junctions by plotting the electrical field components, the velocity contours and the concentration distribution in the micromixer. The vortices at the micro/nanochannel interface were obviously indicators of non-equilibrium behaviour in these regions. At the end, the mixing performance was evaluated by the investigation of different applied voltages, Reynolds numbers and surface charge densities using the mixing index parameter, and the results showed that more efficient mixing occurred when the applied voltage and surface charge density magnitude were increased and the Reynolds number was decreased.

Electrostatic model for protein adsorption in ion-exchange chromatography and application to monoclonal antibodies, lysozyme and chymotrypsinogen A.

PubMed

Guélat, Bertrand; Ströhlein, Guido; Lattuada, Marco; Morbidelli, Massimo

2010-08-27

A model for the adsorption equilibrium of proteins in ion-exchange chromatography explicitly accounting for the effect of pH and salt concentration in the limit of highly diluted systems was developed. It is based on the use of DLVO theory to estimate the electrostatic interactions between the charged surface of the ion-exchanger and the proteins. The corresponding charge distributions were evaluated as a function of pH and salt concentration using a molecular approach. The model was verified for the adsorption equilibrium of lysozyme, chymotrypsinogen A and four industrial monoclonal antibodies on two strong cation-exchangers. The adsorption equilibrium constants of these proteins were determined experimentally at various pH values and salt concentrations and the model was fitted with a good agreement using three adjustable parameters for each protein in the whole range of experimental conditions. Despite the simplifications of the model regarding the geometry of the protein-ion-exchanger system, the physical meaning of the parameters was retained. 2010 Elsevier B.V. All rights reserved.

Improved partition equilibrium model for predicting analyte response in electrospray ionization mass spectrometry.

PubMed

Du, Lihong; White, Robert L

2009-02-01

A previously proposed partition equilibrium model for quantitative prediction of analyte response in electrospray ionization mass spectrometry is modified to yield an improved linear relationship. Analyte mass spectrometer response is modeled by a competition mechanism between analyte and background electrolytes that is based on partition equilibrium considerations. The correlation between analyte response and solution composition is described by the linear model over a wide concentration range and the improved model is shown to be valid for a wide range of experimental conditions. The behavior of an analyte in a salt solution, which could not be explained by the original model, is correctly predicted. The ion suppression effects of 16:0 lysophosphatidylcholine (LPC) on analyte signals are attributed to a combination of competition for excess charge and reduction of total charge due to surface tension effects. In contrast to the complicated mathematical forms that comprise the original model, the simplified model described here can more easily be employed to predict analyte mass spectrometer responses for solutions containing multiple components. Copyright (c) 2008 John Wiley & Sons, Ltd.

Metastable electronic populations and relaxation of Fe(I), Fe(II), and Fe(III) in MgO observed by Mössbauer emission spectroscopy

NASA Astrophysics Data System (ADS)

Tuczek, F.; Spiering, H.; Gütlich, P.

1990-06-01

Magnetic-field Mössbauer emission spectra of 57Co in MgO single crystals covering a broad velocity range and measured up to high signal-to-noise ratios are presented. In accordance with a previous study, three charge states of 57Fe are found after 57Co(EC)57Fe (EC stands for electron capture). The evaluation of the Fe(III) fraction indicates nonthermalized populations of the 6A1 ground-state Zeeman levels. The field, temperature, and angular dependences of these populations are evaluated and display qualitative differences to the findings in 57Co/LiNbO3. The implications of the cubic symmetry on the spin-selective ground-state population are considered. In addition, a completely analogous phenomenon is evidenced for the first time within an Fe(II) electronic manifold, namely, the Γ5g ground state of Fe(II) in MgO, after the nuclear decay. In contrast to the Fe(III) case, these populations are not static within the Mössbauer time window. It turns out that the attainment of thermal equilibrium can be conveniently observed by changing the field value, evidencing a direct relaxation process at 4.2 K within Γ5g. The relaxation rates are compatible with static strain data; an initial alignment is observed. Finally, there is strong evidence that the Fe(I) fraction is also populated out of thermal equilibrium. In addition to these ground-state spectra, two features are present that may be attributed to metastable excited states of Fe(II) and Fe(III). It is described in detail how these various contributions can be disentangled.

Effect of phenytoin on sodium conductances in rat hippocampal CA1 pyramidal neurons

PubMed Central

Zeng, Zhen; Hill-Yardin, Elisa L.; Williams, David; O'Brien, Terence; Serelis, Andris

2016-01-01

The antiepileptic drug phenytoin (PHT) is thought to reduce the excitability of neural tissue by stabilizing sodium channels (NaV) in inactivated states. It has been suggested the fast-inactivated state (IF) is the main target, although slow inactivation (IS) has also been implicated. Other studies on local anesthetics with similar effects on sodium channels have implicated the NaV voltage sensor interactions. In this study, we reexamined the effect of PHT in both equilibrium and dynamic transitions between fast and slower forms of inactivation in rat hippocampal CA1 pyramidal neurons. The effects of PHT were observed on fast and slow inactivation processes, as well as on another identified “intermediate” inactivation process. The effect of enzymatic removal of IF was also studied, as well as effects on the residual persistent sodium current (INaP). A computational model based on a gating charge interaction was derived that reproduced a range of PHT effects on NaV equilibrium and state transitions. No effect of PHT on IF was observed; rather, PHT appeared to facilitate the occupancy of other closed states, either through enhancement of slow inactivation or through formation of analogous drug-bound states. The overall significance of these observations is that our data are inconsistent with the commonly held view that the archetypal NaV channel inhibitor PHT stabilizes fast inactivation states, and we demonstrate that conventional slow activation “IS” and the more recently identified intermediate-duration inactivation process “II” are the primary functional targets of PHT. In addition, we show that the traditional explanatory frameworks based on the “modulated receptor hypothesis” can be substituted by simple, physiologically plausible interactions with voltage sensors. Additionally, INaP was not preferentially inhibited compared with peak INa at short latencies (50 ms) by PHT. PMID:27489371

Synthesis, characterization, crystal structure and solution studies of a novel proton transfer (charge transfer) complex of 2,2‧-dipyridylamine with 2,6-pyridine dicarboxylic acid

NASA Astrophysics Data System (ADS)

Ghasemi, Khaled; Rezvani, Ali Reza; Shokrollahi, Ardeshir; Zarghampour, Fereshteh; Moghimi, Abolghasem; García-Granda, Santiago; Mendoza-Meroño, Rafael

2015-06-01

Reaction between 2,2‧-dipyridylamine (DPA) and 2,6-pyridine dicarboxylic acid (dipicolinic acid, dipicH2), in water results in the formation of a proton transfer or charge transfer (CT) complex, (DPAH)+(dipicH)-·H2O, 1. The characterization was performed using 1H NMR and FTIR spectroscopy, elemental analysis and X-ray crystallography. The crystal system is triclinic with space group P1. The structural investigations exhibit that the hydrogen bonds and π-π stacking interactions stabilize the crystal structure of proton transfer complex. The protonation constants of 2,6-pyridine dicarboxylic acid, 2,2‧-dipyridylamine and the equilibrium constants for dipic-DPA (1:1) proton transfer system were calculated by potentiometric pH titration method using Hyperquad2008 program. The stoichiometries of the proton transfer species in solution was in agreement with the solid state result.

What Can Be Learned from X-Ray Spectroscopy Concerning Hot Gas in the Local Bubble and Charge Exchange Processes?

NASA Technical Reports Server (NTRS)

Snowden, S. L.

2008-01-01

Both solar wind charge exchange emission and diffuse thermal emission from the Local Bubble are strongly dominated in the soft X-ray band by lines from highly ionized elements. While both processes share many of the same lines, the spectra should differ significantly due to the different production mechanisms, abundances, and ionization states. Despite their distinct spectral signatures, current and past observatories have lacked the spectral resolution to adequately distinguish between the two sources. High-resolution X-ray spectroscopy instrumentation proposed for future missions has the potential to answer fundamental questions such as whether there is any hot plasma in the Local Hot Bubble, and if so, what are the abundances of the emitting plasma and whether the plasma is in equilibrium. Such instrumentation will provide dynamic information about the solar wind including data on ion species which are currently difficult to track. It will also make possible remote sensing of the solar wind.

Clocking Femtosecond Collisional Dynamics via Resonant X-Ray Spectroscopy

NASA Astrophysics Data System (ADS)

van den Berg, Q. Y.; Fernandez-Tello, E. V.; Burian, T.; Chalupský, J.; Chung, H.-K.; Ciricosta, O.; Dakovski, G. L.; Hájková, V.; Hollebon, P.; Juha, L.; Krzywinski, J.; Lee, R. W.; Minitti, M. P.; Preston, T. R.; de la Varga, A. G.; Vozda, V.; Zastrau, U.; Wark, J. S.; Velarde, P.; Vinko, S. M.

2018-02-01

Electron-ion collisional dynamics is of fundamental importance in determining plasma transport properties, nonequilibrium plasma evolution, and electron damage in diffraction imaging applications using bright x-ray free-electron lasers (FELs). Here we describe the first experimental measurements of ultrafast electron impact collisional ionization dynamics using resonant core-hole spectroscopy in a solid-density magnesium plasma, created and diagnosed with the Linac Coherent Light Source x-ray FEL. By resonantly pumping the 1 s →2 p transition in highly charged ions within an optically thin plasma, we have measured how off-resonance charge states are populated via collisional processes on femtosecond time scales. We present a collisional cross section model that matches our results and demonstrates how the cross sections are enhanced by dense-plasma effects including continuum lowering. Nonlocal thermodynamic equilibrium collisional radiative simulations show excellent agreement with the experimental results and provide new insight on collisional ionization and three-body-recombination processes in the dense-plasma regime.

Clocking Femtosecond Collisional Dynamics via Resonant X-Ray Spectroscopy

DOE PAGES

van den Berg, Q. Y.; Fernandez-Tello, E. V.; Burian, T.; ...

2018-02-01

Electron-ion collisional dynamics is of fundamental importance in determining plasma transport properties, nonequilibrium plasma evolution, and electron damage in diffraction imaging applications using bright x-ray free-electron lasers (FELs). Here in this paper, we describe the first experimental measurements of ultrafast electron impact collisional ionization dynamics using resonant core-hole spectroscopy in a solid-density magnesium plasma, created and diagnosed with the Linac Coherent Light Source x-ray FEL. By resonantly pumping the 1s → 2p transition in highly charged ions within an optically thin plasma, we have measured how off-resonance charge states are populated via collisional processes on femtosecond time scales. We presentmore » a collisional cross section model that matches our results and demonstrates how the cross sections are enhanced by dense-plasma effects including continuum lowering. Nonlocal thermodynamic equilibrium collisional radiative simulations show excellent agreement with the experimental results and provide new insight on collisional ionization and three-body-recombination processes in the dense-plasma regime.« less

Relations between heat exchange and Rényi divergences

NASA Astrophysics Data System (ADS)

Wei, Bo-Bo

2018-04-01

In this work, we establish an exact relation which connects the heat exchange between two systems initialized in their thermodynamic equilibrium states at different temperatures and the Rényi divergences between the initial thermodynamic equilibrium state and the final nonequilibrium state of the total system. The relation tells us that the various moments of the heat statistics are determined by the Renyi divergences between the initial equilibrium state and the final nonequilibrium state of the global system. In particular the average heat exchange is quantified by the relative entropy between the initial equilibrium state and the final nonequilibrium state of the global system. The relation is applicable to both finite classical systems and finite quantum systems.

Relations between heat exchange and Rényi divergences.

PubMed

Wei, Bo-Bo

2018-04-01

In this work, we establish an exact relation which connects the heat exchange between two systems initialized in their thermodynamic equilibrium states at different temperatures and the Rényi divergences between the initial thermodynamic equilibrium state and the final nonequilibrium state of the total system. The relation tells us that the various moments of the heat statistics are determined by the Renyi divergences between the initial equilibrium state and the final nonequilibrium state of the global system. In particular the average heat exchange is quantified by the relative entropy between the initial equilibrium state and the final nonequilibrium state of the global system. The relation is applicable to both finite classical systems and finite quantum systems.

Effects of the impurity-host interactions on the nonradiative processes in ZnS:Cr

NASA Astrophysics Data System (ADS)

Tablero, C.

2010-11-01

There is a great deal of controversy about whether the behavior of an intermediate band in the gap of semiconductors is similar or not to the deep-gap levels. It can have significant consequences, for example, on the nonradiative recombination. In order to analyze the behavior of an intermediate band, we have considered the effect of the inward and outward displacements corresponding to breathing and longitudinal modes of Cr-doped ZnS and on the charge density for different processes involved in the nonradiative recombination using first-principles. This metal-doped zinc chalcogenide has a partially filled band within the host semiconductor gap. In contrast to the properties exhibited by deep-gap levels in other systems, we find small variations in the equilibrium configurations, forces, and electronic density around the Cr when the nonradiative recombination mechanisms modify the intermediate band charge. The charge density around the impurity is equilibrated in response to the perturbations in the equilibrium nuclear configuration and the charge of the intermediate band. The equilibration follows a Le Chatelier principle through the modification of the contribution from the impurity to the intermediate band and to the valence band. The intermediate band introduced by Cr in ZnS for the concentrations analyzed makes the electronic capture difficult and later multiphonon emission in the charge-transfer processes, in accordance with experimental results.

Protein Diffusion on Charged Membranes: A Dynamic Mean-Field Model Describes Time Evolution and Lipid Reorganization

PubMed Central

Khelashvili, George; Weinstein, Harel; Harries, Daniel

2008-01-01

As charged macromolecules adsorb and diffuse on cell membranes in a large variety of cell signaling processes, they can attract or repel oppositely charged lipids. This results in lateral membrane rearrangement and affects the dynamics of protein function. To address such processes quantitatively we introduce a dynamic mean-field scheme that allows self-consistent calculations of the equilibrium state of membrane-protein complexes after such lateral reorganization of the membrane components, and serves to probe kinetic details of the process. Applicable to membranes with heterogeneous compositions containing several types of lipids, this comprehensive method accounts for mobile salt ions and charged macromolecules in three dimensions, as well as for lateral demixing of charged and net-neutral lipids in the membrane plane. In our model, the mobility of membrane components is governed by the diffusion-like Cahn-Hilliard equation, while the local electrochemical potential is based on nonlinear Poisson-Boltzmann theory. We illustrate the method by applying it to the adsorption of the anionic polypeptide poly-Lysine on negatively charged lipid membranes composed of binary mixtures of neutral and monovalent lipids, or onto ternary mixtures of neutral, monovalent, and multivalent lipids. Consistent with previous calculations and experiments, our results show that at steady-state multivalent lipids (such as PIP2), but not monovalent lipid (such as phosphatidylserine), will segregate near the adsorbing macromolecules. To address the corresponding diffusion of the adsorbing protein in the membrane plane, we couple lipid mobility with the propagation of the adsorbing protein through a dynamic Monte Carlo scheme. We find that due to their higher mobility dictated by the electrochemical potential, multivalent lipids such as PIP2 more quickly segregate near oppositely charged proteins than do monovalent lipids, even though their diffusion constants may be similar. The segregation, in turn, slows protein diffusion, as lipids introduce an effective drag on the motion of the adsorbate. In contrast, monovalent lipids such as phosphatidylserine only weakly segregate, and the diffusions of protein and lipid remain largely uncorrelated. PMID:18065451

Analytical gradients for MP2, double hybrid functionals, and TD‐DFT with polarizable embedding described by fluctuating charges

PubMed Central

Carnimeo, Ivan; Cappelli, Chiara

2015-01-01

A polarizable quantum mechanics (QM)/ molecular mechanics (MM) approach recently developed for Hartree–Fock (HF) and Kohn–Sham (KS) methods has been extended to energies and analytical gradients for MP2, double hybrid functionals, and TD‐DFT models, thus allowing the computation of equilibrium structures for excited electronic states together with more accurate results for ground electronic states. After a detailed presentation of the theoretical background and of some implementation details, a number of test cases are analyzed to show that the polarizable embedding model based on fluctuating charges (FQ) is remarkably more accurate than the corresponding electronic embedding based on a fixed charge (FX) description. In particular, a set of electronegativities and hardnesses has been optimized for interactions between QM and FQ regions together with new repulsion–dispersion parameters. After validation of both the numerical implementation and of the new parameters, absorption electronic spectra have been computed for representative model systems including vibronic effects. The results show remarkable agreement with full QM computations and significant improvement with respect to the corresponding FX results. The last part of the article provides some hints about computation of solvatochromic effects on absorption spectra in aqueous solution as a function of the number of FQ water molecules and on the use of FX external shells to improve the convergence of the results. © 2015 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc. PMID:26399473

Equilibrium constant for calcium ion and ascorbate ion.

PubMed

Tsao, C S

1984-02-15

The combination of calcium and ascorbic acid in water at 25 degrees C has been examined by measuring the change of free calcium ion concentration as ascorbate was added in small increment to a solution of calcium. The data show clearly that complex formation between calcium ion and ascorbate ion occurred. At ionic strength mu = 0.1-0.2, the equilibrium constant of Ca++ and the singly-charged ascorbate ion has been measured to be 2.1 M-1. The precision of the result is better than 5% and the accuracy is estimated to be better than 20%. The application of the equilibrium constants is discussed.

Anatomy of charge-exchange straggling

NASA Astrophysics Data System (ADS)

Sigmund, P.; Osmani, O.; Schinner, A.

2014-11-01

We have studied charge-exchange straggling theoretically for swift krypton and silicon ions and five target gases in the MeV/u energy regime. We find a pronounced two-peak structure for all ion-target combinations. The peak at the highest energy appears around the velocity where the bare ion and the one-electron ion are equally abundant in the equilibrium charge distribution. Correspondingly, the low-energy peak appears near the cross-over between the charge fractions of the two- and the three-electron ion. The possibility of further peaks at lower energies is discussed. Our findings are compared with recent experimental results on straggling of krypton beams.

Self-regulation mechanism for charged point defects in hybrid halide perovskites

DOE PAGES

Walsh, Aron; Scanlon, David O.; Chen, Shiyou; ...

2014-12-11

Hybrid halide perovskites such as methylammonium lead iodide (CH 3NH 3PbI 3) exhibit unusually low free-carrier concentrations despite being processed at low-temperatures from solution. We demonstrate, through quantum mechanical calculations, that an origin of this phenomenon is a prevalence of ionic over electronic disorder in stoichiometric materials. Schottky defect formation provides a mechanism to self-regulate the concentration of charge carriers through ionic compensation of charged point defects. The equilibrium charged vacancy concentration is predicted to exceed 0.4 % at room temperature. Furthermore, this behavior, which goes against established defect conventions for inorganic semiconductors, has implications for photovoltaic performance.

Ion-atom charge-transfer reactions and a hot intercloud medium. [in interstellar space

NASA Technical Reports Server (NTRS)

Steigman, G.

1975-01-01

An investigation is conducted concerning the ionization equilibrium of carbon in a hot intercloud medium (ICM), taking into account various charge-transfer reactions. Attention is given to problems related to observations of carbon along the lines of sight to several unreddened stars. It is pointed out that the observed underabundance of C III and overabundance of C I can be consistent with the presence of a hot, partially ionized ICM, provided that two of the charge-transfer reactions considered are rapid at thermal energies.

Electric Double-Layer Interaction between Dissimilar Charge-Conserved Conducting Plates.

PubMed

Chan, Derek Y C

2015-09-15

Small metallic particles used in forming nanostructured to impart novel optical, catalytic, or tribo-rheological can be modeled as conducting particles with equipotential surfaces that carry a net surface charge. The value of the surface potential will vary with the separation between interacting particles, and in the absence of charge-transfer or electrochemical reactions across the particle surface, the total charge of each particle must also remain constant. These two physical conditions require the electrostatic boundary condition for metallic nanoparticles to satisfy an equipotential whole-of-particle charge conservation constraint that has not been studied previously. This constraint gives rise to a global charge conserved constant potential boundary condition that results in multibody effects in the electric double-layer interaction that are either absent or are very small in the familiar constant potential or constant charge or surface electrochemical equilibrium condition.

First-Principles Quantum Dynamics of Singlet Fission: Coherent versus Thermally Activated Mechanisms Governed by Molecular π Stacking

NASA Astrophysics Data System (ADS)

Tamura, Hiroyuki; Huix-Rotllant, Miquel; Burghardt, Irene; Olivier, Yoann; Beljonne, David

2015-09-01

Singlet excitons in π -stacked molecular crystals can split into two triplet excitons in a process called singlet fission that opens a route to carrier multiplication in photovoltaics. To resolve controversies about the mechanism of singlet fission, we have developed a first principles nonadiabatic quantum dynamical model that reveals the critical role of molecular stacking symmetry and provides a unified picture of coherent versus thermally activated singlet fission mechanisms in different acenes. The slip-stacked equilibrium packing structure of pentacene derivatives is found to enhance ultrafast singlet fission mediated by a coherent superexchange mechanism via higher-lying charge transfer states. By contrast, the electronic couplings for singlet fission strictly vanish at the C2 h symmetric equilibrium π stacking of rubrene. In this case, singlet fission is driven by excitations of symmetry-breaking intermolecular vibrations, rationalizing the experimentally observed temperature dependence. Design rules for optimal singlet fission materials therefore need to account for the interplay of molecular π -stacking symmetry and phonon-induced coherent or thermally activated mechanisms.

Equilibrium thermodynamics and folding kinetics of a short, fast-folding, beta-hairpin.

PubMed

Jimenez-Cruz, Camilo A; Garcia, Angel E

2014-04-14

Equilibrium thermodynamics of a short beta-hairpin are studied using unbiased all-atom replica exchange molecular dynamics simulations in explicit solvent. An exploratory analysis of the free energy landscape of the system is provided in terms of various structural characteristics, for both the folded and unfolded ensembles. We find that the favorable interactions between the ends introduced by the tryptophan cap, along with the flexibility of the turn region, explain the remarkable stability of the folded state. Charging of the N termini results in effective roughening of the free energy landscape and stabilization of non-native contacts. Folding-unfolding dynamics are further discussed using a set of 2413 independent molecular dynamics simulations, 2 ns to 20 ns long, at the melting temperature of the beta-hairpin. A novel method for the construction of Markov models consisting of an iterative refinement of the discretization in reduced dimensionality is presented and used to generate a detailed kinetic network of the system. The hairpin is found to fold heterogeneously on sub-microsecond timescales, with the relative position of the tryptophan side chains driving the selection of the specific pathway.

Charging and Screening in Nonpolar Solutions of Nonionizable Surfactants

NASA Astrophysics Data System (ADS)

Behrens, Sven

2010-03-01

Nonpolar liquids do not easily accommodate electric charges, but surfactant additives are often found to dramatically increase the solution conductivity and promote surface charging of suspended colloid particles. Such surfactant-mediated electrostatic effects have been associated with equilibrium charge fluctuations among reverse surfactant micelles and in some cases with the statistically rare ionization of individual surfactant molecules. Here we present experimental evidence that even surfactants without any ionizable group can mediate charging and charge screening in nonpolar oils, and that they can do so at surfactant concentrations well below the critical micelle concentration (cmc). Precision conductometry, light scattering, and Karl-Fischer titration of sorbitan oleate solutions in hexane, paired with electrophoretic mobility measurements on suspended polymer particles, reveal a distinctly electrostatic action of the surfactant. We interpret our observations in terms of a charge fluctuation model and argue that the observed charging processes are likely facilitated, but not limited, by the presence of ionizable impurities.

A dynamic parking charge optimal control model under perspective of commuters' evolutionary game behavior

NASA Astrophysics Data System (ADS)

Lin, XuXun; Yuan, PengCheng

2018-01-01

In this research we consider commuters' dynamic learning effect by modeling the trip mode choice behavior from a new perspective of dynamic evolutionary game theory. We explore the behavior pattern of different types of commuters and study the evolution path and equilibrium properties under different traffic conditions. We further establish a dynamic parking charge optimal control (referred to as DPCOC) model to alter commuters' trip mode choice while minimizing the total social cost. Numerical tests show. (1) Under fixed parking fee policy, the evolutionary results are completely decided by the travel time and the only method for public transit induction is to increase the parking charge price. (2) Compared with fixed parking fee policy, DPCOC policy proposed in this research has several advantages. Firstly, it can effectively turn the evolutionary path and evolutionary stable strategy to a better situation while minimizing the total social cost. Secondly, it can reduce the sensitivity of trip mode choice behavior to traffic congestion and improve the ability to resist interferences and emergencies. Thirdly, it is able to control the private car proportion to a stable state and make the trip behavior more predictable for the transportation management department. The research results can provide theoretical basis and decision-making references for commuters' mode choice prediction, dynamic setting of urban parking charge prices and public transit induction.

Diagnostics of Particles emitted from a Laser generated Plasma: Experimental Data and Simulations

NASA Astrophysics Data System (ADS)

Costa, Giuseppe; Torrisi, Lorenzo

2018-01-01

The charge particle emission form laser-generated plasma was studied experimentally and theoretically using the COMSOL simulation code. The particle acceleration was investigated using two lasers at two different regimes. A Nd:YAG laser, with 3 ns pulse duration and 1010 W/cm2 intensity, when focused on solid target produces a non-equilibrium plasma with average temperature of about 30-50 eV. An Iodine laser with 300 ps pulse duration and 1016 W/cm2 intensity produces plasmas with average temperatures of the order of tens keV. In both cases charge separation occurs and ions and electrons are accelerated at energies of the order of 200 eV and 1 MeV per charge state in the two cases, respectively. The simulation program permits to plot the charge particle trajectories from plasma source in vacuum indicating how they can be deflected by magnetic and electrical fields. The simulation code can be employed to realize suitable permanent magnets and solenoids to deflect ions toward a secondary target or detectors, to focalize ions and electrons, to realize electron traps able to provide significant ion acceleration and to realize efficient spectrometers. In particular it was applied to the study two Thomson parabola spectrometers able to detect ions at low and at high laser intensities. The comparisons between measurements and simulation is presented and discussed.

Computer simulations of the solvatochromism of betaine-30

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

Mente, S.R.; Maroncelli, M.

1999-09-09

Monte Carlo simulations of the pyridinium N-phenolate dye betaine-30 in 12 solvents (20 solvent representations) were performed in order to explore the molecular basis of the E{sub T}(30) scale of solvent polarity. Ab initio (HF/6-31G{sup *}) and semiempirical (AM1 and INDO/S) electronic structure calculations were used to determine the geometry and charge distribution of betaine-30 in its S{sub 0} and S{sub 1} states. The solvent effect on the betaine absorption spectrum was assumed to derive from electrostatic interactions between the effective charge distributions of solvent molecules and the charge shift brought about by the S{sub 0} {r_arrow} S{sub 1} transition.more » Two models for this charge shift, one obtained from INDO/S calculations and the other an idealized two-site model, were used for the spectral calculations. Good agreement between simulated and observed {Delta}E{sub T} shifts (E{sub T}(30) values measured relative to the nonpolar standard tetramethylsilane) was found for both charge-shift models. In water and other hydroxylic solvents, the O atom of the betaine solute was observed to form moderately strong hydrogen bonds to between one and two solvent molecules. The contribution of these specifically coordinated molecules to the {Delta}E{sub T} shift was found to be large, (30--60%) and comparable to experimental estimates. Additional simulations of acetonitrile and methanol in equilibrium with the S{sub 1} state of betaine-30 were used to determine reorganization energies in these solvents and to decide the extent to which the solvent response to the S{sub 0} {leftrightarrow} S{sub 1} transition conforms to linear response predictions. In both solvents, the spectral distributions observed in the S{sub 0} state simulations were {approximately} 15% narrower than those in the S{sub 1} simulations, indicating only a relatively small departure from linear behavior. Reorganization energies were also estimated for a number of other solvents and compared to values reported in previous experimental and theoretical studies.« less

Comparison of the Marcus and Pekar partitions in the context of non-equilibrium, polarizable-continuum solvation models

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

You, Zhi-Qiang; Herbert, John M., E-mail: herbert@chemistry.ohio-state.edu; Mewes, Jan-Michael

2015-11-28

The Marcus and Pekar partitions are common, alternative models to describe the non-equilibrium dielectric polarization response that accompanies instantaneous perturbation of a solute embedded in a dielectric continuum. Examples of such a perturbation include vertical electronic excitation and vertical ionization of a solution-phase molecule. Here, we provide a general derivation of the accompanying polarization response, for a quantum-mechanical solute described within the framework of a polarizable continuum model (PCM) of electrostatic solvation. Although the non-equilibrium free energy is formally equivalent within the two partitions, albeit partitioned differently into “fast” versus “slow” polarization contributions, discretization of the PCM integral equations failsmore » to preserve certain symmetries contained in these equations (except in the case of the conductor-like models or when the solute cavity is spherical), leading to alternative, non-equivalent matrix equations. Unlike the total equilibrium solvation energy, however, which can differ dramatically between different formulations, we demonstrate that the equivalence of the Marcus and Pekar partitions for the non-equilibrium solvation correction is preserved to high accuracy. Differences in vertical excitation and ionization energies are <0.2 eV (and often <0.01 eV), even for systems specifically selected to afford a large polarization response. Numerical results therefore support the interchangeability of the Marcus and Pekar partitions, but also caution against relying too much on the fast PCM charges for interpretive value, as these charges differ greatly between the two partitions, especially in polar solvents.« less

Calculating and Visualizing Thermodynamic Equilibrium: A Tutorial on the Isolated System with an Internal Adiabatic Piston

ERIC Educational Resources Information Center

Ferreira, Joao Paulo M.

2007-01-01

The problem of the equilibrium state of an isolated composite system with a movable internal adiabatic wall is a recurrent one in the literature. Classical equilibrium thermodynamics is unable to predict the equilibrium state, unless supplemented with information about the process taking place. This conclusion is clearly demonstrated in this…

Fluorescence lifetime components reveal kinetic intermediate states upon equilibrium denaturation of carbonic anhydrase II

NASA Astrophysics Data System (ADS)

Nemtseva, Elena V.; Lashchuk, Olesya O.; Gerasimova, Marina A.; Melnik, Tatiana N.; Nagibina, Galina S.; Melnik, Bogdan S.

2018-01-01

In most cases, intermediate states of multistage folding proteins are not ‘visible’ under equilibrium conditions but are revealed in kinetic experiments. Time-resolved fluorescence spectroscopy was used in equilibrium denaturation studies. The technique allows for detecting changes in the conformation and environment of tryptophan residues in different structural elements of carbonic anhydrase II which in its turn has made it possible to study the intermediate states of carbonic anhydrase II under equilibrium conditions. The results of equilibrium and kinetic experiments using wild-type bovine carbonic anhydrase II and its mutant form with the substitution of leucine for alanine at position 139 (L139A) were compared. The obtained lifetime components of intrinsic tryptophan fluorescence allowed for revealing that, the same as in kinetic experiments, under equilibrium conditions the unfolding of carbonic anhydrase II ensues through formation of intermediate states.

Fluorescence lifetime components reveal kinetic intermediate states upon equilibrium denaturation of carbonic anhydrase II.

PubMed

Nemtseva, Elena V; Lashchuk, Olesya O; Gerasimova, Marina A; Melnik, Tatiana N; Nagibina, Galina S; Melnik, Bogdan S

2017-12-21

In most cases, intermediate states of multistage folding proteins are not 'visible' under equilibrium conditions but are revealed in kinetic experiments. Time-resolved fluorescence spectroscopy was used in equilibrium denaturation studies. The technique allows for detecting changes in the conformation and environment of tryptophan residues in different structural elements of carbonic anhydrase II which in its turn has made it possible to study the intermediate states of carbonic anhydrase II under equilibrium conditions. The results of equilibrium and kinetic experiments using wild-type bovine carbonic anhydrase II and its mutant form with the substitution of leucine for alanine at position 139 (L139A) were compared. The obtained lifetime components of intrinsic tryptophan fluorescence allowed for revealing that, the same as in kinetic experiments, under equilibrium conditions the unfolding of carbonic anhydrase II ensues through formation of intermediate states.

Coherent Structures and Chaos Control in High-Power Microwave and Charged-Particle Beam Devices

DTIC Science & Technology

2009-01-31

34Equilibrium Theory of an Intense Elliptic Beam for High - Power Ribbon-Beam Klystron Applications," Proc. 2007 Part. Accel. Conf. p. 2316. Courant...34Equilibrium Theory of an Intense Elliptic Beam for High - Power Ribbon-Beam Klystron Applications," C. Chen and J. Zhou, Proc. 2007 Part. Accel. Conf. (2007...accelerator focusing systems. Over 600 high - power , high -efficiency klystrons , for example, may be needed to provide rf power for the acceleration

From Wang-Chen System with Only One Stable Equilibrium to a New Chaotic System Without Equilibrium

NASA Astrophysics Data System (ADS)

Pham, Viet-Thanh; Wang, Xiong; Jafari, Sajad; Volos, Christos; Kapitaniak, Tomasz

2017-06-01

Wang-Chen system with only one stable equilibrium as well as the coexistence of hidden attractors has attracted increasing interest due to its striking features. In this work, the effect of state feedback on Wang-Chen system is investigated by introducing a further state variable. It is worth noting that a new chaotic system without equilibrium is obtained. We believe that the system is an interesting example to illustrate the conversion of hidden attractors with one stable equilibrium to hidden attractors without equilibrium.

Packings of a charged line on a sphere.

PubMed

Alben, Silas

2008-12-01

We find equilibrium configurations of open and closed lines of charge on a sphere, and track them with respect to varying sphere radius. Closed lines transition from a circle to a spiral-like shape through two low-wave-number bifurcations-"baseball seam" and "twist"-which minimize Coulomb energy. The spiral shape is the unique stable equilibrium of the closed line. Other unstable equilibria arise through tip-splitting events. An open line transitions smoothly from an arc of a great circle to a spiral as the sphere radius decreases. Under repulsive potentials with faster-than-Coulomb power-law decay, the spiral is tighter in initial stages of sphere shrinkage, but at later stages of shrinkage the equilibria for all repulsive potentials converge on a spiral with uniform spacing between turns. Multiple stable equilibria of the open line are observed.

Numerical Analysis on Non-Equilibrium Mechanism of Laser-Supported Detonation Wave Using Multiply-Charged Ionization

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

Shiraishi, Hiroyuki

Laser-Supported Detonation (LSD), one type of Laser-Supported Plasma (LSP), is considered as the most important phenomena because it can generate high pressure and high temperature for laser absorption. In this study, I have numerically simulated the 1-D LSD waves propagating through a helium gas, in which Multiply-charged ionization model is considered for describing an accurate ionization process.

Electrokinetic flow in a capillary with a charge-regulating surface polymer layer.

PubMed

Keh, Huan J; Ding, Jau M

2003-07-15

An analytical study of the steady electrokinetic flow in a long uniform capillary tube or slit is presented. The inside wall of the capillary is covered by a layer of adsorbed or covalently bound charge-regulating polymer in equilibrium with the ambient electrolyte solution. In this solvent-permeable and ion-penetrable surface polyelectrolyte layer, ionogenic functional groups and frictional segments are assumed to distribute at uniform densities. The electrical potential and space charge density distributions in the cross section of the capillary are obtained by solving the linearized Poisson-Boltzmann equation. The fluid velocity profile due to the application of an electric field and a pressure gradient through the capillary is obtained from the analytical solution of a modified Navier-Stokes/Brinkman equation. Explicit formulas for the electroosmotic velocity, the average fluid velocity and electric current density on the cross section, and the streaming potential in the capillary are also derived. The results demonstrate that the direction of the electroosmotic flow and the magnitudes of the fluid velocity and electric current density are dominated by the fixed charge density inside the surface polymer layer, which is determined by the regulation characteristics such as the dissociation equilibrium constants of the ionogenic functional groups in the surface layer and the concentration of the potential-determining ions in the bulk solution.

Dynamical formation of a Reissner-Nordström black hole with scalar hair in a cavity

NASA Astrophysics Data System (ADS)

Sanchis-Gual, Nicolas; Degollado, Juan Carlos; Herdeiro, Carlos; Font, José A.; Montero, Pedro J.

2016-08-01

In a recent Letter [Sanchis-Gual et al., Phys. Rev. Lett. 116, 141101 (2016)], we presented numerical relativity simulations, solving the full Einstein-Maxwell-Klein-Gordon equations, of superradiantly unstable Reissner-Nordström black holes (BHs), enclosed in a cavity. Low frequency, spherical perturbations of a charged scalar field trigger this instability. The system's evolution was followed into the nonlinear regime, until it relaxed into an equilibrium configuration, found to be a hairy BH: a charged horizon in equilibrium with a scalar field condensate, whose phase is oscillating at the (final) critical frequency. Here, we investigate the impact of adding self-interactions to the scalar field. In particular, we find sufficiently large self-interactions suppress the exponential growth phase, known from linear theory, and promote a nonmonotonic behavior of the scalar field energy. Furthermore, we discuss in detail the influence of the various parameters in this model: the initial BH charge, the initial scalar perturbation, the scalar field charge, the mass, and the position of the cavity's boundary (mirror). We also investigate the "explosive" nonlinear regime previously reported to be akin to a bosenova. A mode analysis shows that the "explosions" can be interpreted as the decay into the BH of modes that exit the superradiant regime.

Counter-ions at single charged wall: Sum rules.

PubMed

Samaj, Ladislav

2013-09-01

For inhomogeneous classical Coulomb fluids in thermal equilibrium, like the jellium or the two-component Coulomb gas, there exists a variety of exact sum rules which relate the particle one-body and two-body densities. The necessary condition for these sum rules is that the Coulomb fluid possesses good screening properties, i.e. the particle correlation functions or the averaged charge inhomogeneity, say close to a wall, exhibit a short-range (usually exponential) decay. In this work, we study equilibrium statistical mechanics of an electric double layer with counter-ions only, i.e. a globally neutral system of equally charged point-like particles in the vicinity of a plain hard wall carrying a fixed uniform surface charge density of opposite sign. At large distances from the wall, the one-body and two-body counter-ion densities go to zero slowly according to the inverse-power law. In spite of the absence of screening, all known sum rules are shown to hold for two exactly solvable cases of the present system: in the weak-coupling Poisson-Boltzmann limit (in any spatial dimension larger than one) and at a special free-fermion coupling constant in two dimensions. This fact indicates an extended validity of the sum rules and provides a consistency check for reasonable theoretical approaches.

On the time needed to reach an equilibrium structure of the radiation belts

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

Ripoll, J. -F.; Loran, V.; Cunningham, Gregory Scott

In this paper, we complement the notion of equilibrium states of the radiation belts with a discussion on the dynamics and time needed to reach equilibrium. We solve for the equilibrium states obtained using 1D radial diffusion with recently developed hiss and chorus lifetimes at constant values of Kp = 1, 3 and 6. We find that the equilibrium states at moderately low Kp, when plotted vs L-shell (L) and energy (E), display the same interesting S-shape for the inner edge of the outer belt as recently observed by the Van Allen Probes. The S-shape is also produced as themore » radiation belts dynamically evolve toward the equilibrium state when initialized to simulate the buildup after a massive dropout or to simulate loss due to outward diffusion from a saturated state. Physically, this shape, intimately linked with the slot structure, is due to the dependence of electron loss rate (originating from wave-particle interactions) on both energy and L-shell. Equilibrium electron flux profiles are governed by the Biot number (τ Diffusion/τ loss), with large Biot number corresponding to low fluxes and low Biot number to large fluxes. The time it takes for the flux at a specific (L, E) to reach the value associated with the equilibrium state, starting from these different initial states, is governed by the initial state of the belts, the property of the dynamics (diffusion coefficients), and the size of the domain of computation. Its structure shows a rather complex scissor form in the (L, E) plane. The equilibrium value (phase space density or flux) is practically reachable only for selected regions in (L, E) and geomagnetic activity. Convergence to equilibrium requires hundreds of days in the inner belt for E > 300 keV and moderate Kp (≤3). It takes less time to reach equilibrium during disturbed geomagnetic conditions (Kp ≥ 3), when the system evolves faster. Restricting our interest to the slot region, below L = 4, we find that only small regions in (L, E) space can reach the equilibrium value: E ~ [200, 300] keV for L = [3.7, 4] at Kp = 1, E ~ [0.6, 1] MeV for L = [3, 4] at Kp = 3, and E ~ 300 keV for L = [3.5, 4] at Kp = 6 assuming no new incoming electrons.« less

On the time needed to reach an equilibrium structure of the radiation belts

DOE PAGES

Ripoll, J. -F.; Loran, V.; Cunningham, Gregory Scott; ...

2016-08-01

In this paper, we complement the notion of equilibrium states of the radiation belts with a discussion on the dynamics and time needed to reach equilibrium. We solve for the equilibrium states obtained using 1D radial diffusion with recently developed hiss and chorus lifetimes at constant values of Kp = 1, 3 and 6. We find that the equilibrium states at moderately low Kp, when plotted vs L-shell (L) and energy (E), display the same interesting S-shape for the inner edge of the outer belt as recently observed by the Van Allen Probes. The S-shape is also produced as themore » radiation belts dynamically evolve toward the equilibrium state when initialized to simulate the buildup after a massive dropout or to simulate loss due to outward diffusion from a saturated state. Physically, this shape, intimately linked with the slot structure, is due to the dependence of electron loss rate (originating from wave-particle interactions) on both energy and L-shell. Equilibrium electron flux profiles are governed by the Biot number (τ Diffusion/τ loss), with large Biot number corresponding to low fluxes and low Biot number to large fluxes. The time it takes for the flux at a specific (L, E) to reach the value associated with the equilibrium state, starting from these different initial states, is governed by the initial state of the belts, the property of the dynamics (diffusion coefficients), and the size of the domain of computation. Its structure shows a rather complex scissor form in the (L, E) plane. The equilibrium value (phase space density or flux) is practically reachable only for selected regions in (L, E) and geomagnetic activity. Convergence to equilibrium requires hundreds of days in the inner belt for E > 300 keV and moderate Kp (≤3). It takes less time to reach equilibrium during disturbed geomagnetic conditions (Kp ≥ 3), when the system evolves faster. Restricting our interest to the slot region, below L = 4, we find that only small regions in (L, E) space can reach the equilibrium value: E ~ [200, 300] keV for L = [3.7, 4] at Kp = 1, E ~ [0.6, 1] MeV for L = [3, 4] at Kp = 3, and E ~ 300 keV for L = [3.5, 4] at Kp = 6 assuming no new incoming electrons.« less

[The accuracy of rapid equilibrium assumption in steady-state enzyme kinetics is the function of equilibrium segment structure and properties].

PubMed

Vrzheshch, P V

2015-01-01

Quantitative evaluation of the accuracy of the rapid equilibrium assumption in the steady-state enzyme kinetics was obtained for an arbitrary mechanism of an enzyme-catalyzed reaction. This evaluation depends only on the structure and properties of the equilibrium segment, but doesn't depend on the structure and properties of the rest (stationary part) of the kinetic scheme. The smaller the values of the edges leaving equilibrium segment in relation to values of the edges within the equilibrium segment, the higher the accuracy of determination of intermediate concentrations and reaction velocity in a case of the rapid equilibrium assumption.

Stochastic pumping of non-equilibrium steady-states: how molecules adapt to a fluctuating environment.

PubMed

Astumian, R D

2018-01-11

In the absence of input energy, a chemical reaction in a closed system ineluctably relaxes toward an equilibrium state governed by a Boltzmann distribution. The addition of a catalyst to the system provides a way for more rapid equilibration toward this distribution, but the catalyst can never, in and of itself, drive the system away from equilibrium. In the presence of external fluctuations, however, a macromolecular catalyst (e.g., an enzyme) can absorb energy and drive the formation of a steady state between reactant and product that is not determined solely by their relative energies. Due to the ubiquity of non-equilibrium steady states in living systems, the development of a theory for the effects of external fluctuations on chemical systems has been a longstanding focus of non-equilibrium thermodynamics. The theory of stochastic pumping has provided insight into how a non-equilibrium steady-state can be formed and maintained in the presence of dissipation and kinetic asymmetry. This effort has been greatly enhanced by a confluence of experimental and theoretical work on synthetic molecular machines designed explicitly to harness external energy to drive non-equilibrium transport and self-assembly.

Charged particle spectra in 32S + 32S interactions at 200 GeV/nucleon from CCD-imaged nuclear collisions in a streamer chamber

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

Teitelbaum, Lawrence Paul

1992-04-01

We have measured the transverse momentum spectra 1/p T dN/dp T and rapidity distributions dN/dy of negatively charged hadrons and protons for central 32S + 32S interactions at 200 GeV/nucleon incident energy. The negative hadron dN/dy distribution is too broad to be accounted for by thermal models which demand isotropic particle emission. It is compatible with models which emphasize longitudinal dynamics, by either a particle production mechanism, as in the Lund fragmentation model, or by introducing one-dimensional hydrodynamic expansion, as in the Landau model. The proton dN/dy distribution, although showing no evidence for a peak in the target fragmentation region,more » exhibits limited nuclear stopping power. We estimate the mean rapidity shift of participant target protons to be Δy ~ 1.5, greater than observed for pp collisions, less than measured in central pA collisions, and much less than would be observed for a single equilibrated fireball at midrapidity. Both the negative hadron and proton dN/dy distributions can be fit by a symmetric Landau two-fireball model. Although the spectrum possesses a two-component structure, a comparison to pp data at comparable center-of-mass energy shows no evidence for enhanced production at low p T. The two-component structure can be explained by a thermal and chemical equilibrium model which takes into account the kinematics of resonance decay. Using an expression motivated by longitudinal expansion we find the same temperature for both the protons and negative hadrons at freezeout, T f ~ 170 MeV. We conclude that the charged particle spectra of negative hadrons and protons can be accommodated in a simple collision picture of limited nuclear stopping, evolution through a state of thermal equilibrium, followed by longitudinal hydrodynamic expansion until freezeout.« less

Charged particle spectra in [sup 32]S + [sup 32]S interactions at 200 GeV/nucleon from CCD-imaged nuclear collisions in a streamer chamber

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

Teitelbaum, L.P.

1992-04-01

We have measured the transverse momentum spectra 1/p[sub T] dN/dp[sub T] and rapidity distributions dN/dy of negatively charged hadrons and protons for central [sup 32]S + [sup 32]S interactions at 200 GeV/nucleon incident energy. The negative hadron dN/dy distribution is too broad to be accounted for by thermal models which demand isotropic particle emission. It is compatible with models which emphasize longitudinal dynamics, by either a particle production mechanism, as in the Lund fragmentation model, or by introducing one-dimensional hydrodynamic expansion, as in the Landau model. The proton dN/dy distribution, although showing no evidence for a peak in the targetmore » fragmentation region, exhibits limited nuclear stopping power. We estimate the mean rapidity shift of participant target protons to be [Delta]y [approximately] 1.5, greater than observed for pp collisions, less than measured in central pA collisions, and much less than would be observed for a single equilibrated fireball at midrapidity. Both the negative hadron and proton dN/dy distributions can be fit by a symmetric Landau two-fireball model. Although the spectrum possesses a two-component structure, a comparison to pp data at comparable center-of-mass energy shows no evidence for enhanced production at low p[sub T]. The two-component structure can be explained by a thermal and chemical equilibrium model which takes into account the kinematics of resonance decay. Using an expression motivated by longitudinal expansion we find the same temperature for both the protons and negative hadrons at freezeout, T[sub f] [approximately] 170 MeV. We conclude that the charged particle spectra of negative hadrons and protons can be accommodated in a simple collision picture of limited nuclear stopping, evolution through a state of thermal equilibrium, followed by longitudinal hydrodynamic expansion until freezeout.« less

Local Nash equilibrium in social networks.

PubMed

Zhang, Yichao; Aziz-Alaoui, M A; Bertelle, Cyrille; Guan, Jihong

2014-08-29

Nash equilibrium is widely present in various social disputes. As of now, in structured static populations, such as social networks, regular, and random graphs, the discussions on Nash equilibrium are quite limited. In a relatively stable static gaming network, a rational individual has to comprehensively consider all his/her opponents' strategies before they adopt a unified strategy. In this scenario, a new strategy equilibrium emerges in the system. We define this equilibrium as a local Nash equilibrium. In this paper, we present an explicit definition of the local Nash equilibrium for the two-strategy games in structured populations. Based on the definition, we investigate the condition that a system reaches the evolutionary stable state when the individuals play the Prisoner's dilemma and snow-drift game. The local Nash equilibrium provides a way to judge whether a gaming structured population reaches the evolutionary stable state on one hand. On the other hand, it can be used to predict whether cooperators can survive in a system long before the system reaches its evolutionary stable state for the Prisoner's dilemma game. Our work therefore provides a theoretical framework for understanding the evolutionary stable state in the gaming populations with static structures.

Local Nash Equilibrium in Social Networks

PubMed Central

Zhang, Yichao; Aziz-Alaoui, M. A.; Bertelle, Cyrille; Guan, Jihong

2014-01-01

Nash equilibrium is widely present in various social disputes. As of now, in structured static populations, such as social networks, regular, and random graphs, the discussions on Nash equilibrium are quite limited. In a relatively stable static gaming network, a rational individual has to comprehensively consider all his/her opponents' strategies before they adopt a unified strategy. In this scenario, a new strategy equilibrium emerges in the system. We define this equilibrium as a local Nash equilibrium. In this paper, we present an explicit definition of the local Nash equilibrium for the two-strategy games in structured populations. Based on the definition, we investigate the condition that a system reaches the evolutionary stable state when the individuals play the Prisoner's dilemma and snow-drift game. The local Nash equilibrium provides a way to judge whether a gaming structured population reaches the evolutionary stable state on one hand. On the other hand, it can be used to predict whether cooperators can survive in a system long before the system reaches its evolutionary stable state for the Prisoner's dilemma game. Our work therefore provides a theoretical framework for understanding the evolutionary stable state in the gaming populations with static structures. PMID:25169150

Local Nash Equilibrium in Social Networks

NASA Astrophysics Data System (ADS)

Zhang, Yichao; Aziz-Alaoui, M. A.; Bertelle, Cyrille; Guan, Jihong

2014-08-01

Nash equilibrium is widely present in various social disputes. As of now, in structured static populations, such as social networks, regular, and random graphs, the discussions on Nash equilibrium are quite limited. In a relatively stable static gaming network, a rational individual has to comprehensively consider all his/her opponents' strategies before they adopt a unified strategy. In this scenario, a new strategy equilibrium emerges in the system. We define this equilibrium as a local Nash equilibrium. In this paper, we present an explicit definition of the local Nash equilibrium for the two-strategy games in structured populations. Based on the definition, we investigate the condition that a system reaches the evolutionary stable state when the individuals play the Prisoner's dilemma and snow-drift game. The local Nash equilibrium provides a way to judge whether a gaming structured population reaches the evolutionary stable state on one hand. On the other hand, it can be used to predict whether cooperators can survive in a system long before the system reaches its evolutionary stable state for the Prisoner's dilemma game. Our work therefore provides a theoretical framework for understanding the evolutionary stable state in the gaming populations with static structures.

Electron-rich driven electrochemical solid-state amorphization in Li-Si alloys.

PubMed

Wang, Zhiguo; Gu, Meng; Zhou, Yungang; Zu, Xiaotao; Connell, Justin G; Xiao, Jie; Perea, Daniel; Lauhon, Lincoln J; Bang, Junhyeok; Zhang, Shengbai; Wang, Chongmin; Gao, Fei

2013-09-11

The physical and chemical behaviors of materials used in energy storage devices, such as lithium-ion batteries (LIBs), are mainly controlled by an electrochemical process, which normally involves insertion/extraction of ions into/from a host lattice with a concurrent flow of electrons to compensate charge balance. The fundamental physics and chemistry governing the behavior of materials in response to the ions insertion/extraction is not known. Herein, a combination of in situ lithiation experiments and large-scale ab initio molecular dynamics simulations are performed to explore the mechanisms of the electrochemically driven solid-state amorphization in Li-Si systems. We find that local electron-rich condition governs the electrochemically driven solid-state amorphization of Li-Si alloys. This discovery provides the fundamental explanation of why lithium insertion in semiconductor and insulators leads to amorphization, whereas in metals, it leads to a crystalline alloy. The present work correlates electrochemically driven reactions with ion insertion, electron transfer, lattice stability, and phase equilibrium.

Electron-Rich Driven Electrochemical Solid-State Amorphization in Li-Si Alloys

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

Wang, Zhiguo; Gu, Meng; Zhou, Yungang

2013-08-14

The physical and chemical behaviors of materials used in energy storage devices, such as lithium-ion batteries (LIBs), are mainly controlled by an electrochemical process, which normally involves insertion/extraction of ions into/from a host lattice with a concurrent flow of electrons to compensate charge balance. The fundamental physics and chemistry governing the behavior of materials in response to the ions insertion/extraction is not known. Herein, a combination of in situ lithiation experiments and large-scale ab initio molecular dynamics simulations are performed to explore the mechanisms of the electrochemically driven solid-state amorphization in Li-Si systems. We find that local electron-rich condition governsmore » the electrochemically driven solid-state amorphization of Li-Si alloys. This discovery provides the fundamental explanation of why lithium insertion in semiconductor and insulators leads to amorphization, whereas in metals, it leads to a crystalline alloy. The present work correlates electrochemically driven reactions with ion insertion, electron transfer, lattice stability and phase equilibrium.« less

The Core of Allosteric Motion in Thermus caldophilus l-Lactate Dehydrogenase*

PubMed Central

Ikehara, Yoko; Arai, Kazuhito; Furukawa, Nayuta; Ohno, Tadashi; Miyake, Tatsuya; Fushinobu, Shinya; Nakajima, Masahiro; Miyanaga, Akimasa; Taguchi, Hayao

2014-01-01

For Thermus caldophilus l-lactate dehydrogenase (TcLDH), fructose 1,6-bisphosphate (FBP) reduced the pyruvate S0.5 value 103-fold and increased the Vmax value 4-fold at 30 °C and pH 7.0, indicating that TcLDH has a much more T state-sided allosteric equilibrium than Thermus thermophilus l-lactate dehydrogenase, which has only two amino acid replacements, A154G and H179Y. The inactive (T) and active (R) state structures of TcLDH were determined at 1.8 and 2.0 Å resolution, respectively. The structures indicated that two mobile regions, MR1 (positions 172–185) and MR2 (positions 211–221), form a compact core for allosteric motion, and His179 of MR1 forms constitutive hydrogen bonds with MR2. The Q4(R) mutation, which comprises the L67E, H68D, E178K, and A235R replacements, increased Vmax 4-fold but reduced pyruvate S0.5 only 5-fold in the reaction without FBP. In contrast, the P2 mutation, comprising the R173Q and R216L replacements, did not markedly increase Vmax, but 102-reduced pyruvate S0.5, and additively increased the FBP-independent activity of the Q4(R) enzyme. The two types of mutation consistently increased the thermal stability of the enzyme. The MR1-MR2 area is a positively charged cluster, and its center approaches another positively charged cluster (N domain cluster) across the Q-axis subunit interface by 5 Å, when the enzyme undergoes the T to R transition. Structural and kinetic analyses thus revealed the simple and unique allosteric machinery of TcLDH, where the MR1-MR2 area pivotally moves during the allosteric motion and mediates the allosteric equilibrium through electrostatic repulsion within the protein molecule. PMID:25258319

Dielectric elastomer membranes undergoing inhomogeneous deformation

NASA Astrophysics Data System (ADS)

He, Tianhu; Zhao, Xuanhe; Suo, Zhigang

2009-10-01

Dielectric elastomers are capable of large deformation subject to an electric voltage and are promising for use as actuators, sensors, and generators. Because of large deformation, nonlinear equations of states, and diverse modes of failure, modeling the process of electromechanical transduction has been challenging. This paper studies a membrane of a dielectric elastomer deformed into an out-of-plane axisymmetric shape, a configuration used in a family of commercial devices known as the universal muscle actuators. The kinematics of deformation and charging, together with thermodynamics, leads to equations that govern the state of equilibrium. Numerical results indicate that the field in the membrane can be very inhomogeneous, and that the membrane is susceptible to several modes of failure, including electrical breakdown, loss of tension, and rupture by stretch. Care is needed in the design to balance the requirements of averting various modes of failure while using the material efficiently.

The detailed balance principle and the reciprocity theorem between photocarrier collection and dark carrier distribution in solar cells

NASA Astrophysics Data System (ADS)

Rau, Uwe; Brendel, Rolf

1998-12-01

It is shown that a recently described general relationship between the local collection efficiency of solar cells and the dark carrier concentration (reciprocity theorem) directly follows from the principle of detailed balance. We derive the relationship for situations where transport of charge carriers occurs between discrete states as well as for the situation where electronic transport is described in terms of continuous functions. Combining both situations allows to extend the range of applicability of the reciprocity theorem to all types of solar cells, including, e.g., metal-insulator-semiconductor-type, electrochemical solar cells, as well as the inclusion of the impurity photovoltaic effect. We generalize the theorem further to situations where the occupation probability of electronic states is governed by Fermi-Dirac statistics instead of Boltzmann statistics as underlying preceding work. In such a situation the reciprocity theorem is restricted to small departures from equilibrium.

Impacts of energy consumption and emissions on the trip cost without late arrival at the equilibrium state

NASA Astrophysics Data System (ADS)

Tang, Tie-Qiao; Wang, Tao; Chen, Liang; Shang, Hua-Yan

2017-08-01

In this paper, we apply a car-following model, fuel consumption model, emission model and electricity consumption model to explore the influences of energy consumption and emissions on each commuter's trip costs without late arrival at the equilibrium state. The numerical results show that the energy consumption and emissions have significant impacts on each commuter's trip cost without late arrival at the equilibrium state. The fuel cost and emission cost prominently enhance each commuter's trip cost and the trip cost increases with the number of vehicles, which shows that considering the fuel cost and emission cost in the trip cost will destroy the equilibrium state. However, the electricity cost slightly enhances each commuter's trip cost, but the trip cost is still approximately a constant, which indicates that considering the electricity cost in the trip cost does not destroy the equilibrium state.

Charging of Aggregate Grains in Astrophysical Environments

NASA Astrophysics Data System (ADS)

Ma, Qianyu; Matthews, Lorin S.; Land, Victor; Hyde, Truell W.

2013-02-01

The charging of dust grains in astrophysical environments has been investigated with the assumption that these grains are homogeneous spheres. However, there is evidence which suggests that many grains in astrophysical environments are irregularly shaped aggregates. Recent studies have shown that aggregates acquire higher charge-to-mass ratios due to their complex structures, which in turn may alter their subsequent dynamics and evolution. In this paper, the charging of aggregates is examined including secondary electron emission and photoemission in addition to primary plasma currents. The results show that the equilibrium charge on aggregates can differ markedly from spherical grains with the same mass, but that the charge can be estimated for a given environment based on structural characteristics of the grain. The "small particle effect" due to secondary electron emission is also important for de terming the charge of micron-sized aggregates consisting of nano-sized particles.

Quantum Kinetics and the Zeno Ansatz: Sterile Neutrino Dark Matter in the Early Universe

NASA Astrophysics Data System (ADS)

Dvornikov, Olexiy V.

We solved the quantum kinetic equations for the evolution of neutrino states in the early universe. Starting at high temperatures, we evolve neutrino states to observe the resonant conversion of active-to-sterile neutrinos in a lepton asymmetric (more neutrinos than anti-neutrinos) universe. We find that at high temperatures, the high neutrino scattering and oscillation rates enforce a local equilibrium that balances the growth of coherence at the oscillation rate and the damping of coherence through scattering. This equilibrium, which we call a "quantum kinetic equilibrium," appears to approximately hold throughout the neutrino evolution, from the initial conditions through resonances that may be non adiabatic. Using this quantum kinetic equilibrium informs a proper choice of the initial conditions of the neutrino state and the relaxation process that occurs to this equilibrium when the initial conditions (as are typically chosen in the literature) are not coincident with the equilibrium values. We also discuss how to use this equilibrium to reduce the computational expense of solving the full quantum kinetic equations for neutrino states evolving in the early universe.

Quasiparticle Coherence, Collective Modes, and Competing Order in Cuprate Superconductors

NASA Astrophysics Data System (ADS)

Hinton, James Patrick

In recent years, the study of cuprate superconductors has been dominated by the investigation of normal state properties. Of particular interest is the nature of interactions between superconductivity and other incipient orders which emerge above the superconducting transition temperature, Tc. The discovery of charge density wave (CDW) correlations in YBa2Cu3O6+x (YBCO) and HgBa2CuO 4+d (Hg-1201) has established that some form of charge order is ubiquitous in the cuprates. In this work, we explore the non-equilibrium dynamics of systems which sit near the boundary between superconductivity and competing orders. Ultrafast pump-probe spectroscopy is ideally suited to the study of competing order. Exciting the sample with an optical pulse perturbs the system from equilibrium, altering the balance between the co-existing orders. The return to equilibrium is then monitored by a time-delayed probe pulse, revealing multiple decay processes as well as collective excitations. We first apply this technique to Hg-1201, conducting a detailed study of the phase diagram. At temperatures near Tc, the pump pulse induces a non-equilibrium quasiparticle population. At Tc we observe a doping-dependent peak in the relaxation time of these quasiparticles which we associate with a divergence in the coherence time of the fluctuating CDW. Using heterodyne probing in the transient grating geometry, we are able to disentangle the transient reflectivity components associated with superconductivity and the pseudogap, domonstrating competition across the phase diagram. We also discuss the observation of a sharp transition in the nature of the pseudogap signal at ˜ 11% doping. In YBCO, we explore the temperature and doping dependence of coherent oscillations excited by the pump pulse. We associate these oscillations with the excitation of the CDW amplitude mode, and model their temperature dependence within the framework of a Landau model of competing orders. We conclude with an investigation of pseudogap dynamics in the electron doped compound Nd2-xCexCuO4+d as a function of temperature and doping. Near optimal doping, we observe the impulsive excitation of a critically damped mode, with time-temperature scaling consistent with quantum-critical fluctuations. This mode competes with superconductivity in a dynamical fashion, such that the suppression of this mode below T c can be lifted via photo-evaporation of the superconducting condensate.

Effect of Stochastic Charge Fluctuations on Dust Dynamics

NASA Astrophysics Data System (ADS)

Matthews, Lorin; Shotorban, Babak; Hyde, Truell

2017-10-01

The charging of particles in a plasma environment occurs through the collection of electrons and ions on the particle surface. Depending on the particle size and the plasma density, the standard deviation of the number of collected elementary charges, which fluctuates due to the randomness in times of collisions with electrons or ions, may be a significant fraction of the equilibrium charge. We use a discrete stochastic charging model to simulate the variations in charge across the dust surface as well as in time. The resultant asymmetric particle potentials, even for spherical grains, has a significant impact on the particle coagulation rate as well as the structure of the resulting aggregates. We compare the effects on particle collisions and growth in typical laboratory and astrophysical plasma environments. This work was supported by the National Science Foundation under Grant PHY-1414523.

Electrostatic attraction of charged drops of water inside dropwise cluster

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

Shavlov, A. V.; Tyumen State Oil and Gas University, 38, Volodarskogo Str., Tyumen 625000; Dzhumandzhi, V. A.

2013-08-15

Based on the analytical solution of the Poisson-Boltzmann equation, we demonstrate that inside the electrically neutral system of charges an electrostatic attraction can occur between the like-charged particles, where charge Z ≫ 1 (in terms of elementary charge) and radius R > 0, whereas according to the literature, only repulsion is possible inside non-electrically neutral systems. We calculate the free energy of the charged particles of water inside a cluster and demonstrate that its minimum is when the interdroplet distance equals several Debye radii defined based on the light plasma component. The deepest minimum depth is in a cluster withmore » close spatial packing of drops by type, in a face-centered cubic lattice, if almost all the electric charge of one sign is concentrated on the drops and that of the other sign is concentrated on the light compensation carriers of charge, where the charge moved by equilibrium carriers is rather small.« less

Discrete stochastic charging of aggregate grains

NASA Astrophysics Data System (ADS)

Matthews, Lorin S.; Shotorban, Babak; Hyde, Truell W.

2018-05-01

Dust particles immersed in a plasma environment become charged through the collection of electrons and ions at random times, causing the dust charge to fluctuate about an equilibrium value. Small grains (with radii less than 1 μm) or grains in a tenuous plasma environment are sensitive to single additions of electrons or ions. Here we present a numerical model that allows examination of discrete stochastic charge fluctuations on the surface of aggregate grains and determines the effect of these fluctuations on the dynamics of grain aggregation. We show that the mean and standard deviation of charge on aggregate grains follow the same trends as those predicted for spheres having an equivalent radius, though aggregates exhibit larger variations from the predicted values. In some plasma environments, these charge fluctuations occur on timescales which are relevant for dynamics of aggregate growth. Coupled dynamics and charging models show that charge fluctuations tend to produce aggregates which are much more linear or filamentary than aggregates formed in an environment where the charge is stationary.

Symmetry and structure of carbon-nitrogen complexes in gallium arsenide from infrared spectroscopy and first-principles calculations

NASA Astrophysics Data System (ADS)

Künneth, Christopher; Kölbl, Simon; Wagner, Hans Edwin; Häublein, Volker; Kersch, Alfred; Alt, Hans Christian

2018-04-01

Molecular-like carbon-nitrogen complexes in GaAs are investigated both experimentally and theoretically. Two characteristic high-frequency stretching modes at 1973 and 2060 cm-1, detected by Fourier transform infrared absorption (FTIR) spectroscopy, appear in carbon- and nitrogen-implanted and annealed layers. From isotopic substitution, it is deduced that the chemical composition of the underlying complexes is CN2 and C2N, respectively. Piezospectroscopic FTIR measurements reveal that both centers have tetragonal symmetry. For density functional theory (DFT) calculations, linear entities are substituted for the As anion, with the axis oriented along the 〈1 0 0 〉 direction, in accordance with the experimentally ascertained symmetry. The DFT calculations support the stability of linear N-C-N and C-C-N complexes in the GaAs host crystal in the charge states ranging from + 3 to -3. The valence bonds of the complexes are analyzed using molecular-like orbitals from DFT. It turns out that internal bonds and bonds to the lattice are essentially independent of the charge state. The calculated vibrational mode frequencies are close to the experimental values and reproduce precisely the isotopic mass splitting from FTIR experiments. Finally, the formation energies show that under thermodynamic equilibrium CN2 is more stable than C2N.

Laboratory Studies of Thermal Energy Charge Transfer of Silicon and Iron Ions in Astrophysical Plasmas

NASA Technical Reports Server (NTRS)

Kwong, Victor H. S.

1997-01-01

The laser ablation/ion storage facility at the UNLV Physics Department is dedicated to the study of atomic processes in low temperature plasmas. Our current program is directed to the study of charge transfer of multiply charged ions and neutrals that are of importance to astrophysics at energies less than 1 eV (about 10(exp 4) K). Specifically, we measure the charge transfer rate coefficient of ions such as N(2+), Si(3+), Si(3+), with helium and Fe(2+) with molecular and atomic hydrogen. All these ions are found in a variety of astrophysical plasmas. Their electron transfer reactions with neutral atoms can affect the ionization equilibrium of the plasma.

Induced-Charge Enhancement of the Diffusion Potential in Membranes with Polarizable Nanopores

NASA Astrophysics Data System (ADS)

Ryzhkov, I. I.; Lebedev, D. V.; Solodovnichenko, V. S.; Shiverskiy, A. V.; Simunin, M. M.

2017-12-01

When a charged membrane separates two salt solutions of different concentrations, a potential difference appears due to interfacial Donnan equilibrium and the diffusion junction. Here, we report a new mechanism for the generation of a membrane potential in polarizable conductive membranes via an induced surface charge. It results from an electric field generated by the diffusion of ions with different mobilities. For uncharged membranes, this effect strongly enhances the diffusion potential and makes it highly sensitive to the ion mobilities ratio, electrolyte concentration, and pore size. Theoretical predictions on the basis of the space-charge model extended to polarizable nanopores fully agree with experimental measurements in KCl and NaCl aqueous solutions.

Non-equilibrium thermodynamics, maximum entropy production and Earth-system evolution.

PubMed

Kleidon, Axel

2010-01-13

The present-day atmosphere is in a unique state far from thermodynamic equilibrium. This uniqueness is for instance reflected in the high concentration of molecular oxygen and the low relative humidity in the atmosphere. Given that the concentration of atmospheric oxygen has likely increased throughout Earth-system history, we can ask whether this trend can be generalized to a trend of Earth-system evolution that is directed away from thermodynamic equilibrium, why we would expect such a trend to take place and what it would imply for Earth-system evolution as a whole. The justification for such a trend could be found in the proposed general principle of maximum entropy production (MEP), which states that non-equilibrium thermodynamic systems maintain steady states at which entropy production is maximized. Here, I justify and demonstrate this application of MEP to the Earth at the planetary scale. I first describe the non-equilibrium thermodynamic nature of Earth-system processes and distinguish processes that drive the system's state away from equilibrium from those that are directed towards equilibrium. I formulate the interactions among these processes from a thermodynamic perspective and then connect them to a holistic view of the planetary thermodynamic state of the Earth system. In conclusion, non-equilibrium thermodynamics and MEP have the potential to provide a simple and holistic theory of Earth-system functioning. This theory can be used to derive overall evolutionary trends of the Earth's past, identify the role that life plays in driving thermodynamic states far from equilibrium, identify habitability in other planetary environments and evaluate human impacts on Earth-system functioning. This journal is © 2010 The Royal Society

Ionization equilibrium at the transition from valence-band to acceptor-band migration of holes in boron-doped diamond

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

Poklonski, N. A., E-mail: poklonski@bsu.by; Vyrko, S. A.; Poklonskaya, O. N.

A quasi-classical model of ionization equilibrium in the p-type diamond between hydrogen-like acceptors (boron atoms which substitute carbon atoms in the crystal lattice) and holes in the valence band (v-band) is proposed. The model is applicable on the insulator side of the insulator–metal concentration phase transition (Mott transition) in p-Dia:B crystals. The densities of the spatial distributions of impurity atoms (acceptors and donors) and of holes in the crystal are considered to be Poissonian, and the fluctuations of their electrostatic potential energy are considered to be Gaussian. The model accounts for the decrease in thermal ionization energy of boron atomsmore » with increasing concentration, as well as for electrostatic fluctuations due to the Coulomb interaction limited to two nearest point charges (impurity ions and holes). The mobility edge of holes in the v-band is assumed to be equal to the sum of the threshold energy for diffusion percolation and the exchange energy of the holes. On the basis of the virial theorem, the temperature T{sub j} is determined, in the vicinity of which the dc band-like conductivity of holes in the v-band is approximately equal to the hopping conductivity of holes via the boron atoms. For compensation ratio (hydrogen-like donor to acceptor concentration ratio) K ≈ 0.15 and temperature T{sub j}, the concentration of “free” holes in the v-band and their jumping (turbulent) drift mobility are calculated. Dependence of the differential energy of thermal ionization of boron atoms (at the temperature 3T{sub j}/2) as a function of their concentration N is calculated. The estimates of the extrapolated into the temperature region close to T{sub j} hopping drift mobility of holes hopping from the boron atoms in the charge states (0) to the boron atoms in the charge states (−1) are given. Calculations based on the model show good agreement with electrical conductivity and Hall effect measurements for p-type diamond with boron atom concentrations in the range from 3 × 10{sup 17} to 3 × 10{sup 20 }cm{sup −3}, i.e., up to the Mott transition. The model uses no fitting parameters.« less

An energetic scale for equilibrium H/D fractionation factors illuminates hydrogen bond free energies in proteins

PubMed Central

Cao, Zheng; Bowie, James U

2014-01-01

Equilibrium H/D fractionation factors have been extensively employed to qualitatively assess hydrogen bond strengths in protein structure, enzyme active sites, and DNA. It remains unclear how fractionation factors correlate with hydrogen bond free energies, however. Here we develop an empirical relationship between fractionation factors and free energy, allowing for the simple and quantitative measurement of hydrogen bond free energies. Applying our empirical relationship to prior fractionation factor studies in proteins, we find: [1] Within the folded state, backbone hydrogen bonds are only marginally stronger on average in α-helices compared to β-sheets by ∼0.2 kcal/mol. [2] Charge-stabilized hydrogen bonds are stronger than neutral hydrogen bonds by ∼2 kcal/mol on average, and can be as strong as –7 kcal/mol. [3] Changes in a few hydrogen bonds during an enzyme catalytic cycle can stabilize an intermediate state by –4.2 kcal/mol. [4] Backbone hydrogen bonds can make a large overall contribution to the energetics of conformational changes, possibly playing an important role in directing conformational changes. [5] Backbone hydrogen bonding becomes more uniform overall upon ligand binding, which may facilitate participation of the entire protein structure in events at the active site. Our energetic scale provides a simple method for further exploration of hydrogen bond free energies. PMID:24501090

Influence of neural adaptation on dynamics and equilibrium state of neural activities in a ring neural network

NASA Astrophysics Data System (ADS)

Takiyama, Ken

2017-12-01

How neural adaptation affects neural information processing (i.e. the dynamics and equilibrium state of neural activities) is a central question in computational neuroscience. In my previous works, I analytically clarified the dynamics and equilibrium state of neural activities in a ring-type neural network model that is widely used to model the visual cortex, motor cortex, and several other brain regions. The neural dynamics and the equilibrium state in the neural network model corresponded to a Bayesian computation and statistically optimal multiple information integration, respectively, under a biologically inspired condition. These results were revealed in an analytically tractable manner; however, adaptation effects were not considered. Here, I analytically reveal how the dynamics and equilibrium state of neural activities in a ring neural network are influenced by spike-frequency adaptation (SFA). SFA is an adaptation that causes gradual inhibition of neural activity when a sustained stimulus is applied, and the strength of this inhibition depends on neural activities. I reveal that SFA plays three roles: (1) SFA amplifies the influence of external input in neural dynamics; (2) SFA allows the history of the external input to affect neural dynamics; and (3) the equilibrium state corresponds to the statistically optimal multiple information integration independent of the existence of SFA. In addition, the equilibrium state in a ring neural network model corresponds to the statistically optimal integration of multiple information sources under biologically inspired conditions, independent of the existence of SFA.

Reorganization energy upon charging a single molecule on an insulator measured by atomic force microscopy

NASA Astrophysics Data System (ADS)

Fatayer, Shadi; Schuler, Bruno; Steurer, Wolfram; Scivetti, Ivan; Repp, Jascha; Gross, Leo; Persson, Mats; Meyer, Gerhard

2018-05-01

Intermolecular single-electron transfer on electrically insulating films is a key process in molecular electronics1-4 and an important example of a redox reaction5,6. Electron-transfer rates in molecular systems depend on a few fundamental parameters, such as interadsorbate distance, temperature and, in particular, the Marcus reorganization energy7. This crucial parameter is the energy gain that results from the distortion of the equilibrium nuclear geometry in the molecule and its environment on charging8,9. The substrate, especially ionic films10, can have an important influence on the reorganization energy11,12. Reorganization energies are measured in electrochemistry13 as well as with optical14,15 and photoemission spectroscopies16,17, but not at the single-molecule limit and nor on insulating surfaces. Atomic force microscopy (AFM), with single-charge sensitivity18-22, atomic-scale spatial resolution20 and operable on insulating films, overcomes these challenges. Here, we investigate redox reactions of single naphthalocyanine (NPc) molecules on multilayered NaCl films. Employing the atomic force microscope as an ultralow current meter allows us to measure the differential conductance related to transitions between two charge states in both directions. Thereby, the reorganization energy of NPc on NaCl is determined as (0.8 ± 0.2) eV, and density functional theory (DFT) calculations provide the atomistic picture of the nuclear relaxations on charging. Our approach presents a route to perform tunnelling spectroscopy of single adsorbates on insulating substrates and provides insight into single-electron intermolecular transport.

The binding of quinone to the photosynthetic reaction centers: kinetics and thermodynamics of reactions occurring at the QB-site in zwitterionic and anionic liposomes.

PubMed

Mavelli, Fabio; Trotta, Massimo; Ciriaco, Fulvio; Agostiano, Angela; Giotta, Livia; Italiano, Francesca; Milano, Francesco

2014-07-01

Liposomes represent a versatile biomimetic environment for studying the interaction between integral membrane proteins and hydrophobic ligands. In this paper, the quinone binding to the QB-site of the photosynthetic reaction centers (RC) from Rhodobacter sphaeroides has been investigated in liposomes prepared with either the zwitterionic phosphatidylcholine (PC) or the negatively charged phosphatidylglycerol (PG) to highlight the role of the different phospholipid polar heads. Quinone binding (K Q) and interquinone electron transfer (L AB) equilibrium constants in the two type of liposomes were obtained by charge recombination reaction of QB-depleted RC in the presence of increasing amounts of ubiquinone-10 over the temperature interval 6-35 °C. The kinetic of the charge recombination reactions has been fitted by numerically solving the ordinary differential equations set associated with a detailed kinetic scheme involving electron transfer reactions coupled with quinone release and uptake. The entire set of traces at each temperature was accurately fitted using the sole quinone release constants (both in a neutral and a charge separated state) as adjustable parameters. The temperature dependence of the quinone exchange rate at the QB-site was, hence, obtained. It was found that the quinone exchange regime was always fast for PC while it switched from slow to fast in PG as the temperature rose above 20 °C. A new method was introduced in this paper for the evaluation of constant K Q using the area underneath the charge recombination traces as the indicator of the amount of quinone bound to the QB-site.

Stability boundaries for command augmentation systems

NASA Technical Reports Server (NTRS)

Shrivastava, P. C.

1987-01-01

The Stability Augmentation System (SAS) is a special case of the Command Augmentation System (CAS). Control saturation imposes bounds on achievable commands. The state equilibrium depends only on the open loop dynamics and control deflection. The control magnitude to achieve a desired command equilibrium is independent of the feedback gain. A feedback controller provides the desired response, maintains the system equilibrium under disturbances, but it does not affect the equilibrium values of states and control. The saturation boundaries change with commands, but the location of the equilibrium points in the saturated region remains unchanged. Nonzero command vectors yield saturation boundaries that are asymmetric with respect to the state equilibrium. Except for the saddle point case with MCE control law, the stability boundaries change with commands. For the cases of saddle point and unstable nodes, the region of stability decreases with increasing command magnitudes.

Charge Transfer Rate in Collisions of H + Ions with Si Atoms

NASA Astrophysics Data System (ADS)

Kimura, M.; Sannigrahi, A. B.; Gu, J. P.; Hirsch, G.; Buenker, R. J.; Shimamura, I.

1996-12-01

Charge transfer in Si(3P, 1D) + H+ collisions is studied theoretically by using a semiclassical molecular representation with six molecular channels for the triplet manifold and four channels for the singlet manifold at collision energies above 30 eV, and by using a fully quantum mechanical approach with two molecular channels for both triplet and singlet manifolds below 30 eV. The ab initio potential curves and nonadiabatic coupling matrix elements for the HSi+ system are obtained from multireference single- and double-excitation configuration interaction (MRD-CI) calculations employing a relatively large basis set. The present rate coefficients for charge transfer to Si+(4P) formation resulting from H+ + Si(3P) collisions are found to be large with values from 1 x 10-10 cm-3 s-1 at 1000 K to 1 x 10-8 cm-3 s-1 at 100,000 K. The rate coefficient for Si+(2P) formation, resulting from H+ + Si(3P) collisions, is found to be much smaller because of a larger energy defect from the initial state. These calculated rates are much larger than those reported by Baliunas & Butler, who estimated a value of 10-11 cm-3 s-1 in their coronal plasma study. The present result may be relevant to the description of the silicon ionization equilibrium.

Lattice-mediated magnetic order melting in TbMnO3

NASA Astrophysics Data System (ADS)

Baldini, Edoardo; Kubacka, Teresa; Mallett, Benjamin P. P.; Ma, Chao; Koohpayeh, Seyed M.; Zhu, Yimei; Bernhard, Christian; Johnson, Steven L.; Carbone, Fabrizio

2018-03-01

Recent ultrafast magnetic-sensitive measurements [Johnson et al., Phys. Rev. B 92, 184429 (2015), 10.1103/PhysRevB.92.184429; Bothschafter et al., Phys. Rev. B 96, 184414 (2017), 10.1103/PhysRevB.96.184414] have revealed a delayed melting of the long-range cycloid spin order in TbMnO3 following photoexcitation across the fundamental Mott-Hubbard gap. The microscopic mechanism behind this slow transfer of energy from the photoexcited carriers to the spin degrees of freedom is still elusive and not understood. Here, we address this problem by combining spectroscopic ellipsometry, ultrafast broadband optical spectroscopy, and ab initio calculations. Upon photoexcitation, we observe the emergence of a complex collective response, which is due to high-energy coherent optical phonons coupled to the out-of-equilibrium charge density. This response precedes the magnetic order melting and is interpreted as the fingerprint of the formation of anti-Jahn-Teller polarons. We propose that the charge localization in a long-lived self-trapped state hinders the emission of magnons and other spin-flip mechanisms, causing the energy transfer from the charge to the spin system to be mediated by the reorganization of the lattice. Furthermore, we provide evidence for the coherent excitation of a phonon mode associated with the ferroelectric phase transition.

Nonlinear responses of chiral fluids from kinetic theory

NASA Astrophysics Data System (ADS)

Hidaka, Yoshimasa; Pu, Shi; Yang, Di-Lun

2018-01-01

The second-order nonlinear responses of inviscid chiral fluids near local equilibrium are investigated by applying the chiral kinetic theory (CKT) incorporating side-jump effects. It is shown that the local equilibrium distribution function can be nontrivially introduced in a comoving frame with respect to the fluid velocity when the quantum corrections in collisions are involved. For the study of anomalous transport, contributions from both quantum corrections in anomalous hydrodynamic equations of motion and those from the CKT and Wigner functions are considered under the relaxation-time (RT) approximation, which result in anomalous charge Hall currents propagating along the cross product of the background electric field and the temperature (or chemical-potential) gradient and of the temperature and chemical-potential gradients. On the other hand, the nonlinear quantum correction on the charge density vanishes in the classical RT approximation, which in fact satisfies the matching condition given by the anomalous equation obtained from the CKT.

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.

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.

New instrument for tribocharge measurement due to single particle impacts.

PubMed

Watanabe, Hideo; Ghadiri, Mojtaba; Matsuyama, Tatsushi; Ding, Yu Long; Pitt, Kendal G

2007-02-01

During particulate solid processing, particle-particle and particle-wall collisions can generate electrostatic charges. This may lead to a variety of problems ranging from fire and explosion hazards to segregation, caking, and blocking. A fundamental understanding of the particle charging in such situations is therefore essential. For this purpose we have developed a new device that can measure charge transfer due to impact between a single particle and a metal plate. The device consists of an impact test system and two sets of Faraday cage and preamplifier for charge measurement. With current amplifiers, high-resolution measurements of particle charges of approximately 1 and 10 fC have been achieved before and after the impact, respectively. The device allows charge measurements of single particles with a size as small as approximately 100 microm impacting on the target at different incident angles with a velocity up to about 80 m/s. Further analyses of the charge transfer as a function of particle initial charge define an equilibrium charge, i.e., an initial charge level prior to impact for which no net charge transfer would occur as a result of impact.

New instrument for tribocharge measurement due to single particle impacts

NASA Astrophysics Data System (ADS)

Watanabe, Hideo; Ghadiri, Mojtaba; Matsuyama, Tatsushi; Long Ding, Yu; Pitt, Kendal G.

2007-02-01

During particulate solid processing, particle-particle and particle-wall collisions can generate electrostatic charges. This may lead to a variety of problems ranging from fire and explosion hazards to segregation, caking, and blocking. A fundamental understanding of the particle charging in such situations is therefore essential. For this purpose we have developed a new device that can measure charge transfer due to impact between a single particle and a metal plate. The device consists of an impact test system and two sets of Faraday cage and preamplifier for charge measurement. With current amplifiers, high-resolution measurements of particle charges of approximately 1 and 10fC have been achieved before and after the impact, respectively. The device allows charge measurements of single particles with a size as small as ˜100μm impacting on the target at different incident angles with a velocity up to about 80m/s. Further analyses of the charge transfer as a function of particle initial charge define an equilibrium charge, i.e., an initial charge level prior to impact for which no net charge transfer would occur as a result of impact.

Shear-induced laning transition in a confined colloidal film

NASA Astrophysics Data System (ADS)

Gerloff, Sascha; Vezirov, Tarlan A.; Klapp, Sabine H. L.

2017-06-01

Using Brownian dynamics simulations, we investigate a dense system of charged colloids exposed to shear flow in a confined (slit-pore) geometry. The equilibrium system at zero flow consists of three well-pronounced layers with a squarelike crystalline in-plane structure. We demonstrate that, for sufficiently large shear rates, the middle layer separates into two sublayers where the particles organize into moving lanes with opposite velocities. The formation of this "microlaned" state results in a destruction of the applied shear profile; it also has a strong impact on the structure of the system, and on its rheology as measured by the elements of the stress tensor. At higher shear rates, we observe a disordered state and finally a recrystallization reminiscent of the behavior of bilayer films. We also discuss the system size dependence and the robustness of the microlaned state against variations of the slit-pore width. In fact, for a pore width allowing for four layers, we observe a similar shear-induced state in which the system splits into two domains with opposite velocities.

Bilinear magnetoelectric resistance as a probe of three-dimensional spin texture in topological surface states

NASA Astrophysics Data System (ADS)

He, Pan; Zhang, Steven S.-L.; Zhu, Dapeng; Liu, Yang; Wang, Yi; Yu, Jiawei; Vignale, Giovanni; Yang, Hyunsoo

2018-05-01

Surface states of three-dimensional topological insulators exhibit the phenomenon of spin-momentum locking, whereby the orientation of an electron spin is determined by its momentum. Probing the spin texture of these states is of critical importance for the realization of topological insulator devices, but the main technique currently available is spin- and angle-resolved photoemission spectroscopy. Here we reveal a close link between the spin texture and a new kind of magnetoresistance, which depends on the relative orientation of the current with respect to the magnetic field as well as the crystallographic axes, and scales linearly with both the applied electric and magnetic fields. This bilinear magnetoelectric resistance can be used to map the spin texture of topological surface states by simple transport measurements. For a prototypical Bi2Se3 single layer, we can map both the in-plane and out-of-plane components of the spin texture (the latter arising from hexagonal warping). Theoretical calculations suggest that the bilinear magnetoelectric resistance originates from conversion of a non-equilibrium spin current into a charge current under application of the external magnetic field.

Electron transport in doped fullerene molecular junctions

NASA Astrophysics Data System (ADS)

Kaur, Milanpreet; Sawhney, Ravinder Singh; Engles, Derick

The effect of doping on the electron transport of molecular junctions is analyzed in this paper. The doped fullerene molecules are stringed to two semi-infinite gold electrodes and analyzed at equilibrium and nonequilibrium conditions of these device configurations. The contemplation is done using nonequilibrium Green’s function (NEGF)-density functional theory (DFT) to evaluate its density of states (DOS), transmission coefficient, molecular orbitals, electron density, charge transfer, current, and conductance. We conclude from the elucidated results that Au-C16Li4-Au and Au-C16Ne4-Au devices behave as an ordinary p-n junction diode and a Zener diode, respectively. Moreover, these doped fullerene molecules do not lose their metallic nature when sandwiched between the pair of gold electrodes.

Energetic, structural and electronic properties of metal vacancies in strained AlN/GaN interfaces.

PubMed

Kioseoglou, J; Pontikis, V; Komninou, Ph; Pavloudis, Th; Chen, J; Karakostas, Th

2015-04-01

AlN/GaN heterostructures have been studied using density-functional pseudopotential calculations yielding the formation energies of metal vacancies under the influence of local interfacial strains, the associated charge distribution and the energies of vacancy-induced electronic states. Interfaces are built normal to the polar <0 0 0 1> direction of the wurtzite structure by joining two single crystals of AlN and GaN that are a few atomic layers thick; thus, periodic boundary conditions generate two distinct heterophase interfaces. We show that the formation energy of vacancies is a function of their distance from the interfaces: the vacancy-interface interaction is found repulsive or attractive, depending on the type of the interface. When the interaction is attractive, the vacancy formation energy decreases with increasing the associated electric charge, and hence the equilibrium vacancy concentration at the interface is greater. This finding can reveal the well-known morphological differences existing between the two types of investigated interfaces. Moreover, we found that the electric charge is strongly localized around the Ga vacancy, while in the case of Al vacancies is almost uniformly distributed throughout the AlN/GaN heterostructure. Crucially, for the applications of heterostructures, metal vacancies introduce deep states in the calculated bandgap at energy levels from 0.5 to 1 eV above the valence band maximum (VBM). It is, therefore, predicted that vacancies could initiate 'green luminescence' i.e. light emission in the energy range of 2.5 eV stemming from electronic transitions between these extra levels, and the conduction band, or energy levels, due to shallow donors.

Self-force as probe of internal structure

NASA Astrophysics Data System (ADS)

Isoyama, Soichiro; Poisson, Eric

2012-08-01

The self-force acting on a (scalar or electric) charge held in place outside a massive body contains information about the body’s composition, and can therefore be used as a probe of internal structure. We explore this theme by computing the (scalar or electromagnetic) self-force when the body is a spherical ball of perfect fluid in hydrostatic equilibrium, under the assumption that its rest-mass density and pressure are related by a polytropic equation of state. The body is strongly self-gravitating, and all computations are performed in exact general relativity. The dependence on internal structure is best revealed by expanding the self-force in powers of r-10, with r0 denoting the radial position of the charge outside the body. To the leading order, the self-force scales as r-30 and depends only on the square of the charge and the body’s mass; the leading self-force is universal. The dependence on internal structure is seen at the next order, r-50, through a structure factor that depends on the equation of state. We compute this structure factor for relativistic polytropes, and show that for a fixed mass, it increases linearly with the body’s radius in the case of the scalar self-force, and quadratically with the body’s radius in the case of the electromagnetic self-force. In both cases we find that for a fixed mass and radius, the self-force is smaller if the body is more centrally dense, and larger if the mass density is more uniformly distributed.

Minimal excitation states for heat transport in driven quantum Hall systems

NASA Astrophysics Data System (ADS)

Vannucci, Luca; Ronetti, Flavio; Rech, Jérôme; Ferraro, Dario; Jonckheere, Thibaut; Martin, Thierry; Sassetti, Maura

2017-06-01

We investigate minimal excitation states for heat transport into a fractional quantum Hall system driven out of equilibrium by means of time-periodic voltage pulses. A quantum point contact allows for tunneling of fractional quasiparticles between opposite edge states, thus acting as a beam splitter in the framework of the electron quantum optics. Excitations are then studied through heat and mixed noise generated by the random partitioning at the barrier. It is shown that levitons, the single-particle excitations of a filled Fermi sea recently observed in experiments, represent the cleanest states for heat transport since excess heat and mixed shot noise both vanish only when Lorentzian voltage pulses carrying integer electric charge are applied to the conductor. This happens in the integer quantum Hall regime and for Laughlin fractional states as well, with no influence of fractional physics on the conditions for clean energy pulses. In addition, we demonstrate the robustness of such excitations to the overlap of Lorentzian wave packets. Even though mixed and heat noise have nonlinear dependence on the voltage bias, and despite the noninteger power-law behavior arising from the fractional quantum Hall physics, an arbitrary superposition of levitons always generates minimal excitation states.

Structural and electronic properties of AlN(0001) surface under partial N coverage as determined by ab initio approach

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

Strak, Pawel; Sakowski, Konrad; Kempisty, Pawel

2015-09-07

Properties of bare and nitrogen-covered Al-terminated AlN(0001) surface were determined using density functional theory (DFT) calculations. At a low nitrogen coverage, the Fermi level is pinned by Al broken bond states located below conduction band minimum. Adsorption of nitrogen is dissociative with an energy gain of 6.05 eV/molecule at a H3 site creating an overlap with states of three neighboring Al surface atoms. During this adsorption, electrons are transferred from Al broken bond to topmost N adatom states. Accompanying charge transfer depends on the Fermi level. In accordance with electron counting rule (ECR), the DFT results confirm the Fermi levelmore » is not pinned at the critical value of nitrogen coverage θ{sub N}(1) = 1/4 monolayer (ML), but it is shifted from an Al-broken bond state to Np{sub z} state. The equilibrium thermodynamic potential of nitrogen in vapor depends drastically on the Fermi level pinning being shifted by about 4 eV for an ECR state at 1/4 ML coverage. For coverage above 1/4 ML, adsorption is molecular with an energy gain of 1.5 eV at a skewed on-top position above an Al surface atom. Electronic states of the admolecule are occupied as in the free molecule, no electron transfer occurs and adsorption of a N{sub 2} molecule does not depend on the Fermi level. The equilibrium pressure of molecular nitrogen above an AlN(0001) surface depends critically on the Fermi level position, being very low and very high for low and high coverage, respectively. From this fact, one can conclude that at typical growth conditions, the Fermi level is not pinned, and the adsorption and incorporation of impurities depend on the position of Fermi level in the bulk.« less

THE EFFECT OF METASTABLE EQUILIBRIUM STATES ON THE PARTITIONING OF NITRATE BETWEEN THE GAS AND AEROSOL PHASES. (R824793)

EPA Science Inventory

With the aid of three atmospheric aerosol equilibrium models, we quantify the effect of metastable equilibrium states (efflorescence branch) in comparison to stable (deliquescence branch) on the partitioning of total nitrate between the gas and aerosol phases. On average, efflore...

Imaging the equilibrium state and magnetization dynamics of partially built hard disk write heads

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

Valkass, R. A. J., E-mail: rajv202@ex.ac.uk; Yu, W.; Shelford, L. R.

Four different designs of partially built hard disk write heads with a yoke comprising four repeats of NiFe (1 nm)/CoFe (50 nm) were studied by both x-ray photoemission electron microscopy (XPEEM) and time-resolved scanning Kerr microscopy (TRSKM). These techniques were used to investigate the static equilibrium domain configuration and the magnetodynamic response across the entire structure, respectively. Simulations and previous TRSKM studies have made proposals for the equilibrium domain configuration of similar structures, but no direct observation of the equilibrium state of the writers has yet been made. In this study, static XPEEM images of the equilibrium state of writer structures weremore » acquired using x-ray magnetic circular dichroism as the contrast mechanism. These images suggest that the crystalline anisotropy dominates the equilibrium state domain configuration, but competition with shape anisotropy ultimately determines the stability of the equilibrium state. Dynamic TRSKM images were acquired from nominally identical devices. These images suggest that a longer confluence region may hinder flux conduction from the yoke into the pole tip: the shorter confluence region exhibits clear flux beaming along the symmetry axis, whereas the longer confluence region causes flux to conduct along one edge of the writer. The observed variations in dynamic response agree well with the differences in the equilibrium magnetization configuration visible in the XPEEM images, confirming that minor variations in the geometric design of the writer structure can have significant effects on the process of flux beaming.« less

Bifurcation and Stability Analysis of the Equilibrium States in Thermodynamic Systems in a Small Vicinity of the Equilibrium Values of Parameters

NASA Astrophysics Data System (ADS)

Barsuk, Alexandr A.; Paladi, Florentin

2018-04-01

The dynamic behavior of thermodynamic system, described by one order parameter and one control parameter, in a small neighborhood of ordinary and bifurcation equilibrium values of the system parameters is studied. Using the general methods of investigating the branching (bifurcations) of solutions for nonlinear equations, we performed an exhaustive analysis of the order parameter dependences on the control parameter in a small vicinity of the equilibrium values of parameters, including the stability analysis of the equilibrium states, and the asymptotic behavior of the order parameter dependences on the control parameter (bifurcation diagrams). The peculiarities of the transition to an unstable state of the system are discussed, and the estimates of the transition time to the unstable state in the neighborhood of ordinary and bifurcation equilibrium values of parameters are given. The influence of an external field on the dynamic behavior of thermodynamic system is analyzed, and the peculiarities of the system dynamic behavior are discussed near the ordinary and bifurcation equilibrium values of parameters in the presence of external field. The dynamic process of magnetization of a ferromagnet is discussed by using the general methods of bifurcation and stability analysis presented in the paper.

Time-dependent chemo-electro-mechanical behavior of hydrogel-based structures

NASA Astrophysics Data System (ADS)

Leichsenring, Peter; Wallmersperger, Thomas

2018-03-01

Charged hydrogels are ionic polymer gels and belong to the class of smart materials. These gels are multiphasic materials which consist of a solid phase, a fluid phase and an ionic phase. Due to the presence of bound charges these materials are stimuli-responsive to electrical or chemical loads. The application of electrical or chemical stimuli as well as mechanical loads lead to a viscoelastic response. On the macroscopic scale, the response is governed by a local reversible release or absorption of water which, in turn, leads to a local decrease or increase of mass and a respective volume change. Furthermore, the chemo-electro-mechanical equilibrium of a hydrogel depends on the chemical composition of the gel and the surrounding solution bath. Due to the presence of bound charges in the hydrogel, this system can be understood as an osmotic cell where differences in the concentration of mobile ions in the gel and solution domain lead to an osmotic pressure difference. In the present work, a continuum-based numerical model is presented in order to describe the time-dependent swelling behavior of hydrogels. The numerical model is based on the Theory of Porous Media and captures the fluid-solid, fluid-ion and ion-ion interactions. As a direct consequence of the chemo-electro-mechanical equilibrium, the corresponding boundary conditions are defined following the equilibrium conditions. For the interaction of the hydrogel with surrounding mechanical structures, also respective jump condtions are formulated. Finaly, numerical results of the time-dependent behavior of a hydrogel-based chemo-sensor will be presented.

Equilibrium expert: an add-in to Microsoft Excel for multiple binding equilibrium simulations and parameter estimations.

PubMed

Raguin, Olivier; Gruaz-Guyon, Anne; Barbet, Jacques

2002-11-01

An add-in to Microsoft Excel was developed to simulate multiple binding equilibriums. A partition function, readily written even when the equilibrium is complex, describes the experimental system. It involves the concentrations of the different free molecular species and of the different complexes present in the experiment. As a result, the software is not restricted to a series of predefined experimental setups but can handle a large variety of problems involving up to nine independent molecular species. Binding parameters are estimated by nonlinear least-square fitting of experimental measurements as supplied by the user. The fitting process allows user-defined weighting of the experimental data. The flexibility of the software and the way it may be used to describe common experimental situations and to deal with usual problems such as tracer reactivity or nonspecific binding is demonstrated by a few examples. The software is available free of charge upon request.

Temperature lapse rates at restricted thermodynamic equilibrium. Part II: Saturated air and further discussions

NASA Astrophysics Data System (ADS)

Björnbom, Pehr

2016-03-01

In the first part of this work equilibrium temperature profiles in fluid columns with ideal gas or ideal liquid were obtained by numerically minimizing the column energy at constant entropy, equivalent to maximizing column entropy at constant energy. A minimum in internal plus potential energy for an isothermal temperature profile was obtained in line with Gibbs' classical equilibrium criterion. However, a minimum in internal energy alone for adiabatic temperature profiles was also obtained. This led to a hypothesis that the adiabatic lapse rate corresponds to a restricted equilibrium state, a type of state in fact discussed already by Gibbs. In this paper similar numerical results for a fluid column with saturated air suggest that also the saturated adiabatic lapse rate corresponds to a restricted equilibrium state. The proposed hypothesis is further discussed and amended based on the previous and the present numerical results and a theoretical analysis based on Gibbs' equilibrium theory.

Amorphous ices explained in terms of nonequilibrium phase transitions in supercooled water

NASA Astrophysics Data System (ADS)

Limmer, David; Chandler, David

2013-03-01

We analyze the phase diagram of supercooled water out-of-equilibrium using concepts from space-time thermodynamics and the dynamic facilitation theory of the glass transition, together with molecular dynamics simulations. We find that when water is driven out-of-equilibrium, it can exist in multiple amorphous states. In contrast, we find that when water is at equilibrium, it can exist in only one liquid state. The amorphous non-equilibrium states are solids, distinguished from the liquid by their lack of mobility, and distinguished from each other by their different densities and local structure. This finding explains the experimentally observed polyamorphism of water as a class of nonequilibrium phenomena involving glasses of different densities. While the amorphous solids can be long lived, they are thermodynamically unstable. When allowed to relax to equilibrium, they crystallize with pathways that pass first through liquid state configurations and then to ordered ice.

Energetics of halogen impurities in thorium dioxide

NASA Astrophysics Data System (ADS)

Kuganathan, Navaratnarajah; Ghosh, Partha S.; Arya, Ashok K.; Dey, Gautam K.; Grimes, Robin W.

2017-11-01

Defect energies for halogen impurity atoms (Cl, Br and I) in thoria are calculated using the generalized gradient approximation and projector augmented plane wave potentials under the framework of density functional theory. The energy to place a halogen atom at a pre-existing lattice site is the incorporation energy. Seven sites are considered: octahedral interstitial, O vacancy, Th vacancy, Th-O di-vacancy cluster (DV) and the three O-Th-O tri-vacancy cluster (NTV) configurations. For point defects and vacancy clusters, neutral and all possible defect charge states up to full formal charge are considered. The most favourable incorporation site for Cl is the singly charged positive oxygen vacancy while for Br and I it is the NTV1 cluster. By considering the energy to form the defect sites, solution energies are generated. These show that in both ThO2-x and ThO2 the most favourable solution equilibrium site for halides is the single positively charged oxygen vacancy (although in ThO2, I demonstrates the same solubility in the NTV1 and DV clusters). Solution energies are much lower in ThO2-x than in ThO2 indicating that stoichiometry is a significant factor in determining solubility. In ThO2, all three halogens are highly insoluble and in ThO2-x Br and I remain insoluble. Although ½Cl2 is soluble in ThO2-x alternative phases such as ZrCl4 exist which are of lower energy.

Nonlinear road pricing for congestion and the environment.

DOT National Transportation Integrated Search

2012-03-30

Under nonlinear road pricing (or tolling), the price charged is not strictly proportional to the distance travelled inside a tolling area, the generalized travel cost is not link-wise additive, and finding a user equilibrium distribution is typically...

Effect of Layer Charge on CO2 and H2O Intercalations in Swelling Clays.

PubMed

Rao, Qi; Leng, Yongsheng

2016-11-08

The effect of layer charge on the intercalation of supercritical carbon dioxide (scCO 2 )-H 2 O mixture in Na-montmorillonite clay interlayers under T = 323 K and P = 90 bar geologic sequestration conditions has been further investigated. This effect includes the charge amount and its location (within either octahedral or tetrahedral layers due to isomorphic substitutions). Two clay models with different layer charges are used in this study. Simulation results show that the increase of charge amount shifts the monolayer-to-bilayer (1W-to-2W) hydration transition toward the lower relative humidity (RH), increasing water sorption at the expense of reducing the overall sorption amount of CO 2 in the clay interlayer. However, the combination of the influence of charge amount and charge location leads to insignificant changes in equilibrium basal spacings of the high- and low-charge clays. Molecular dynamics simulations show that the CO 2 dimers, which are frequently seen in low-charge clay interlayers, vanish in high-charge clay interlayers even at low RH of 30%.

Experiments on Dust Grain Charging

NASA Technical Reports Server (NTRS)

Abbas, M. N.; Craven, P. D.; Spann, J. F.; Tankosic, D.; LeClair, A.; West, E. A.

2004-01-01

Dust particles in various astrophysical environments are charged by a variety of mechanisms generally involving collisional processes with other charged particles and photoelectric emission with UV radiation from nearby sources. The sign and the magnitude of the particle charge are determined by the competition between the charging processes by UV radiation and collisions with charged particles. Knowledge of the particle charges and equilibrium potentials is important for understanding of a number of physical processes. The charge of a dust grain is thus a fundamental parameter that influences the physics of dusty plasmas, processes in the interplanetary medium and interstellar medium, interstellar dust clouds, planetary rings, cometary and outer atmospheres of planets etc. In this paper we present some results of experiments on charging of dust grains carried out on a laboratory facility capable levitating micron size dust grains in an electrodynamic balance in simulated space environments. The charging/discharging experiments were carried out by exposing the dust grains to energetic electron beams and UV radiation. Photoelectric efficiencies and yields of micron size dust grains of SiO2, and lunar simulates obtained from NASA-JSC will be presented.

Stochastic many-particle model for LFP electrodes

NASA Astrophysics Data System (ADS)

Guhlke, Clemens; Gajewski, Paul; Maurelli, Mario; Friz, Peter K.; Dreyer, Wolfgang

2018-02-01

In the framework of non-equilibrium thermodynamics, we derive a new model for many-particle electrodes. The model is applied to LiFePO4 (LFP) electrodes consisting of many LFP particles of nanometer size. The phase transition from a lithium-poor to a lithium-rich phase within LFP electrodes is controlled by both different particle sizes and surface fluctuations leading to a system of stochastic differential equations. An explicit relation between battery voltage and current controlled by the thermodynamic state variables is derived. This voltage-current relation reveals that in thin LFP electrodes lithium intercalation from the particle surfaces into the LFP particles is the principal rate-limiting process. There are only two constant kinetic parameters in the model describing the intercalation rate and the fluctuation strength, respectively. The model correctly predicts several features of LFP electrodes, viz. the phase transition, the observed voltage plateaus, hysteresis and the rate-limiting capacity. Moreover we study the impact of both the particle size distribution and the active surface area on the voltage-charge characteristics of the electrode. Finally we carefully discuss the phase transition for varying charging/discharging rates.

FT-Raman, FT-IR spectra and total energy distribution of 3-pentyl-2,6-diphenylpiperidin-4-one: DFT method.

PubMed

Subashchandrabose, S; Saleem, H; Erdogdu, Y; Rajarajan, G; Thanikachalam, V

2011-11-01

FT-Raman and FT-IR spectra were recorded for 3-pentyl-2,6-diphenylpiperidin-4-one (PDPO) sample in solid state. The equilibrium geometries, harmonic vibrational frequencies, infrared and the Raman scattering intensities were computed using DFT/6-31G(d,p) level. Results obtained at this level of theory were used for a detailed interpretation of the infrared and Raman spectra, based on the total energy distribution (TED) of the normal modes. Molecular parameters such as bond lengths, bond angles and dihedral angles were calculated and compared with X-ray diffraction data. This comparison was good agreement. The intra-molecular charge transfer was calculated by means of natural bond orbital analysis (NBO). Hyperconjugative interaction energy was more during the π-π* transition. Energy gap of the molecule was found using HOMO and LUMO calculation, hence the less band gap, which seems to be more stable. Atomic charges of the carbon, nitrogen and oxygen were calculated using same level of calculation. Copyright © 2011 Elsevier B.V. All rights reserved.

Motion of charged particles in planetary magnetospheres with nonelectromagnetic forces

NASA Technical Reports Server (NTRS)

Huang, T. S.; Hill, T. W.; Wolf, R. A.

1988-01-01

Expressions are derived for the mirror point, the bounce period, the second adiabatic invariant, and the bounce-averaged azimuthal drift velocity as functions of equatorial pitch angle for a charged particle in a dipole magnetic field in the presence of centrifugal, gravitational, and Coriolis forces. These expressions are evaluated numerically, and the results are displayed graphically. The average azimuthal drift speed for a flux tube containing a thermal equilibrium plasma distribution is also evaluated.

3D dust clouds (Yukawa Balls) in strongly coupled dusty plasmas

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

Melzer, A.; Passvogel, M.; Miksch, T.

2010-06-16

Three-dimensional finite systems of charged dust particles confined to concentric spherical shells in a dusty plasma, so-called 'Yukawa balls', have been studied with respect to their static and dynamic properties. Here, we review the charging of particles in a dusty plasma discharge by computer simulations and the respective particle arrangements. The normal mode spectrum of Yukawa balls is measured from the 3D thermal Brownian motion of the dust particles around their equilibrium positions.

A molecular model of proteoglycan-associated electrostatic forces in cartilage mechanics.

PubMed

Buschmann, M D; Grodzinsky, A J

1995-05-01

Measured values of the swelling pressure of charged proteoglycans (PG) in solution (Williams RPW, and Comper WD; Biophysical Chemistry 36:223, 1990) and the ionic strength dependence of the equilibrium modulus of PG-rich articular cartilage (Eisenberg SR, and Grodzinsky AJ; J Orthop Res 3: 148, 1985) are compared to the predictions of two models. Each model is a representation of electrostatic forces arising from charge present on spatially fixed macromolecules and spatially mobile micro-ions. The first is a macroscopic continuum model based on Donnan equilibrium that includes no molecular-level structure and assumes that the electrical potential is spatially invariant within the polyelectrolyte medium (i.e. zero electric field). The second model is based on a microstructural, molecular-level solution of the Poisson-Boltzmann (PB) equation within a unit cell containing a charged glycosaminoglycan (GAG) molecule and its surrounding atmosphere of mobile ions. This latter approach accounts for the space-varying electrical potential and electrical field between the GAG constituents of the PG. In computations involving no adjustable parameters, the PB-cell model agrees with the measured pressure of PG solutions to within experimental error (10%), whereas the ideal Donnan model overestimates the pressure by up to 3-fold. In computations involving one adjustable parameter for each model, the PB-cell model predicts the ionic strength dependence of the equilibrium modulus of articular cartilage. Near physiological ionic strength, the Donnan model overpredicts the modulus data by 2-fold, but the two models coincide for low ionic strengths (C0 < 0.025M) where the spatially invariant Donnan potential is a closer approximation to the PB potential distribution. The PB-cell model result indicates that electrostatic forces between adjacent GAGs predominate in determining the swelling pressure of PG in the concentration range found in articular cartilage (20-80 mg/ml). The PB-cell model is also consistent with data (Eisenberg and Grodzinsky, 1985, Lai WM, Hou JS, and Mow VC; J Biomech Eng 113: 245, 1991) showing that these electrostatic forces account for approximately 1/2 (290kPa) the equilibrium modulus of cartilage at physiological ionic strength while absolute swelling pressures may be as low as approximately 25-100kPa. This important property of electrostatic repulsion between GAGs that are highly charged but spaced a few Debye lengths apart allows cartilage to resist compression (high modulus) without generating excessive intratissue swelling pressures.

Dynamic study of sub-micro sized LiFePO4 cathodes by in-situ tender X-ray absorption near edge structure

NASA Astrophysics Data System (ADS)

Wang, Dongniu; Wang, Huixin; Yang, Jinli; Zhou, Jigang; Hu, Yongfeng; Xiao, Qunfeng; Fang, Haitao; Sham, Tsun-Kong

2016-01-01

Olivine-type phosphates (LiMPO4, M = Fe, Mn, Co) are promising cathode materials for lithium-ion batteries that are generally accepted to follow first order equilibrium phase transformations. Herein, the phase transformation dynamics of sub-micro sized LiFePO4 particles with limited rate capability at a low current density of 0.14 C was investigated. An in-situ X-ray Absorption Near Edge Structure (XANES) measurement was conducted at the Fe and P K-edge for the dynamic studies upon lithiation and delithiation. Fe K-edge XANES spectra demonstrate that not only lithium-rich intermediate phase LixFePO4 (x = 0.6-0.75), but also lithium-poor intermediate phase LiyFePO4 (y = 0.1-0.25) exist during the charge and discharge, respectively. Furthermore, during charge and discharge, a fluctuation of the FePO4 and LiFePO4 fractions obtained by liner combination fitting around the imaginary phase fractions followed Faraday's law and the equilibrium first-order two-phase transformation versus reaction time is present, respectively. The charging and discharging process has a reversible phase transformation dynamics with symmetric structural evolution routes. P K-edge XANES spectra reveal an enrichment of PF6-1 anions at the surface of the electrode during charging.

Multiscale Multiphysics and Multidomain Models I: Basic Theory

PubMed Central

Wei, Guo-Wei

2013-01-01

This work extends our earlier two-domain formulation of a differential geometry based multiscale paradigm into a multidomain theory, which endows us the ability to simultaneously accommodate multiphysical descriptions of aqueous chemical, physical and biological systems, such as fuel cells, solar cells, nanofluidics, ion channels, viruses, RNA polymerases, molecular motors and large macromolecular complexes. The essential idea is to make use of the differential geometry theory of surfaces as a natural means to geometrically separate the macroscopic domain of solvent from the microscopic domain of solute, and dynamically couple continuum and discrete descriptions. Our main strategy is to construct energy functionals to put on an equal footing of multiphysics, including polar (i.e., electrostatic) solvation, nonpolar solvation, chemical potential, quantum mechanics, fluid mechanics, molecular mechanics, coarse grained dynamics and elastic dynamics. The variational principle is applied to the energy functionals to derive desirable governing equations, such as multidomain Laplace-Beltrami (LB) equations for macromolecular morphologies, multidomain Poisson-Boltzmann (PB) equation or Poisson equation for electrostatic potential, generalized Nernst-Planck (NP) equations for the dynamics of charged solvent species, generalized Navier-Stokes (NS) equation for fluid dynamics, generalized Newton's equations for molecular dynamics (MD) or coarse-grained dynamics and equation of motion for elastic dynamics. Unlike the classical PB equation, our PB equation is an integral-differential equation due to solvent-solute interactions. To illustrate the proposed formalism, we have explicitly constructed three models, a multidomain solvation model, a multidomain charge transport model and a multidomain chemo-electro-fluid-MD-elastic model. Each solute domain is equipped with distinct surface tension, pressure, dielectric function, and charge density distribution. In addition to long-range Coulombic interactions, various non-electrostatic solvent-solute interactions are considered in the present modeling. We demonstrate the consistency between the non-equilibrium charge transport model and the equilibrium solvation model by showing the systematical reduction of the former to the latter at equilibrium. This paper also offers a brief review of the field. PMID:25382892

Multiscale Multiphysics and Multidomain Models I: Basic Theory.

PubMed

Wei, Guo-Wei

2013-12-01

This work extends our earlier two-domain formulation of a differential geometry based multiscale paradigm into a multidomain theory, which endows us the ability to simultaneously accommodate multiphysical descriptions of aqueous chemical, physical and biological systems, such as fuel cells, solar cells, nanofluidics, ion channels, viruses, RNA polymerases, molecular motors and large macromolecular complexes. The essential idea is to make use of the differential geometry theory of surfaces as a natural means to geometrically separate the macroscopic domain of solvent from the microscopic domain of solute, and dynamically couple continuum and discrete descriptions. Our main strategy is to construct energy functionals to put on an equal footing of multiphysics, including polar (i.e., electrostatic) solvation, nonpolar solvation, chemical potential, quantum mechanics, fluid mechanics, molecular mechanics, coarse grained dynamics and elastic dynamics. The variational principle is applied to the energy functionals to derive desirable governing equations, such as multidomain Laplace-Beltrami (LB) equations for macromolecular morphologies, multidomain Poisson-Boltzmann (PB) equation or Poisson equation for electrostatic potential, generalized Nernst-Planck (NP) equations for the dynamics of charged solvent species, generalized Navier-Stokes (NS) equation for fluid dynamics, generalized Newton's equations for molecular dynamics (MD) or coarse-grained dynamics and equation of motion for elastic dynamics. Unlike the classical PB equation, our PB equation is an integral-differential equation due to solvent-solute interactions. To illustrate the proposed formalism, we have explicitly constructed three models, a multidomain solvation model, a multidomain charge transport model and a multidomain chemo-electro-fluid-MD-elastic model. Each solute domain is equipped with distinct surface tension, pressure, dielectric function, and charge density distribution. In addition to long-range Coulombic interactions, various non-electrostatic solvent-solute interactions are considered in the present modeling. We demonstrate the consistency between the non-equilibrium charge transport model and the equilibrium solvation model by showing the systematical reduction of the former to the latter at equilibrium. This paper also offers a brief review of the field.

Low Mach number fluctuating hydrodynamics for electrolytes

NASA Astrophysics Data System (ADS)

Péraud, Jean-Philippe; Nonaka, Andy; Chaudhri, Anuj; Bell, John B.; Donev, Aleksandar; Garcia, Alejandro L.

2016-11-01

We formulate and study computationally the low Mach number fluctuating hydrodynamic equations for electrolyte solutions. We are interested in studying transport in mixtures of charged species at the mesoscale, down to scales below the Debye length, where thermal fluctuations have a significant impact on the dynamics. Continuing our previous work on fluctuating hydrodynamics of multicomponent mixtures of incompressible isothermal miscible liquids [A. Donev et al., Phys. Fluids 27, 037103 (2015), 10.1063/1.4913571], we now include the effect of charged species using a quasielectrostatic approximation. Localized charges create an electric field, which in turn provides additional forcing in the mass and momentum equations. Our low Mach number formulation eliminates sound waves from the fully compressible formulation and leads to a more computationally efficient quasi-incompressible formulation. We demonstrate our ability to model saltwater (NaCl) solutions in both equilibrium and nonequilibrium settings. We show that our algorithm is second order in the deterministic setting and for length scales much greater than the Debye length gives results consistent with an electroneutral approximation. In the stochastic setting, our model captures the predicted dynamics of equilibrium and nonequilibrium fluctuations. We also identify and model an instability that appears when diffusive mixing occurs in the presence of an applied electric field.

Generation of Suprathermal Electrons by Collective Processes in Collisional Plasma

NASA Astrophysics Data System (ADS)

Tigik, S. F.; Ziebell, L. F.; Yoon, P. H.

2017-11-01

The ubiquity of high-energy tails in the charged particle velocity distribution functions (VDFs) observed in space plasmas suggests the existence of an underlying process responsible for taking a fraction of the charged particle population out of thermal equilibrium and redistributing it to suprathermal velocity and energy ranges. The present Letter focuses on a new and fundamental physical explanation for the origin of suprathermal electron velocity distribution function (EVDF) in a collisional plasma. This process involves a newly discovered electrostatic bremsstrahlung (EB) emission that is effective in a plasma in which binary collisions are present. The steady-state EVDF dictated by such a process corresponds to a Maxwellian core plus a quasi-inverse power-law tail, which is a feature commonly observed in many space plasma environments. In order to demonstrate this, the system of self-consistent particle- and wave-kinetic equations are numerically solved with an initially Maxwellian EVDF and Langmuir wave spectral intensity, which is a state that does not reflect the presence of EB process, and hence not in force balance. The EB term subsequently drives the system to a new force-balanced steady state. After a long integration period it is demonstrated that the initial Langmuir fluctuation spectrum is modified, which in turn distorts the initial Maxwellian EVDF into a VDF that resembles the said core-suprathermal VDF. Such a mechanism may thus be operative at the coronal source region, which is characterized by high collisionality.

Simulation of Charged Systems in Heterogeneous Dielectric Media via a True Energy Functional

NASA Astrophysics Data System (ADS)

Jadhao, Vikram; Solis, Francisco J.; de la Cruz, Monica Olvera

2012-11-01

For charged systems in heterogeneous dielectric media, a key obstacle for molecular dynamics (MD) simulations is the need to solve the Poisson equation in the media. This obstacle can be bypassed using MD methods that treat the local polarization charge density as a dynamic variable, but such approaches require access to a true free energy functional, one that evaluates to the equilibrium electrostatic energy at its minimum. In this Letter, we derive the needed functional. As an application, we develop a Car-Parrinello MD method for the simulation of free charges present near a spherical emulsion droplet separating two immiscible liquids with different dielectric constants. Our results show the presence of nonmonotonic ionic profiles in the dielectric with a lower dielectric constant.

Strong coupling electrostatics for randomly charged surfaces: antifragility and effective interactions.

PubMed

Ghodrat, Malihe; Naji, Ali; Komaie-Moghaddam, Haniyeh; Podgornik, Rudolf

2015-05-07

We study the effective interaction mediated by strongly coupled Coulomb fluids between dielectric surfaces carrying quenched, random monopolar charges with equal mean and variance, both when the Coulomb fluid consists only of mobile multivalent counterions and when it consists of an asymmetric ionic mixture containing multivalent and monovalent (salt) ions in equilibrium with an aqueous bulk reservoir. We analyze the consequences that follow from the interplay between surface charge disorder, dielectric and salt image effects, and the strong electrostatic coupling that results from multivalent counterions on the distribution of these ions and the effective interaction pressure they mediate between the surfaces. In a dielectrically homogeneous system, we show that the multivalent counterions are attracted towards the surfaces with a singular, disorder-induced potential that diverges logarithmically on approach to the surfaces, creating a singular but integrable counterion density profile that exhibits an algebraic divergence at the surfaces with an exponent that depends on the surface charge (disorder) variance. This effect drives the system towards a state of lower thermal 'disorder', one that can be described by a renormalized temperature, exhibiting thus a remarkable antifragility. In the presence of an interfacial dielectric discontinuity, the singular behavior of counterion density at the surfaces is removed but multivalent counterions are still accumulated much more strongly close to randomly charged surfaces as compared with uniformly charged ones. The interaction pressure acting on the surfaces displays in general a highly non-monotonic behavior as a function of the inter-surface separation with a prominent regime of attraction at small to intermediate separations. This attraction is caused directly by the combined effects from charge disorder and strong coupling electrostatics of multivalent counterions, which dominate the surface-surface repulsion due to the (equal) mean charges on the two surfaces and the osmotic pressure of monovalent ions residing between them. These effects can be quite significant even with a small degree of surface charge disorder relative to the mean surface charge. The strong coupling, disorder-induced attraction is typically much stronger than the van der Waals interaction between the surfaces, especially within a range of several nanometers for the inter-surface separation, where such effects are predicted to be most pronounced.

Proximity effects in cold gases of multiply charged atoms (Review)

NASA Astrophysics Data System (ADS)

Chikina, I.; Shikin, V.

2016-07-01

Possible proximity effects in gases of cold, multiply charged atoms are discussed. Here we deal with rarefied gases with densities nd of multiply charged (Z ≫ 1) atoms at low temperatures in the well-known Thomas-Fermi (TF) approximation, which can be used to evaluate the statistical properties of single atoms. In order to retain the advantages of the TF formalism, which is successful for symmetric problems, the external boundary conditions accounting for the finiteness of the density of atoms (donors), nd ≠ 0, are also symmetrized (using a spherical Wigner-Seitz cell) and formulated in a standard way that conserves the total charge within the cell. The model shows that at zero temperature in a rarefied gas of multiply charged atoms there is an effective long-range interaction Eproxi(nd), the sign of which depends on the properties of the outer shells of individual atoms. The long-range character of the interaction Eproxi is evaluated by comparing it with the properties of the well-known London dispersive attraction ELond(nd) < 0, which is regarded as a long-range interaction in gases. For the noble gases argon, krypton, and xenon Eproxi>0 and for the alkali and alkaline-earth elements Eproxi < 0. At finite temperatures, TF statistics manifests a new, anomalously large proximity effect, which reflects the tendency of electrons localized at Coulomb centers to escape into the continuum spectrum. The properties of thermal decay are interesting in themselves as they determine the important phenomenon of dissociation of neutral complexes into charged fragments. This phenomenon appears consistently in the TF theory through the temperature dependence of the different versions of Eproxi. The anomaly in the thermal proximity effect shows up in the following way: for T ≠ 0 there is no equilibrium solution of TS statistics for single multiply charged atoms in a vacuum when the effect is present. Instability is suppressed in a Wigner-Seitz model under the assumption that there are no electron fluxes through the outer boundary R3 ∝ n-1d of a Wigner-Seitz cell. Eproxi corresponds to the definition of the correlation energy in a gas of interacting particles. This review is written so as to enable comparison of the results of the TF formalism with the standard assumptions of the correlation theory for classical plasmas. The classic example from work on weak solutions (including charged solutions)—the use of semi-impermeable membranes for studies of osmotic pressure—is highly appropriate for problems involving Eproxi. Here we are speaking of one or more sharp boundaries formed by the ionic component of a many-particle problem. These may be a metal-vacuum boundary in a standard Casimir cell in a study of the vacuum properties in the 2l gap between conducting media of different kinds or different layered systems (quantum wells) in semiconductors, etc. As the mobile part of the equilibrium near a sharp boundary, electrons can (should) escape beyond the confines of the ion core into a gap 2l with a probability that depends, among other factors, on the properties of Eproxi for the electron cloud inside the conducting walls of the Casimir cell (quantum well). The analog of the Casimir sandwich in semiconductors is the widely used multilayer heterostructures referred to as quantum wells of width 2l with sides made of suitable doped materials, which ensure statistical equilibrium exchange of electrons between the layers of the multilayer structure. The thermal component of the proximity effects in semiconducting quantum wells provides an idea of many features of the dissociation process in doped semiconductors. In particular, a positive Eproxi > 0 (relative to the bottom of the conduction band) indicates that TF donors with a finite density nd ≠ 0 form a degenerate, semiconducting state in the semiconductor. At zero temperature, there is a finite density of free carriers which increases with a power-law dependence on T.

Prediction of gas/particle partitioning of polybrominated diphenyl ethers (PBDEs) in global air: A theoretical study

NASA Astrophysics Data System (ADS)

Li, Y.-F.; Ma, W.-L.; Yang, M.

2015-02-01

Gas/particle (G/P) partitioning of semi-volatile organic compounds (SVOCs) is an important process that primarily governs their atmospheric fate, long-range atmospheric transport, and their routes of entering the human body. All previous studies on this issue are hypothetically based on equilibrium conditions, the results of which do not predict results from monitoring studies well in most cases. In this study, a steady-state model instead of an equilibrium-state model for the investigation of the G/P partitioning behavior of polybrominated diphenyl ethers (PBDEs) was established, and an equation for calculating the partition coefficients under steady state (KPS) of PBDEs (log KPS = log KPE + logα) was developed in which an equilibrium term (log KPE = log KOA + logfOM -11.91 where fOM is organic matter content of the particles) and a non-equilibrium term (log α, caused by dry and wet depositions of particles), both being functions of log KOA (octanol-air partition coefficient), are included. It was found that the equilibrium is a special case of steady state when the non-equilibrium term equals zero. A criterion to classify the equilibrium and non-equilibrium status of PBDEs was also established using two threshold values of log KOA, log KOA1, and log KOA2, which divide the range of log KOA into three domains: equilibrium, non-equilibrium, and maximum partition domain. Accordingly, two threshold values of temperature t, tTH1 when log KOA = log KOA1 and tTH2 when log KOA = log KOA2, were identified, which divide the range of temperature also into the same three domains for each PBDE congener. We predicted the existence of the maximum partition domain (the values of log KPS reach a maximum constant of -1.53) that every PBDE congener can reach when log KOA ≥ log KOA2, or t ≤ tTH2. The novel equation developed in this study was applied to predict the G/P partition coefficients of PBDEs for our Chinese persistent organic pollutants (POPs) Soil and Air Monitoring Program, Phase 2 (China-SAMP-II) program and other monitoring programs worldwide, including in Asia, Europe, North America, and the Arctic, and the results matched well with all the monitoring data, except those obtained at e-waste sites due to the unpredictable PBDE emissions at these sites. This study provided evidence that the newly developed steady-state-based equation is superior to the equilibrium-state-based equation that has been used in describing the G/P partitioning behavior over decades. We suggest that the investigation on G/P partitioning behavior for PBDEs should be based onsteady-state, not equilibrium state, and equilibrium is just a special case of steady-state when non-equilibrium factors can be ignored. We also believe that our new equation provides a useful tool for environmental scientists in both monitoring and modeling research on G/P partitioning of PBDEs and can be extended to predict G/P partitioning behavior for other SVOCs as well.

Infinite-mode squeezed coherent states and non-equilibrium statistical mechanics (phase-space-picture approach)

NASA Technical Reports Server (NTRS)

Yeh, Leehwa

1993-01-01

The phase-space-picture approach to quantum non-equilibrium statistical mechanics via the characteristic function of infinite-mode squeezed coherent states is introduced. We use quantum Brownian motion as an example to show how this approach provides an interesting geometrical interpretation of quantum non-equilibrium phenomena.

THE EFFECT OF METASTABLE EQUILIBRIUM STATES ON THE PARTITIONING OF NITRATE BETWEEN THE GAS AND AEROSOL PHASES. (R826371C005)

EPA Science Inventory

With the aid of three atmospheric aerosol equilibrium models, we quantify the effect of metastable equilibrium states (efflorescence branch) in comparison to stable (deliquescence branch) on the partitioning of total nitrate between the gas and aerosol phases. On average, effl...

Turbulence Modeling Effects on the Prediction of Equilibrium States of Buoyant Shear Flows

NASA Technical Reports Server (NTRS)

Zhao, C. Y.; So, R. M. C.; Gatski, T. B.

2001-01-01

The effects of turbulence modeling on the prediction of equilibrium states of turbulent buoyant shear flows were investigated. The velocity field models used include a two-equation closure, a Reynolds-stress closure assuming two different pressure-strain models and three different dissipation rate tensor models. As for the thermal field closure models, two different pressure-scrambling models and nine different temperature variance dissipation rate, Epsilon(0) equations were considered. The emphasis of this paper is focused on the effects of the Epsilon(0)-equation, of the dissipation rate models, of the pressure-strain models and of the pressure-scrambling models on the prediction of the approach to equilibrium turbulence. Equilibrium turbulence is defined by the time rate (if change of the scaled Reynolds stress anisotropic tensor and heat flux vector becoming zero. These conditions lead to the equilibrium state parameters. Calculations show that the Epsilon(0)-equation has a significant effect on the prediction of the approach to equilibrium turbulence. For a particular Epsilon(0)-equation, all velocity closure models considered give an equilibrium state if anisotropic dissipation is accounted for in one form or another in the dissipation rate tensor or in the Epsilon(0)-equation. It is further found that the models considered for the pressure-strain tensor and the pressure-scrambling vector have little or no effect on the prediction of the approach to equilibrium turbulence.

TD-DFT Insight into Photodissociation of Co-C Bond in Coenzyme B12

NASA Astrophysics Data System (ADS)

Kozlowski, Pawel; Liu, Hui; Kornobis, Karina; Lodowski, Piotr; Jaworska, Maria

2013-12-01

Coenzyme B12 (AdoCbl) is one of the most biologically active forms of vitamin B12, and continues to be a topic of active research interest. The mechanism of Co-C bond cleavage in AdoCbl, and the corresponding enzymatic reactions are however, not well understood at the molecular level. In this work, time-dependent density functional theory (TD-DFT) has been applied to investigate the photodissociation of coenzyme B12. To reduce computational cost, while retaining the major spectroscopic features of AdoCbl, a truncated model based on ribosylcobalamin (RibCbl) was used to simulate Co-C photodissociation. Equilibrium geometries of RibCbl were obtained by optimization at the DFT/BP86/TZVP level of theory, and low-lying excited states were calculated by TD-DFT using the same functional and basis set. The calculated singlet states, and absorption spectra were simulated in both the gas phase, and water, using the polarizable continuum model (PCM). Both spectra were in reasonable agreement with experimental data, and potential energy curves based on vertical excitations were plotted to explore the nature of Co-C bond dissociation. It was found that a repulsive 3(σCo-C → σ*Co-C) triplet state became dissociative at large Co-C bond distance, similar to a previous observation for methylcobalamin (MeCbl). Furthermore, potential energy surfaces (PESs) obtained as a function of both Co-CRib and Co-NIm distances, identify the S1 state as a key intermediate generated during photoexcitation of RibCbl, attributed to a mixture of a MLCT (metal-to-ligand charge transfer) and a σ bonding-ligand charge transfer (SBLCT) states.

Unique equilibrium states for Bonatti–Viana diffeomorphisms

NASA Astrophysics Data System (ADS)

Climenhaga, Vaughn; Fisher, Todd; Thompson, Daniel J.

2018-06-01

We show that the robustly transitive diffeomorphisms constructed by Bonatti and Viana have unique equilibrium states for natural classes of potentials. In particular, we characterize the SRB measure as the unique equilibrium state for a suitable geometric potential. The techniques developed are applicable to a wide class of DA diffeomorphisms, and persist under C 1 perturbations of the map. These results are an application of general machinery developed by the first and last named authors.

A potential low cost adsorbent for the removal of cationic dyes from aqueous solutions

NASA Astrophysics Data System (ADS)

Uddin, Md. Tamez; Rahman, Md. Arifur; Rukanuzzaman, Md.; Islam, Md. Akhtarul

2017-10-01

This study was aimed at using mango leaf powder (MLP) as a potential adsorbent for the removal of methylene blue (MB) from aqueous solutions. Characterization of the adsorbent was carried out with scanning electron microscopy, Fourier transform infrared spectroscopy, and nitrogen adsorption-desorption analysis. The pH at the point of zero charge of the adsorbent was determined by titration method and was found a value to be 5.6 ± 0.2. Batch studies were performed to evaluate the influence of various experimental parameters like initial solution pH, contact time, initial concentration of dye and adsorbent dosage on the removal of MB. An adsorption-desorption study was carried out resulting the mechanism of adsorption was carried out by electrostatic force of attraction. The adsorption equilibrium time required for the adsorption of MB on MLP was almost 2 h and 85 ± 5% of the total amount of dye uptake was found to occur in the first rapid phase (30 min). The Langmuir and Freundlich isotherm models were used for modeling the adsorption equilibrium. The experimental equilibrium data could be well interpreted by Langmuir isotherm with maximum adsorption capacity of 156 mg/g. To state the sorption kinetics, the fits of pseudo-first-order and pseudo-second-order kinetic models were investigated. It was obtained that the adsorption process followed the pseudo-second-order rate kinetics. The above findings suggest that MLP can be effectively used for decontamination of dye containing wastewater.

Stochastic driven systems far from equilibrium

NASA Astrophysics Data System (ADS)

Kim, Kyung Hyuk

We study the dynamics and steady states of two systems far from equilibrium: a 1-D driven lattice gas and a driven Brownian particle with inertia. (1) We investigate the dynamical scaling behavior of a 1-D driven lattice gas model with two species of particles hopping in opposite directions. We confirm numerically that the dynamic exponent is equal to z = 1.5. We show analytically that a quasi-particle representation relates all phase points to a special phase line directly related to the single-species asymmetric simple exclusion process. Quasi-particle two-point correlations decay exponentially, and in such a manner that quasi-particles of opposite charge dynamically screen each other with a special balance. The balance encompasses all over the phase space. These results indicate that the model belongs to the Kardar-Parisi-Zhang (KPZ) universality class. (2) We investigate the non-equilibrium thermodynamics of a Brownian particle with inertia under feedback control of its inertia. We find such open systems can act as a molecular refrigerator due to an entropy pumping mechanism. We extend the fluctuation theorems to the refrigerator. The entropy pumping modifies both the Jarzynski equality and the fluctuation theorems. We discover that the entropy pumping has a dual role of work and heat. We also investigate the thermodynamics of the particle under a hydrodynamic interaction described by a Langevin equation with a multiplicative noise. The Stratonovich stochastic integration prescription involved in the definition of heat is shown to be the unique physical choice.

Geometric approach to nuclear pasta phases

NASA Astrophysics Data System (ADS)

Kubis, Sebastian; Wójcik, Włodzimierz

2016-12-01

By use of the variational methods and differential geometry in the framework of the liquid drop model we formulate appropriate equilibrium equations for pasta phases with imposed periodicity. The extension of the Young-Laplace equation in the case of charged fluid is obtained. The β equilibrium and virial theorem are also generalized. All equations are shown in gauge invariant form. For the first time, the pasta shape stability analysis is carried out. The proper stability condition in the form of the generalized Jacobi equation is derived. The presented formalism is tested on some particular cases.

Solvent-Controlled Branching of Localized versus Delocalized Singlet Exciton States and Equilibration with Charge Transfer in a Structurally Well-Defined Tetracene Dimer

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

Cook, Jasper D.; Carey, Thomas J.; Arias, Dylan H.

A detailed photophysical picture is elaborated for a structurally well-defined and symmetrical bis-tetracene dimer in solution. The molecule was designed for interrogation of the initial photophysical steps (S 1 → 1TT) in intramolecular singlet fission (SF). (Triisopropylsilyl)acetylene substituents on the dimer TIPS-BT1 as well as a monomer model TIPS-Tc enable a comparison of photophysical properties, including transient absorption dynamics, as solvent polarity is varied. In nonpolar toluene solutions, TIPS-BT1 decays via radiative and nonradiative pathways to the ground state with no evidence for dynamics related to the initial stages of SF. This contrasts with the behavior of the previously reportedmore » unsubstituted dimer BT1 and is likely a consequence of energetic perturbations to the singlet excited-state manifold of TIPS-BT1 by the (trialkylsilyl)acetylene substituents. In polar benzonitrile, two key findings emerge. First, photoexcited TIPS-BT1 shows a bifurcation into both arm-localized (S 1-loc) and dimer-delocalized (S 1-dim) singlet exciton states. The S 1-loc decays to the ground state, and weak temperature dependence of its emissive signatures suggests that once it is formed, it is isolated from S 1-dim. Emissive signatures of the S 1-dim state, on the other hand, are strongly temperature-dependent, and transient absorption dynamics show that S1-dim equilibrates with an intramolecular charge-transfer state in 50 ps at room temperature. This equilibrium decays to the ground state with little evidence for formation of long-lived triplets nor 1TT. These detailed studies spectrally characterize many of the key states in intramolecular SF in this class of dimers but highlight the need to tune electronic coupling and energetics for the S 1 → 1TT photoreaction.« less

Solvent-Controlled Branching of Localized versus Delocalized Singlet Exciton States and Equilibration with Charge Transfer in a Structurally Well-Defined Tetracene Dimer

DOE PAGES

Cook, Jasper D.; Carey, Thomas J.; Arias, Dylan H.; ...

2017-11-04

A detailed photophysical picture is elaborated for a structurally well-defined and symmetrical bis-tetracene dimer in solution. The molecule was designed for interrogation of the initial photophysical steps (S 1 → 1TT) in intramolecular singlet fission (SF). (Triisopropylsilyl)acetylene substituents on the dimer TIPS-BT1 as well as a monomer model TIPS-Tc enable a comparison of photophysical properties, including transient absorption dynamics, as solvent polarity is varied. In nonpolar toluene solutions, TIPS-BT1 decays via radiative and nonradiative pathways to the ground state with no evidence for dynamics related to the initial stages of SF. This contrasts with the behavior of the previously reportedmore » unsubstituted dimer BT1 and is likely a consequence of energetic perturbations to the singlet excited-state manifold of TIPS-BT1 by the (trialkylsilyl)acetylene substituents. In polar benzonitrile, two key findings emerge. First, photoexcited TIPS-BT1 shows a bifurcation into both arm-localized (S 1-loc) and dimer-delocalized (S 1-dim) singlet exciton states. The S 1-loc decays to the ground state, and weak temperature dependence of its emissive signatures suggests that once it is formed, it is isolated from S 1-dim. Emissive signatures of the S 1-dim state, on the other hand, are strongly temperature-dependent, and transient absorption dynamics show that S1-dim equilibrates with an intramolecular charge-transfer state in 50 ps at room temperature. This equilibrium decays to the ground state with little evidence for formation of long-lived triplets nor 1TT. These detailed studies spectrally characterize many of the key states in intramolecular SF in this class of dimers but highlight the need to tune electronic coupling and energetics for the S 1 → 1TT photoreaction.« less

Persistent photoconductivity due to trapping of induced charges in Sn/ZnO thin film based UV photodetector

NASA Astrophysics Data System (ADS)

Yadav, Harish Kumar; Sreenivas, K.; Gupta, Vinay

2010-05-01

Photoconductivity relaxation in rf magnetron sputtered ZnO thin films integrated with ultrathin tin metal overlayer is investigated. Charge carriers induced at the ZnO-metal interface by the tin metal overlayer compensates the surface lying trap centers and leads to the enhanced photoresponse. On termination of ultraviolet radiation, recombination of the photoexcited electrons with the valence band holes leaves the excess carriers deeply trapped at the recombination center and holds the dark conductivity level at a higher value. Equilibrium between the recombination centers and valence band, due to trapped charges, eventually stimulates the persistent photoconductivity in the Sn/ZnO photodetectors.

Nonequilibrium quantum dynamics and transport: from integrability to many-body localization

NASA Astrophysics Data System (ADS)

Vasseur, Romain; Moore, Joel E.

2016-06-01

We review the non-equilibrium dynamics of many-body quantum systems after a quantum quench with spatial inhomogeneities, either in the Hamiltonian or in the initial state. We focus on integrable and many-body localized systems that fail to self-thermalize in isolation and for which the standard hydrodynamical picture breaks down. The emphasis is on universal dynamics, non-equilibrium steady states and new dynamical phases of matter, and on phase transitions far from thermal equilibrium. We describe how the infinite number of conservation laws of integrable and many-body localized systems lead to complex non-equilibrium states beyond the traditional dogma of statistical mechanics.

Mimicking Nonequilibrium Steady States with Time-Periodic Driving

DTIC Science & Technology

2016-08-29

nonequilibrium steady states, and vice versa, within the theoretical framework of discrete-state stochastic thermodynamics . Nonequilibrium steady states...equilibrium [2], spontaneous relaxation towards equilibrium [3], nonequilibrium steady states generated by fixed thermodynamic forces [4], and stochastic pumps...paradigm, a system driven by fixed thermodynamic forces—such as temperature gradients or chemical potential differences— reaches a steady state in

Response of GaAs charge storage devices to transient ionizing radiation

NASA Astrophysics Data System (ADS)

Hetherington, D. L.; Klem, J. F.; Hughes, R. C.; Weaver, H. T.

Charge storage devices in which non-equilibrium depletion regions represent stored charge are sensitive to ionizing radiation. This results since the radiation generates electron-hole pairs that neutralize excess ionized dopant charge. Silicon structures, such as dynamic RAM or CCD cells are particularly sensitive to radiation since carrier diffusion lengths in this material are often much longer than the depletion width, allowing collection of significant quantities of charge from quasi-neutral sections of the device. For GaAs the situation is somewhat different in that minority carrier diffusion lengths are shorter than in silicon, and although mobilities are higher, we expect a reduction of radiation sensitivity as suggested by observations of reduced quantum efficiency in GaAs solar cells. Dynamic memory cells in GaAs have potential increased retention times. In this paper, we report the response of a novel GaAs dynamic memory element to transient ionizing radiation. The charge readout technique is nondestructive over a reasonable applied voltage range and is more sensitive to stored charge than a simple capacitor.

Dynamic Charge Storage in Ionic Liquids-Filled Nanopores: Insight from a Computational Cyclic Voltammetry Study.

PubMed

He, Yadong; Huang, Jingsong; Sumpter, Bobby G; Kornyshev, Alexei A; Qiao, Rui

2015-01-02

Understanding the dynamic charge storage in nanoporous electrodes with room-temperature ionic liquid electrolytes is essential for optimizing them to achieve supercapacitors with high energy and power densities. Herein, we report coarse-grained molecular dynamics simulations of the cyclic voltammetry of supercapacitors featuring subnanometer pores and model ionic liquids. We show that the cyclic charging and discharging of nanopores are governed by the interplay between the external field-driven ion transport and the sloshing dynamics of ions inside of the pore. The ion occupancy along the pore length depends strongly on the scan rate and varies cyclically during charging/discharging. Unlike that at equilibrium conditions or low scan rates, charge storage at high scan rates is dominated by counterions while the contribution by co-ions is marginal or negative. These observations help explain the perm-selective charge storage observed experimentally. We clarify the mechanisms underlying these dynamic phenomena and quantify their effects on the efficiency of the dynamic charge storage in nanopores.

Identified particle distributions in pp and Au+Au collisions at square root of (sNN)=200 GeV.

PubMed

Adams, J; Adler, C; Aggarwal, M M; Ahammed, Z; Amonett, J; Anderson, B D; Anderson, M; Arkhipkin, D; Averichev, G S; Badyal, S K; Balewski, J; Barannikova, O; Barnby, L S; Baudot, J; Bekele, S; Belaga, V V; Bellwied, R; Berger, J; Bezverkhny, B I; Bhardwaj, S; Bhaskar, P; Bhati, A K; Bichsel, H; Billmeier, A; Bland, L C; Blyth, C O; Bonner, B E; Botje, M; Boucham, A; Brandin, A; Bravar, A; Cadman, R V; Cai, X Z; Caines, H; Calderón de la Barca Sánchez, M; Carroll, J; Castillo, J; Castro, M; Cebra, D; Chaloupka, P; Chattopadhyay, S; Chen, H F; Chen, Y; Chernenko, S P; Cherney, M; Chikanian, A; Choi, B; Christie, W; Coffin, J P; Cormier, T M; Cramer, J G; Crawford, H J; Das, D; Das, S; Derevschikov, A A; Didenko, L; Dietel, T; Dong, X; Draper, J E; Du, F; Dubey, A K; Dunin, V B; Dunlop, J C; Dutta Majumdar, M R; Eckardt, V; Efimov, L G; Emelianov, V; Engelage, J; Eppley, G; Erazmus, B; Estienne, M; Fachini, P; Faine, V; Faivre, J; Fatemi, R; Filimonov, K; Filip, P; Finch, E; Fisyak, Y; Flierl, D; Foley, K J; Fu, J; Gagliardi, C A; Ganti, M S; Gutierrez, T D; Gagunashvili, N; Gans, J; Gaudichet, L; Germain, M; Geurts, F; Ghazikhanian, V; Ghosh, P; Gonzalez, J E; Grachov, O; Grigoriev, V; Gronstal, S; Grosnick, D; Guedon, M; Guertin, S M; Gupta, A; Gushin, E; Hallman, T J; Hardtke, D; Harris, J W; Heinz, M; Henry, T W; Heppelmann, S; Herston, T; Hippolyte, B; Hirsch, A; Hjort, E; Hoffmann, G W; Horsley, M; Huang, H Z; Huang, S L; Humanic, T J; Igo, G; Ishihara, A; Jacobs, P; Jacobs, W W; Janik, M; Johnson, I; Jones, P G; Judd, E G; Kabana, S; Kaneta, M; Kaplan, M; Keane, D; Kiryluk, J; Kisiel, A; Klay, J; Klein, S R; Klyachko, A; Koetke, D D; Kollegger, T; Konstantinov, A S; Kopytine, M; Kotchenda, L; Kovalenko, A D; Kramer, M; Kravtsov, P; Krueger, K; Kuhn, C; Kulikov, A I; Kumar, A; Kunde, G J; Kunz, C L; Kutuev, R Kh; Kuznetsov, A A; Lamont, M A C; Landgraf, J M; Lange, S; Lansdell, C P; Lasiuk, B; Laue, F; Lauret, J; Lebedev, A; Lednický, R; Leontiev, V M; LeVine, M J; Li, C; Li, Q; Lindenbaum, S J; Lisa, M A; Liu, F; Liu, L; Liu, Z; Liu, Q J; Ljubicic, T; Llope, W J; Long, H; Longacre, R S; Lopez-Noriega, M; Love, W A; Ludlam, T; Lynn, D; Ma, J; Ma, Y G; Magestro, D; Mahajan, S; Mangotra, L K; Mahapatra, D P; Majka, R; Manweiler, R; Margetis, S; Markert, C; Martin, L; Marx, J; Matis, H S; Matulenko, Yu A; McShane, T S; Meissner, F; Melnick, Yu; Meschanin, A; Messer, M; Miller, M L; Milosevich, Z; Minaev, N G; Mironov, C; Mishra, D; Mitchell, J; Mohanty, B; Molnar, L; Moore, C F; Mora-Corral, M J; Morozov, V; de Moura, M M; Munhoz, M G; Nandi, B K; Nayak, S K; Nayak, T K; Nelson, J M; Nevski, P; Nikitin, V A; Nogach, L V; Norman, B; Nurushev, S B; Odyniec, G; Ogawa, A; Okorokov, V; Oldenburg, M; Olson, D; Paic, G; Pandey, S U; Pal, S K; Panebratsev, Y; Panitkin, S Y; Pavlinov, A I; Pawlak, T; Perevoztchikov, V; Peryt, W; Petrov, V A; Phatak, S C; Picha, R; Planinic, M; Pluta, J; Porile, N; Porter, J; Poskanzer, A M; Potekhin, M; Potrebenikova, E; Potukuchi, B V K S; Prindle, D; Pruneau, C; Putschke, J; Rai, G; Rakness, G; Raniwala, R; Raniwala, S; Ravel, O; Ray, R L; Razin, S V; Reichhold, D; Reid, J G; Renault, G; Retiere, F; Ridiger, A; Ritter, H G; Roberts, J B; Rogachevski, O V; Romero, J L; Rose, A; Roy, C; Ruan, L J; Sahoo, R; Sakrejda, I; Salur, S; Sandweiss, J; Savin, I; Schambach, J; Scharenberg, R P; Schmitz, N; Schroeder, L S; Schweda, K; Seger, J; Seliverstov, D; Seyboth, P; Shahaliev, E; Shao, M; Sharma, M; Shestermanov, K E; Shimanskii, S S; Singaraju, R N; Simon, F; Skoro, G; Smirnov, N; Snellings, R; Sood, G; Sorensen, P; Sowinski, J; Spinka, H M; Srivastava, B; Stanislaus, S; Stock, R; Stolpovsky, A; Strikhanov, M; Stringfellow, B; Struck, C; Suaide, A A P; Sugarbaker, E; Suire, C; Sumbera, M; Surrow, B; Symons, T J M; de Toledo, A Szanto; Szarwas, P; Tai, A; Takahashi, J; Tang, A H; Thein, D; Thomas, J H; Tikhomirov, V; Tokarev, M; Tonjes, M B; Trainor, T A; Trentalange, S; Tribble, R E; Trivedi, M D; Trofimov, V; Tsai, O; Ullrich, T; Underwood, D G; Van Buren, G; VanderMolen, A M; Vasiliev, A N; Vasiliev, M; Vigdor, S E; Viyogi, Y P; Voloshin, S A; Waggoner, W; Wang, F; Wang, G; Wang, X L; Wang, Z M; Ward, H; Watson, J W; Wells, R; Westfall, G D; Whitten, C; Wieman, H; Willson, R; Wissink, S W; Witt, R; Wood, J; Wu, J; Xu, N; Xu, Z; Xu, Z Z; Yakutin, A E; Yamamoto, E; Yang, J; Yepes, P; Yurevich, V I; Zanevski, Y V; Zborovský, I; Zhang, H; Zhang, H Y; Zhang, W M; Zhang, Z P; Zołnierczuk, P A; Zoulkarneev, R; Zoulkarneeva, J; Zubarev, A N

2004-03-19

Transverse mass and rapidity distributions for charged pions, charged kaons, protons, and antiprotons are reported for square root of [sNN]=200 GeV pp and Au+Au collisions at Relativistic Heary Ion Collider (RHIC). Chemical and kinetic equilibrium model fits to our data reveal strong radial flow and long duration from chemical to kinetic freeze-out in central Au+Au collisions. The chemical freeze-out temperature appears to be independent of initial conditions at RHIC energies.

Space charge induced surface stresses: implications in ceria and other ionic solids.

PubMed

Sheldon, Brian W; Shenoy, Vivek B

2011-05-27

Volume changes associated with point defects in space charge layers can produce strains that substantially alter thermodynamic equilibrium near surfaces in ionic solids. For example, near-surface compressive stresses exceeding -10 GPa are predicted for ceria. The magnitude of this effect is consistent with anomalous lattice parameter increases that occur in ceria nanoparticles. These stresses should significantly alter defect concentrations and key transport properties in a wide range of materials (e.g., ceria electrolytes in fuel cells). © 2011 American Physical Society

Extracting Aggregation Free Energies of Mixed Clusters from Simulations of Small Systems: Application to Ionic Surfactant Micelles.

PubMed

Zhang, X; Patel, L A; Beckwith, O; Schneider, R; Weeden, C J; Kindt, J T

2017-11-14

Micelle cluster distributions from molecular dynamics simulations of a solvent-free coarse-grained model of sodium octyl sulfate (SOS) were analyzed using an improved method to extract equilibrium association constants from small-system simulations containing one or two micelle clusters at equilibrium with free surfactants and counterions. The statistical-thermodynamic and mathematical foundations of this partition-enabled analysis of cluster histograms (PEACH) approach are presented. A dramatic reduction in computational time for analysis was achieved through a strategy similar to the selector variable method to circumvent the need for exhaustive enumeration of the possible partitions of surfactants and counterions into clusters. Using statistics from a set of small-system (up to 60 SOS molecules) simulations as input, equilibrium association constants for micelle clusters were obtained as a function of both number of surfactants and number of associated counterions through a global fitting procedure. The resulting free energies were able to accurately predict micelle size and charge distributions in a large (560 molecule) system. The evolution of micelle size and charge with SOS concentration as predicted by the PEACH-derived free energies and by a phenomenological four-parameter model fit, along with the sensitivity of these predictions to variations in cluster definitions, are analyzed and discussed.

Role of grain size and particle velocity distribution in secondary electron emission in space plasmas

NASA Technical Reports Server (NTRS)

Chow, V. W.; Mendis, D. A.; Rosenberg, M.

1993-01-01

By virtue of being generally immersed in a plasma environment, cosmic dust is necessarily electrically charged. The fact that secondary emission plays an important role in determining the equilibrium grain potential has long been recognized, but the fact that the grain size plays a crucial role in this equilibrium potential, when secondary emission is important, has not been widely appreciated. Using both conducting and insulating spherical grains of various sizes and also both Maxwellian and generalized Lorentzian plasmas (which are believed to represent certain space plasmas), we have made a detailed study of this problem. In general, we find that the secondary emission yield delta increases with decreasing size and becomes very large for grains whose dimensions are comparable to the primary electron penetration depth, such as in the case of the very small grains observed at comet Halley and inferred in the interstellar medium. Moreover, we observed that delta is larger for insulators and equilibrium potentials are generally more positive when the plasma has a broad non-Maxwellian tail. Interestingly, we find that for thermal energies that are expected in several cosmic regions, grains of different sizes can have opposite charge, the smaller ones being positive while the larger ones are negative. This may have important consequences for grain accretion in polydisperse dusty space plasmas.

Conjugated block copolymers: A building block for high-performance organic photovoltaics

NASA Astrophysics Data System (ADS)

Guo, Changhe

State-of-the-art organic photovoltaics rely on kinetically trapped, partially phase-separated structures of donor/acceptor mixtures to create a high interfacial area for exciton dissociation and networks of bicontinuous phases for charge transport. Nevertheless, intrinsic structural disorder and weak intermolecular interactions in polymer blends limit the performance and stability of organic electronic devices. We demonstrate a potential strategy to control morphology and donor/acceptor heterojunctions through conjugated block copolymer poly(3-hexylthiophene)- block-poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(thiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (P3HT-b-PFTBT). Block copolymers can self-assemble into well-ordered nanostructures ideal for photovoltaic applications. When utilized as the photovoltaic active layer, P3HT-b-PFTBT block copolymer devices demonstrate thermal stability and photoconversion efficiency of 3% well beyond devices composed of the constituent polymer blends. Resonant soft X-ray scattering (RSOXS) is used to elucidate the structural origin for efficient block copolymer photovoltaics. Energy tuning in soft X-ray ranges gives RSOXS chemical sensitivity to characterize organic thin films with compositionally similar phases or complicated multiphase systems. RSOXS reveals that the remarkable performance of P3HT-b-PFTBT devices is due to self-assembly into nanoscale in-plane lamellar morphology, which not only establishes an equilibrium microstructure amenable for exciton dissociation but also provides pathways for efficient charge transport. Furthermore, we find evidence that covalent control of donor/acceptor interfaces in block copolymers has the potential to promote charge separation and optimize the photoconversion process by limiting charge recombination. To visualize the nanostructure in organic thin films, we introduce low energy-loss energy-filtered transmission electron microscopy (EFTEM) as an important alternative approach to generate contrast from differences in optoelectronic properties and enable chemical imaging of organic materials. The widely-studied polymer/fullerene system is used as a test sample to demonstrate the application of this technique for structure characterization in the active layer of organic solar cells. In addition, well-ordered equilibrium nanostructures and covalent control of donor/acceptor interfaces make P3HT-b-PFTBT an excellent model for studying the effect of crystalline texture in the active layer on charge transport and photovoltaic performance. Solvent additives are applied to induce a drastic texture change from mainly face-on to edge-on orientations in crystalline P3HT domains of block copolymer thin films. We find that P3HT- b-PFTBT block copolymer devices demonstrate similar optimal performance, regardless of the dramatic changes in the predominant crystalline orientations adopted in P3HT domains. Our results provide further insights into the molecular organization required for efficient charge transport and device operation.

Selectivity and stoichiometry boosting of beta-cyclodextrin in cationic/anionic surfactant systems: when host-guest equilibrium meets biased aggregation equilibrium.

PubMed

Jiang, Lingxiang; Yu, Caifang; Deng, Manli; Jin, Changwen; Wang, Yilin; Yan, Yun; Huang, Jianbin

2010-02-18

Cationic surfactant/anionic surfactant/beta-CD ternary aqueous systems provide a platform for the coexistence of the host-guest (beta-CD/surfactant) equilibrium and the biased aggregation (monomeric/aggregated surfactants) equilibrium. We report here that the interplay between the two equilibria dominates the systems as follows. (1) The biased aggregation equilibrium imposes an apparent selectivity on the host-guest equilibrium, namely, beta-CD has to always selectively bind the major surfactant (molar fraction > 0.5) even if binding constants of beta-CD to the pair of surfactants are quite similar. (2) In return, the host-guest equilibrium amplifies the bias of the aggregation equilibrium, that is, the selective binding partly removes the major surfactant from the aggregates and leaves the aggregate composition approaching the electroneutral mixing stoichiometry. (3) This composition variation enhances electrostatic attractions between oppositely charged surfactant head groups, thus resulting in less-curved aggregates. In particular, the present apparent host-guest selectivity is of remarkably high values, and the selectivity stems from the bias of the aggregation equilibrium rather than the difference in binding constants. Moreover, beta-CD is defined as a "stoichiometry booster" for the whole class of cationic/anionic surfactant systems, which provides an additional degree of freedom to directly adjust aggregate compositions of the systems. The stoichiometry boosting of the compositions can in turn affect or even determine microstructures and macroproperties of the systems.

Degradable transportation network with the addition of electric vehicles: Network equilibrium analysis

PubMed Central

Zhang, Rui; Yao, Enjian; Yang, Yang

2017-01-01

Introducing electric vehicles (EVs) into urban transportation network brings higher requirement on travel time reliability and charging reliability. Specifically, it is believed that travel time reliability is a key factor influencing travelers’ route choice. Meanwhile, due to the limited cruising range, EV drivers need to better learn about the required energy for the whole trip to make decisions about whether charging or not and where to charge (i.e., charging reliability). Since EV energy consumption is highly related to travel speed, network uncertainty affects travel time and charging demand estimation significantly. Considering the network uncertainty resulted from link degradation, which influences the distribution of travel demand on transportation network and the energy demand on power network, this paper aims to develop a reliability-based network equilibrium framework for accommodating degradable road conditions with the addition of EVs. First, based on the link travel time distribution, the mean and variance of route travel time and monetary expenses related to energy consumption are deduced, respectively. And the charging time distribution of EVs with charging demand is also estimated. Then, a nested structure is considered to deal with the difference of route choice behavior derived by the different uncertainty degrees between the routes with and without degradable links. Given the expected generalized travel cost and a psychological safety margin, a traffic assignment model with the addition of EVs is formulated. Subsequently, a heuristic solution algorithm is developed to solve the proposed model. Finally, the effects of travelers’ risk attitude, network degradation degree, and EV penetration rate on network performance are illustrated through an example network. The numerical results show that the difference of travelers’ risk attitudes does have impact on the route choice, and the widespread adoption of EVs can cut down the total system travel cost effectively when the transportation network is more reliable. PMID:28886167

Degradable transportation network with the addition of electric vehicles: Network equilibrium analysis.

PubMed

Zhang, Rui; Yao, Enjian; Yang, Yang

2017-01-01

Introducing electric vehicles (EVs) into urban transportation network brings higher requirement on travel time reliability and charging reliability. Specifically, it is believed that travel time reliability is a key factor influencing travelers' route choice. Meanwhile, due to the limited cruising range, EV drivers need to better learn about the required energy for the whole trip to make decisions about whether charging or not and where to charge (i.e., charging reliability). Since EV energy consumption is highly related to travel speed, network uncertainty affects travel time and charging demand estimation significantly. Considering the network uncertainty resulted from link degradation, which influences the distribution of travel demand on transportation network and the energy demand on power network, this paper aims to develop a reliability-based network equilibrium framework for accommodating degradable road conditions with the addition of EVs. First, based on the link travel time distribution, the mean and variance of route travel time and monetary expenses related to energy consumption are deduced, respectively. And the charging time distribution of EVs with charging demand is also estimated. Then, a nested structure is considered to deal with the difference of route choice behavior derived by the different uncertainty degrees between the routes with and without degradable links. Given the expected generalized travel cost and a psychological safety margin, a traffic assignment model with the addition of EVs is formulated. Subsequently, a heuristic solution algorithm is developed to solve the proposed model. Finally, the effects of travelers' risk attitude, network degradation degree, and EV penetration rate on network performance are illustrated through an example network. The numerical results show that the difference of travelers' risk attitudes does have impact on the route choice, and the widespread adoption of EVs can cut down the total system travel cost effectively when the transportation network is more reliable.

The effects of ion identity and ionic strength on the dissolution rate of a gibbsitic bauxite

NASA Astrophysics Data System (ADS)

Mogollón, José Luis; Pérez-Diaz, Alberto; Lo Monaco, Salvador

2000-03-01

The influence of cation and anion identity and concentration, on the far from equilibrium dissolution rate of gibbsite, was studied at 298°K. Input solutions, with initial pH = 3.5 and variable salt type and concentration, were flowed at different rates, through columns packed with a unconsolidated gibbsitic bauxite from Los Pijigüaos-Venezuela ore deposit. It was observed cations Na +, K +, Mg 2+ and Ca2+ have no influence on the far from equilibrium dissolution rate. Anions have two different effects: concentration increases of monovalent anions (Cl -, NO 3- and ClO 4-) causes a decrease in the rate, as a function of [anion] (-0.11 ± 0.01); and increases of sulfate concentration causes an increase in the rate as a function of [SO 4=] (0.4 ± 0.1). According to our calculations, these two effects have a remarkable influence upon the lifetime of gibbsite under weathering conditions. Based on Transition State Theory, it is proposed the experimental observations are due to an electrostatic effect on the activated complex (AC ♯) of the gibbsite dissolution reaction. For this AC ♯ the product of the charge of the involved chemical entities is negative. When SO 4= participates in the AC ♯ the product of the charges switches to positive and therefore, the electrostatic interaction increase the dissolution rate. The dissolution rates are independent of the solution saturation degree below ΔGr = - 0.74 kcal/mol. It is inferred that the critical ΔGr is a constant of the solid, not affected by the solution characteristics, e.g., pH, ionic strength, cation and anion identities.

On charged particle equilibrium violation in external photon fields.

PubMed

Bouchard, Hugo; Seuntjens, Jan; Palmans, Hugo

2012-03-01

In a recent paper by Bouchard et al. [Med. Phys. 36(10), 4654-4663 (2009)], a theoretical model of quality correction factors for idealistic so-called plan-class specific reference (PCSR) fields was proposed. The reasoning was founded on the definition of PCSR fields made earlier by Alfonso et al. [Med. Phys. 35(11), 5179-5186 (2008)], requiring the beam to achieve charged particle equilibrium (CPE), in a time-averaged sense, in the reference medium. The relation obtained by Bouchard et al. was derived using Fano's theorem (1954) which states that if CPE is established in a given medium, the dose is independent of point-to-point density variations. A potential misconception on the achievability of the condition required by Fano (1954) might be responsible for false practical conclusions, both in the definition of PCSR fields as well as the theoretical model of quality correction factor. In this paper, the practical achievability of CPE in external beams is treated in detail. The fact that this condition is not achievable in single or composite deliveries is illustrated by an intuitive method and is also formally demonstrated. Fano's theorem is not applicable in external beam radiation dosimetry without (virtually) removing attenuation effects, and therefore, the relation conditionally defined by Bouchard et al. (2009) cannot be valid in practice. A definition of PCSR fields in the recent formalism for nonstandard beams proposed by Alfonso et al. (2008) should be modified, revising the criterion of CPE condition. The authors propose reconsidering the terminology used to describe standard and nonstandard beams. The authors argue that quality correction factors of intensity modulated radiation therapy PCSR fields (i.e., k(Q(pcsr),Q) (f(pcsr),f(ref) )) could be unity under ideal conditions, but it is concluded that further investigation is necessary to confirm that hypothesis.

Spatiotemporal pH dynamics in concentration polarization near ion-selective membranes.

PubMed

Andersen, Mathias B; Rogers, David M; Mai, Junyu; Schudel, Benjamin; Hatch, Anson V; Rempe, Susan B; Mani, Ali

2014-07-08

We present a detailed analysis of the transient pH dynamics for a weak, buffered electrolyte subject to voltage-driven transport through an ion-selective membrane. We show that pH fronts emanate from the concentration polarization zone next to the membrane and that these propagating fronts change the pH in the system several units from its equilibrium value. The analysis is based on a 1D model using the unsteady Poisson-Nernst-Planck equations with nonequilibrium chemistry and without assumptions of electroneutrality or asymptotically thin electric double layers. Nonequilibrium chemical effects, especially for water splitting, are shown to be important for the dynamical and spatiotemporal evolution of the pH fronts. Nonetheless, the model also shows that at steady state the assumption of chemical equilibrium can still lead to good approximations of the global pH distribution. Moreover, our model shows that the transport of the hydronium ion in the extended space charge region is governed by a balance between electromigration and water self-ionization. On the basis of this observation, we present a simple model showing that the net flux of the hydronium ion is proportional to the length of the extended space charge region and the water self-ionization rate. To demonstrate these effects in practice, we have adopted the experiment of Mai et al. (Mai, J.; Miller, H.; Hatch, A. V. Spatiotemporal Mapping of Concentration Polarization Induced pH Changes at Nanoconstrictions. ACS Nano 2012, 6, 10206) as a model problem, and by including the full chemistry and transport, we show that the present model can capture the experimentally observed pH fronts. Our model can, among other things, be used to predict and engineer pH dynamics, which can be essential to the performance of membrane-based systems for biochemical separation and analysis.

Tungsten species in natural ferromanganese oxides related to its different behavior from molybdenum in oxic ocean

NASA Astrophysics Data System (ADS)

Kashiwabara, Teruhiko; Takahashi, Yoshio; Marcus, Matthew A.; Uruga, Tomoya; Tanida, Hajime; Terada, Yasuko; Usui, Akira

2013-04-01

The tungsten (W) species in marine ferromanganese oxides were investigated by wavelength dispersive XAFS method. We found that the W species are in distorted Oh symmetry in natural ferromanganese oxides. The host phase of W is suggested to be Mn oxides by μ-XRF mapping. We also found that the W species forms inner-sphere complexes in hexavalent state and distorted Oh symmetry on synthetic ferrihydrite, goethite, hematite, and δ-MnO2. The molecular-scale information of W indicates that the negatively-charged WO42- ion mainly adsorbs on the negatively-charged Mn oxides phase in natural ferromanganese oxides due to the strong chemical interaction. In addition, preferential adsorption of lighter W isotopes is expected based on the molecular symmetry of the adsorbed species, implying the potential significance of the W isotope systems similar to Mo. Adsorption experiments of W on synthetic ferrihydrite and δ-MnO2 were also conducted. At higher equilibrium concentration, W exhibits behaviors similar to Mo on δ-MnO2 due to their formations of inner-sphere complexes. On the other hand, W shows a much larger adsorption on ferrihydrite than Mo. This is due to the formation of the inner- and outer-sphere complexes for W and Mo on ferrihydrite, respectively. Considering the lower equilibrium concentration such as in oxic seawater, however, the enrichment of W into natural ferromanganese oxides larger than Mo may be controlled by the different stabilities of their inner-sphere complexes on the Mn oxides. These two factors, (i) the stability of inner-sphere complexes on the Mn oxides and (ii) the mode of attachment on ferrihydrite (inner- or outer-sphere complex), are the causes of the different behaviors of W and Mo on the surface of the Fe/Mn (oxyhydr)oxides.

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.

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.

Mimicking Nonequilibrium Steady States with Time-Periodic Driving (Open Source)

DTIC Science & Technology

2016-05-18

nonequilibrium steady states, and vice versa, within the theoretical framework of discrete-state stochastic thermodynamics . Nonequilibrium steady states...equilibrium [2], spontaneous relaxation towards equilibrium [3], nonequilibrium steady states generated by fixed thermodynamic forces [4], and stochastic pumps...paradigm, a system driven by fixed thermodynamic forces—such as temperature gradients or chemical potential differences— reaches a steady state in

Charge transfer and injection barrier at the metal-organic interfaces

NASA Astrophysics Data System (ADS)

Yan, Li

2002-09-01

The metal-organic interface plays a critical role in determining the functionality and performance of many innovative organic based devices. It has attracted extensive research interests in recent years. This thesis presents investigations of the electronic structures of organic materials, such as tris-(8-hydroxyquinoline) aluminum (Alq3) and copper phthalocyanine (CuPc), during their interface formation with metals. The characterization is accomplished by X-ray and ultraviolet photoelectron spectroscopes (XPS and UPS) and inverse photoelectron spectroscopy (IPES). As discussed herein, both occupied and unoccupied electronic states at the interfaces are carefully examined in different aspects. In Chapter 4, the charge transfer and chemical reaction at various metal/Alq3 interfaces are investigated using XPS and UPS to study the electron injection into the Alga film. Electron transfer from the low work function metal and Al/LiF(CsF) bilayer to the Alga has been observed. The role of the dielectric and possible chemistry at the interface are discussed in comparison of the low work function metals. Further in Chapter 5, the origin of the metal-interface dipole and the estimation of charge injection barrier is explored using several organic materials. A thermodynamic equilibrium model is extended to explain the relation between the charge transfer process ad the interface dipole. Further, in Chapter 6 the combination of XPS, UPS and IPES detailed the evolution of both occupied and unoccupied energy states during the alkali metal doping. The energy gap modification in organic due to metal doping is observed directly for the spectra. Chapter 7 provides stability study of the organic thin films under x-ray and UV light. The results verify the usability of UPS and XPS for the organic materials used in the thesis. Chapter 7 also shows the secondary ion mass spectroscopy results of metal diffusion in organic thin films.

Human domination of the biosphere: Rapid discharge of the earth-space battery foretells the future of humankind

PubMed Central

Schramski, John R.; Gattie, David K.; Brown, James H.

2015-01-01

Earth is a chemical battery where, over evolutionary time with a trickle-charge of photosynthesis using solar energy, billions of tons of living biomass were stored in forests and other ecosystems and in vast reserves of fossil fuels. In just the last few hundred years, humans extracted exploitable energy from these living and fossilized biomass fuels to build the modern industrial-technological-informational economy, to grow our population to more than 7 billion, and to transform the biogeochemical cycles and biodiversity of the earth. This rapid discharge of the earth’s store of organic energy fuels the human domination of the biosphere, including conversion of natural habitats to agricultural fields and the resulting loss of native species, emission of carbon dioxide and the resulting climate and sea level change, and use of supplemental nuclear, hydro, wind, and solar energy sources. The laws of thermodynamics governing the trickle-charge and rapid discharge of the earth’s battery are universal and absolute; the earth is only temporarily poised a quantifiable distance from the thermodynamic equilibrium of outer space. Although this distance from equilibrium is comprised of all energy types, most critical for humans is the store of living biomass. With the rapid depletion of this chemical energy, the earth is shifting back toward the inhospitable equilibrium of outer space with fundamental ramifications for the biosphere and humanity. Because there is no substitute or replacement energy for living biomass, the remaining distance from equilibrium that will be required to support human life is unknown. PMID:26178196

Human domination of the biosphere: Rapid discharge of the earth-space battery foretells the future of humankind.

PubMed

Schramski, John R; Gattie, David K; Brown, James H

2015-08-04

Earth is a chemical battery where, over evolutionary time with a trickle-charge of photosynthesis using solar energy, billions of tons of living biomass were stored in forests and other ecosystems and in vast reserves of fossil fuels. In just the last few hundred years, humans extracted exploitable energy from these living and fossilized biomass fuels to build the modern industrial-technological-informational economy, to grow our population to more than 7 billion, and to transform the biogeochemical cycles and biodiversity of the earth. This rapid discharge of the earth's store of organic energy fuels the human domination of the biosphere, including conversion of natural habitats to agricultural fields and the resulting loss of native species, emission of carbon dioxide and the resulting climate and sea level change, and use of supplemental nuclear, hydro, wind, and solar energy sources. The laws of thermodynamics governing the trickle-charge and rapid discharge of the earth's battery are universal and absolute; the earth is only temporarily poised a quantifiable distance from the thermodynamic equilibrium of outer space. Although this distance from equilibrium is comprised of all energy types, most critical for humans is the store of living biomass. With the rapid depletion of this chemical energy, the earth is shifting back toward the inhospitable equilibrium of outer space with fundamental ramifications for the biosphere and humanity. Because there is no substitute or replacement energy for living biomass, the remaining distance from equilibrium that will be required to support human life is unknown.

Relaxation from Steady States Far from Equilibrium and the Persistence of Anomalous Shock Behavior in Weakly Ionized Gases

NASA Technical Reports Server (NTRS)

Rubinstein, Robert; Auslender, Aaron H.

1999-01-01

The decay of anomalous effects on shock waves in weakly ionized gases following plasma generator extinction has been measured in the anticipation that the decay time must correlate well with the relaxation time of the mechanism responsible for the anomalous effects. When the relaxation times cannot be measured directly, they are inferred theoretically, usually assuming that the initial state is nearly in thermal equilibrium. In this paper, it is demonstrated that relaxation from any steady state far from equilibrium, including the state of a weakly ionized gas, can proceed much more slowly than arguments based on relaxation from near equilibrium states might suggest. This result justifies a more careful analysis of the relaxation times in weakly ionized gases and suggests that although the experimental measurements of relaxation times did not lead to an unambiguous conclusion, this approach to understanding the anomalous effects may warrant further investigation.

Role of the tail in the regulated state of myosin 2

PubMed Central

Jung, HyunSuk; Billington, Neil; Thirumurugan, Kavitha; Salzameda, Bridget; Cremo, Christine R.; Chalovich, Joseph M.; Chantler, Peter D.; Knight, Peter J.

2013-01-01

Myosin 2 from vertebrate smooth muscle or non-muscle sources is in equilibrium between compact, inactive monomers and thick filaments under physiological conditions. In the inactive monomer, the two heads pack compactly together and the long tail is folded into three closely-packed segments that are associated chiefly with one of the heads. The molecular basis of the folding of the tail remains unexplained. Using electron microscopy, we show that compact monomers of smooth muscle myosin 2 have the same structure in both the native state and following specific, intramolecular photo-cross-linking between Cys109 of the regulatory light chain (RLC) and segment 3 of the tail. Non-specific cross-linking between lysine residues of the folded monomer by glutaraldehyde also does not perturb the compact conformation, and stabilises it against unfolding at high ionic strength. Sequence comparisons across phyla and myosin 2 isoforms suggest that folding of the tail is stabilised by ionic interactions between the positively-charged N-terminal sequence of the RLC and a negatively-charged region near the start of tail segment 3, and that phosphorylation of the RLC could perturb these interactions. Our results support the view that interactions between the heads and the distal tail perform a critical role in regulating activity of myosin 2 molecules through stabilising the compact monomer conformation. PMID:21419133

Note on zero temperature holographic superfluids

NASA Astrophysics Data System (ADS)

Guo, Minyong; Lan, Shanquan; Niu, Chao; Tian, Yu; Zhang, Hongbao

2016-06-01

In this note, we have addressed various issues on zero temperature holographic superfluids. First, inspired by our numerical evidence for the equality between the superfluid density and particle density, we provide an elegant analytic proof for this equality by a boost trick. Second, using not only the frequency domain analysis but also the time domain analysis from numerical relativity, we identify the hydrodynamic normal modes and calculate out the sound speed, which is shown to increase with the chemical potential and saturate to the value predicted by the conformal field theory in the large chemical potential limit. Third, the generic non-thermalization is demonstrated by the fully nonlinear time evolution from a non-equilibrium state for our zero temperature holographic superfluid. Furthermore, a conserved Noether charge is proposed in support of this behavior.

First principles predictions of electronic and elastic properties of BaPb2As2 in the ThCr2Si2-type structure

NASA Astrophysics Data System (ADS)

Bourourou, Y.; Amari, S.; Yahiaoui, I. E.; Bouhafs, B.

2018-01-01

A first-principles approach is used to predicts the electronic and elastic properties of BaPb2As2 superconductor compound, using full-potential linearized augmented plane wave plus local orbitals (FP-L/APW+lo) scheme within the local density approximation LDA. The calculated equilibrium structural parameter a agree well with the experiment while the c/a ratio is far away from the experimental result. The band structure, density of states, together with the charge density and chemical bonding are discussed. The calculated elastic constants for our compound indicate that it is mechanically stable at ambient pressure. Polycrystalline elastic moduli (Young's, Bulk, shear Modulus and the Poisson's ratio) were calculated according to the Voigte-Reusse-Hill (VRH) average.

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.

Non-equilibrium dynamics and floral trait interactions shape extant angiosperm diversity

PubMed Central

O'Meara, Brian C.; Smith, Stacey D.; Armbruster, W. Scott; Harder, Lawrence D.; Hardy, Christopher R.; Hileman, Lena C.; Hufford, Larry; Litt, Amy; Magallón, Susana; Smith, Stephen A.; Stevens, Peter F.; Fenster, Charles B.; Diggle, Pamela K.

2016-01-01

Why are some traits and trait combinations exceptionally common across the tree of life, whereas others are vanishingly rare? The distribution of trait diversity across a clade at any time depends on the ancestral state of the clade, the rate at which new phenotypes evolve, the differences in speciation and extinction rates across lineages, and whether an equilibrium has been reached. Here we examine the role of transition rates, differential diversification (speciation minus extinction) and non-equilibrium dynamics on the evolutionary history of angiosperms, a clade well known for the abundance of some trait combinations and the rarity of others. Our analysis reveals that three character states (corolla present, bilateral symmetry, reduced stamen number) act synergistically as a key innovation, doubling diversification rates for lineages in which this combination occurs. However, this combination is currently less common than predicted at equilibrium because the individual characters evolve infrequently. Simulations suggest that angiosperms will remain far from the equilibrium frequencies of character states well into the future. Such non-equilibrium dynamics may be common when major innovations evolve rarely, allowing lineages with ancestral forms to persist, and even outnumber those with diversification-enhancing states, for tens of millions of years. PMID:27147092

Non-equilibrium dynamics and floral trait interactions shape extant angiosperm diversity.

PubMed

O'Meara, Brian C; Smith, Stacey D; Armbruster, W Scott; Harder, Lawrence D; Hardy, Christopher R; Hileman, Lena C; Hufford, Larry; Litt, Amy; Magallón, Susana; Smith, Stephen A; Stevens, Peter F; Fenster, Charles B; Diggle, Pamela K

2016-05-11

Why are some traits and trait combinations exceptionally common across the tree of life, whereas others are vanishingly rare? The distribution of trait diversity across a clade at any time depends on the ancestral state of the clade, the rate at which new phenotypes evolve, the differences in speciation and extinction rates across lineages, and whether an equilibrium has been reached. Here we examine the role of transition rates, differential diversification (speciation minus extinction) and non-equilibrium dynamics on the evolutionary history of angiosperms, a clade well known for the abundance of some trait combinations and the rarity of others. Our analysis reveals that three character states (corolla present, bilateral symmetry, reduced stamen number) act synergistically as a key innovation, doubling diversification rates for lineages in which this combination occurs. However, this combination is currently less common than predicted at equilibrium because the individual characters evolve infrequently. Simulations suggest that angiosperms will remain far from the equilibrium frequencies of character states well into the future. Such non-equilibrium dynamics may be common when major innovations evolve rarely, allowing lineages with ancestral forms to persist, and even outnumber those with diversification-enhancing states, for tens of millions of years. © 2016 The Author(s).

Physical and chemical interactions at the interface between atmospheric pressure plasmas and aqueous solutions

NASA Astrophysics Data System (ADS)

Lindsay, Alexander; Byrns, Brandon; Knappe, Detlef; Graves, David; Shannon, Steven

2014-10-01

Transport and reactions of charged species, neutrals, and photons at the interface between plasmas and liquids must be better quantified. The work presented here combines theoretical and experimental investigations of conditions in the gas and liquid phases in proximity to the interface for various discharges. OES is used to determine rotational and vibrational temperatures of OH, NO, and N2+; the relationship between these temperatures that characterize the distribution of internal energy states and gas and electron kinetic temperatures is considered. The deviation of OH rotational states from equilibrium under high humidity conditions is also presented. In contradiction with findings of other groups, high energy rotational states appear to become underpopulated with increasing humidity. In the aqueous phase, concentrations of longer-lived species such as nitrate, nitrite, hydrogen peroxide, and ozone are determined using ion chromatography and colorimetric methods. Spin-traps and electron paramagnetic resonance (EPR) are investigated for characterization of short-lived aqueous radicals like OH, O2-, NO, and ONOO-. Finally, experimental results are compared to a numerical model which couples transport and reactions within and between the bulk gas and liquid phases.

Grain-scale supercharging and breakdown on airless regoliths

NASA Astrophysics Data System (ADS)

Zimmerman, M. I.; Farrell, W. M.; Hartzell, C. M.; Wang, X.; Horanyi, M.; Hurley, D. M.; Hibbitts, K.

2016-10-01

Interactions of the solar wind and emitted photoelectrons with airless bodies have been studied extensively. However, the details of how charged particles interact with the regolith at the scale of a single grain have remained largely uncharacterized. Recent efforts have focused upon determining total surface charge under photoemission and solar wind bombardment and the associated electric field and potential. In this work, theory and simulations are used to show that grain-grain charge differences can exceed classical sheath predictions by several orders of magnitude, sometimes reaching dielectric breakdown levels. Temperature-dependent electrical conductivity works against supercharging by allowing current to leak through individual grains; the balance between internal conduction and surface charging controls the maximum possible grain-to-grain electric field. Understanding the finer details of regolith grain charging, conductive equilibrium, and dielectric breakdown will improve future numerical studies of space weathering and dust levitation on airless bodies.

Solar Wind Access to Lunar Polar Craters: Feedback Between Surface Charging and Plasma Expansion

NASA Technical Reports Server (NTRS)

Zimmerman, M. I.; Farrell, W. M.; Stubbs, T. J.; Halekas, J. S.; Jackson, T. L.

2011-01-01

Determining the plasma environment within permanently shadowed lunar craters is critical to understanding local processes such as surface charging, electrostatic dust transport, volatile sequestration, and space weathering. In order to investigate the nature of this plasma environment, the first two-dimensional kinetic simulations of solar wind expansion into a lunar crater with a self-consistent plasma-surface interaction have been undertaken. The present results reveal how the plasma expansion into a crater couples with the electrically-charged lunar surface to produce a quasi-steady wake structure. In particular, there is a negative feedback between surface charging and ambipolar wake potential that allows an equilibrium to be achieved, with secondary electron emission strongly moderating the process. A range of secondary electron yields is explored, and two distinct limits are highlighted in which either surface charging or ambipoiar expansion is responsible for determining the overall wake structure.

Grain-Scale Supercharging and Breakdown on Airless Regoliths

NASA Technical Reports Server (NTRS)

Zimmerman, M. I.; Farrell, W. M.; Hartzell, C.M.; Wang, X.; Horanyi, M.; Hurley, D. M.; Hibbitts, K.

2016-01-01

Interactions of the solar wind and emitted photoelectrons with airless bodies have been studied extensively. However, the details of how charged particles interact with the regolith at the scale of a single grain have remained largely uncharacterized. Recent efforts have focused upon determining total surface charge under photoemission and solar wind bombardment and the associated electric field and potential. In this work, theory and simulations are used to show that grain-grain charge differences can exceed classical sheath predictions by several orders of magnitude, sometimes reaching dielectric breakdown levels. Temperature-dependent electrical conductivity works against supercharging by allowing current to leak through individual grains; the balance between internal conduction and surface charging controls the maximum possible grain-to-grain electric field. Understanding the finer details of regolith grain charging, conductive equilibrium, and dielectric breakdown will improve future numerical studies of space weathering and dust levitation on airless bodies.

Monte Carlo calculations of diatomic molecule gas flows including rotational mode excitation

NASA Technical Reports Server (NTRS)

Yoshikawa, K. K.; Itikawa, Y.

1976-01-01

The direct simulation Monte Carlo method was used to solve the Boltzmann equation for flows of an internally excited nonequilibrium gas, namely, of rotationally excited homonuclear diatomic nitrogen. The semi-classical transition probability model of Itikawa was investigated for its ability to simulate flow fields far from equilibrium. The behavior of diatomic nitrogen was examined for several different nonequilibrium initial states that are subjected to uniform mean flow without boundary interactions. A sample of 1000 model molecules was observed as the gas relaxed to a steady state starting from three specified initial states. The initial states considered are: (1) complete equilibrium, (2) nonequilibrium, equipartition (all rotational energy states are assigned the mean energy level obtained at equilibrium with a Boltzmann distribution at the translational temperature), and (3) nonequipartition (the mean rotational energy is different from the equilibrium mean value with respect to the translational energy states). In all cases investigated the present model satisfactorily simulated the principal features of the relaxation effects in nonequilibrium flow of diatomic molecules.

Topologically protected modes in non-equilibrium stochastic systems.

PubMed

Murugan, Arvind; Vaikuntanathan, Suriyanarayanan

2017-01-10

Non-equilibrium driving of biophysical processes is believed to enable their robust functioning despite the presence of thermal fluctuations and other sources of disorder. Such robust functions include sensory adaptation, enhanced enzymatic specificity and maintenance of coherent oscillations. Elucidating the relation between energy consumption and organization remains an important and open question in non-equilibrium statistical mechanics. Here we report that steady states of systems with non-equilibrium fluxes can support topologically protected boundary modes that resemble similar modes in electronic and mechanical systems. Akin to their electronic and mechanical counterparts, topological-protected boundary steady states in non-equilibrium systems are robust and are largely insensitive to local perturbations. We argue that our work provides a framework for how biophysical systems can use non-equilibrium driving to achieve robust function.

Biosorption of metal ions from aqueous solutions

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

Chen, Jiaping; Yiacoumi, Sotira

1997-01-01

Copper biosorption from aqueous solutions by calcium alginate is reported in this paper. The experimental section includes potentiometric titrations of biosorbents, batch equilibrium and kinetic studies of copper biosorption, as well as fixed-bed biosorption experiments. The potentiometric titration results show that the surface charge increases with decreasing pH. The biosorption of copper strongly depends on solution pH; the metal ion binding increases from 0 to 90 percent in pH ranging from 1.5 to 5.0. In addition, a decrease in ionic strength results in an increase of copper ion removal. Kinetic studies indicate that mass transfer plays an important role inmore » the biosorption rate. Furthermore, a fixed-bed biosorption experiment shows that calcium alginate has a significant capacity for copper ion removal. The two-pK Basic Stem model successfully represents the surface charge and equilibrium biosorption experimental data. The calculation results demonstrate that the copper removal may result from the binding of free copper and its hydroxide with surface functional groups of the biosorbents.« less

Finite-size versus interface-proximity effects in thin-film epitaxial SrTiO3

NASA Astrophysics Data System (ADS)

De Souza, R. A.; Gunkel, F.; Hoffmann-Eifert, S.; Dittmann, R.

2014-06-01

The equilibrium electrical conductivity of epitaxial SrTiO3 (STO) thin films was investigated as a function of temperature, 950≤ T/K ≤1100, and oxygen partial pressure, 10-23≤ pO2/bar ≤1. Compared with single-crystal STO, nanoscale thin-film STO exhibited with decreasing film thickness an increasingly enhanced electronic conductivity under highly reducing conditions, with a corresponding decrease in the activation enthalpy of conduction. This implies substantial modification of STO's point-defect thermodynamics for nanoscale film thicknesses. We argue, however, against such a finite-size effect and for an interface-proximity effect. Indeed, assuming trapping of oxygen vacancies at the STO surface and concomitant depletion of oxygen vacancies—and accumulation of electrons—in an equilibrium surface space-charge layer, we are able to predict quantitatively the conductivity as a function of temperature, oxygen partial pressure, and film thickness. Particularly complex behavior is predicted for ultrathin films that are consumed entirely by space charge.

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.

Effects of space plasma discharge on the performance of large antenna structures in low Earth orbit

NASA Technical Reports Server (NTRS)

Blume, Hans-Juergen C.

1987-01-01

The anomalous plasma around spacecrafts in low Earth orbit represents the coma of an artificial comet. The plasma discharge is caused by an energetic disturbance of charged particles which were formerly in a state of equilibrium. The plasma can effect the passive and active radio frequency operation of large space antennas by inducing corona discharge or strong arcing in the antenna feeds. One such large space antenna is the 15-meter hoop column antenna which consists of a mesh membrane material (tricot knitted gold plated wire) reflector and carbon fiber tension cords. The atomic oxygen in the plasma discharge state can force the wire base metal particles through the gold lattice and oxydize the metal particles to build a Schottky-barrier contact at the point where the wires meet. This effect can cause strong deviations in the reflector performance in terms of antenna pattern and losses. Also, the carbon-fiber cords can experience a strength reduction of 30 percent over a 40-hour exposure time.

Assessment of Stable Isotope Distribution in Complex Systems

NASA Astrophysics Data System (ADS)

He, Y.; Cao, X.; Wang, J.; Bao, H.

2017-12-01

Biomolecules in living organisms have the potential to approach chemical steady state and even apparent isotope equilibrium because enzymatic reactions are intrinsically reversible. If an apparent local equilibrium can be identified, enzymatic reversibility and its controlling factors may be quantified, which helps to understand complex biochemical processes. Earlier research on isotope fractionation tends to focus on specific process and compare mostly two different chemical species. Using linear regression, "Thermodynamic order", which refers to correlated δ13C and 13β values, has been proposed to be present among many biomolecules by Galimov et al. However, the concept "thermodynamic order" they proposed and the approach they used has been questioned. Here, we propose that the deviation of a complex system from its equilibrium state can be rigorously described as a graph problem as is applied in discrete mathematics. The deviation of isotope distribution from equilibrium state and apparent local isotope equilibrium among a subset of biomolecules can be assessed using an apparent fractionation difference matrix (|Δα|). Applying the |Δα| matrix analysis to earlier published data of amino acids, we show the existence of apparent local equilibrium among different amino acids in potato and a kind of green alga. The existence of apparent local equilibrium is in turn consistent with the notion that enzymatic reactions can be reversible even in living systems. The result also implies that previous emphasis on external carbon source intake may be misplaced when studying isotope distribution in physiology. In addition to the identification of local equilibrium among biomolecules, the difference matrix approach has the potential to explore chemical or isotope equilibrium state in extraterrestrial bodies, to distinguish living from non-living systems, and to classify living species. This approach will benefit from large numbers of systematic data and advanced pattern recognition techniques.

Nanocomplexes of Photolabile Polyelectrolyte and Upconversion Nanoparticles for Near-Infrared Light-Triggered Payload Release.

PubMed

Xiang, Jun; Ge, Feijie; Yu, Bing; Yan, Qiang; Shi, Feng; Zhao, Yue

2018-06-07

A new approach to encapsulating charged cargo molecules into a nanovector and subsequently using near-infrared (NIR) light to trigger the release is demonstrated. NIR light-responsive nanovector was prepared through electrostatic interaction-driven complexation between negatively charged silica-coated upconversion nanoparticles (UCNP@silica, 87 nm hydrodynamic diameter, polydispersity index ∼0.05) and a positively charged UV-labile polyelectrolyte bearing pendants of poly(ethylene glycol) and o-nitrobenzyl side groups; whereas charged fluorescein (FLU) was loaded through a co-complexation process. By controlling the amount of polyelectrolyte, UCNP@silica can be covered by the polymer, whereas remaining dispersed in aqueous solution. Under 980 nm laser excitation, UV light emitted by UCNP is absorbed by photolytic side groups within polyelectrolyte, which results in cleavage of o-nitrobenzyl groups and formation of carboxylic acid groups. Such NIR light-induced partial reversal of positive charge to negative charge on the polyelectrolyte layer disrupts the equilibrium among UCNP@silica, polyelectrolyte, and FLU and, consequently, leads to release of FLU molecules.

Restoring interlayer Josephson coupling in La 1.885 Ba 0.115 CuO 4 by charge transfer melting of stripe order

DOE PAGES

Khanna, V.; Mankowsky, R.; Petrich, M.; ...

2016-06-30

Here, we show that disruption of charge-density-wave (stripe) order by charge transfer excitation, enhances the superconducting phase rigidity in La 1.885Ba 0.115CuO 4. Time-resolved resonant soft x-ray diffraction demonstrates that charge order melting is prompt following near-infrared photoexcitation whereas the crystal structure remains intact for moderate fluences. THz time-domain spectroscopy reveals that, for the first 2 ps following photoexcitation, a new Josephson plasma resonance edge, at higher frequency with respect to the equilibrium edge, is induced indicating enhanced superconducting interlayer coupling. Furthermore, the fluence dependence of the charge-order melting and the enhanced superconducting interlayer coupling are correlated with a saturationmore » limit of ~0.5mJ/cm 2. When using a combination of x-ray and optical spectroscopies we establish a hierarchy of timescales between enhanced superconductivity, melting of charge order, and rearrangement of the crystal structure.« less

Dust Particle Dynamics in The Presence of Highly Magnetized Plasmas

NASA Astrophysics Data System (ADS)

Lynch, Brian; Konopka, Uwe; Thomas, Edward; Merlino, Robert; Rosenberg, Marlene

2016-10-01

Complex plasmas are four component plasmas that contain, in addition to the usual electrons, ions, and neutral atoms, macroscopic electrically charged (nanometer to micrometer) sized ``dust'' particles. These macroscopic particles typically obtain a net negative charge due to the higher mobility of electrons compared to that of ions. Because the electrons, ions, and dust particles are charged, their dynamics may be significantly modified by the presence of electric and magnetic fields. Possible consequences of this modification may be the charging rate and the equilibrium charge. For example, in the presence of a strong horizontal magnetic field (B >1 Tesla), it may be possible to observe dust particle gx B deflection and, from that deflection, determine the dust grain charge. In this poster, we present recent data from performing multiple particle dropping experiments to characterize the g x B deflection in the Magnetized Dusty Plasma Experiment (MDPX). This work is supported by funding from the U. S. Department of Energy Grant Number DE - SC0010485 and the NASA/Jet Propulsion Laboratory, JPL-1543114.

Restoring interlayer Josephson coupling in La 1.885 Ba 0.115 CuO 4 by charge transfer melting of stripe order

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

Khanna, V.; Mankowsky, R.; Petrich, M.

Here, we show that disruption of charge-density-wave (stripe) order by charge transfer excitation, enhances the superconducting phase rigidity in La 1.885Ba 0.115CuO 4. Time-resolved resonant soft x-ray diffraction demonstrates that charge order melting is prompt following near-infrared photoexcitation whereas the crystal structure remains intact for moderate fluences. THz time-domain spectroscopy reveals that, for the first 2 ps following photoexcitation, a new Josephson plasma resonance edge, at higher frequency with respect to the equilibrium edge, is induced indicating enhanced superconducting interlayer coupling. Furthermore, the fluence dependence of the charge-order melting and the enhanced superconducting interlayer coupling are correlated with a saturationmore » limit of ~0.5mJ/cm 2. When using a combination of x-ray and optical spectroscopies we establish a hierarchy of timescales between enhanced superconductivity, melting of charge order, and rearrangement of the crystal structure.« less

Surface-dependent chemical equilibrium constants and capacitances for bare and 3-cyanopropyldimethylchlorosilane coated silica nanochannels.

PubMed

Andersen, Mathias Bækbo; Frey, Jared; Pennathur, Sumita; Bruus, Henrik

2011-01-01

We present a combined theoretical and experimental analysis of the solid-liquid interface of fused-silica nanofabricated channels with and without a hydrophilic 3-cyanopropyldimethylchlorosilane (cyanosilane) coating. We develop a model that relaxes the assumption that the surface parameters C(1), C(2), and pK(+) are constant and independent of surface composition. Our theoretical model consists of three parts: (i) a chemical equilibrium model of the bare or coated wall, (ii) a chemical equilibrium model of the buffered bulk electrolyte, and (iii) a self-consistent Gouy-Chapman-Stern triple-layer model of the electrochemical double layer coupling these two equilibrium models. To validate our model, we used both pH-sensitive dye-based capillary filling experiments as well as electro-osmotic current-monitoring measurements. Using our model we predict the dependence of ζ potential, surface charge density, and capillary filling length ratio on ionic strength for different surface compositions, which can be difficult to achieve otherwise. Copyright © 2010 Elsevier Inc. All rights reserved.

Allowance for effects of thermodynamic nonideality in sedimentation equilibrium distributions reflecting protein dimerization.

PubMed

Wills, Peter R; Scott, David J; Winzor, Donald J

2012-03-01

This reexamination of a high-speed sedimentation equilibrium distribution for α-chymotrypsin under slightly acidic conditions (pH 4.1, I(M) 0.05) has provided experimental support for the adequacy of nearest-neighbor considerations in the allowance for effects of thermodynamic nonideality in the characterization of protein self-association over a moderate concentration range (up to 8 mg/mL). A widely held but previously untested notion about allowance for thermodynamic nonideality effects is thereby verified experimentally. However, it has also been shown that a greater obstacle to better characterization of protein self-association is likely to be the lack of a reliable estimate of monomer net charge, a parameter that has a far more profound effect on the magnitude of the measured equilibrium constant than any deficiency in current procedures for incorporating the effects of thermodynamic nonideality into the analysis of sedimentation equilibrium distributions reflecting reversible protein self-association. Copyright © 2011 Elsevier Inc. All rights reserved.

Real Time Computation of Kinetic Constraints to Support Equilibrium Reconstruction

NASA Astrophysics Data System (ADS)

Eggert, W. J.; Kolemen, E.; Eldon, D.

2016-10-01

A new method for quickly and automatically applying kinetic constraints to EFIT equilibrium reconstructions using readily available data is presented. The ultimate goal is to produce kinetic equilibrium reconstructions in real time and use them to constrain the DCON stability code as part of a disruption avoidance scheme. A first effort presented here replaces CPU-time expensive modules, such as the fast ion pressure profile calculation, with a simplified model. We show with a DIII-D database analysis that we can achieve reasonable predictions for selected applications by modeling the fast ion pressure profile and determining the fit parameters as functions of easily measured quantities including neutron rate and electron temperature on axis. Secondly, we present a strategy for treating Thomson scattering and Charge Exchange Recombination data to automatically form constraints for a kinetic equilibrium reconstruction, a process that historically was performed by hand. Work supported by US DOE DE-AC02-09CH11466 and DE-FC02-04ER54698.

Chaos in charged AdS black hole extended phase space

NASA Astrophysics Data System (ADS)

Chabab, M.; El Moumni, H.; Iraoui, S.; Masmar, K.; Zhizeh, S.

2018-06-01

We present an analytical study of chaos in a charged black hole in the extended phase space in the context of the Poincare-Melnikov theory. Along with some background on dynamical systems, we compute the relevant Melnikov function and find its zeros. Then we analyse these zeros either to identify the temporal chaos in the spinodal region, or to observe spatial chaos in the small/large black hole equilibrium configuration. As a byproduct, we derive a constraint on the Black hole' charge required to produce chaotic behaviour. To the best of our knowledge, this is the first endeavour to understand the correlation between chaos and phase picture in black holes.

Degradation effects on charge carrier transport in P3HT:PCBM solar cells studied by Photo-CELIV and ToF

NASA Astrophysics Data System (ADS)

Stephen, M.; Karuthedath, S.; Sauermann, T.; Genevičius, K.; Juška, G.

2014-10-01

Oxygen induced degradation is one of the major problems in the field of organic photovoltaics. Photo-degradation impacts on performance of inverted bulk hetero junction poly(3-hexylthiophene) : phenyl-C61-butyric acid methyl ester (P3HT:PCBM) solar cells has been investigated by means of charge extraction by linearly increasing voltage (CELIV) and time of flight (ToF) methods. The irreversible loss in short circuit current (Jsc) can be attributed to a combination of adverse effects such as loss in mobility of the charge carrires, increase in trapping effect and sheilding of electric field by equilibrium carriers upon degradation.

Optimal III-nitride HEMTs: from materials and device design to compact model of the 2DEG charge density

NASA Astrophysics Data System (ADS)

Li, Kexin; Rakheja, Shaloo

2017-02-01

In this paper, we develop a physically motivated compact model of the charge-voltage (Q-V) characteristics in various III-nitride high-electron mobility transistors (HEMTs) operating under highly non-equilibrium transport conditions, i.e. high drain-source current. By solving the coupled Schrödinger-Poisson equation and incorporating the two-dimensional electrostatics in the channel, we obtain the charge at the top-of-the-barrier for various applied terminal voltages. The Q-V model accounts for cutting off of the negative momenta states from the drain terminal under high drain-source bias and when the transmission in the channel is quasi-ballistic. We specifically focus on AlGaN and AlInN as barrier materials and InGaN and GaN as the channel material in the heterostructure. The Q-V model is verified and calibrated against numerical results using the commercial TCAD simulator Sentaurus from Synopsys for a 20-nm channel length III-nitride HEMT. With 10 fitting parameters, most of which have a physical origin and can easily be obtained from numerical or experimental calibration, the compact Q-V model allows us to study the limits and opportunities of III-nitride technology. We also identify optimal material and geometrical parameters of the device that maximize the carrier concentration in the HEMT channel in order to achieve superior RF performance. Additionally, the compact charge model can be easily integrated in a hierarchical circuit simulator, such as Keysight ADS and CADENCE, to facilitate circuit design and optimization of various technology parameters.

Density functional description of size-dependent effects at nucleation on neutral and charged nanoparticles

NASA Astrophysics Data System (ADS)

Shchekin, Alexander K.; Lebedeva, Tatiana S.

2017-03-01

A numerical study of size-dependent effects in the thermodynamics of a small droplet formed around a solid nanoparticle has been performed within the square-gradient density functional theory. The Lennard-Jones fluid with the Carnahan-Starling model for the hard-sphere contribution to intermolecular interaction in liquid and vapor phases and interfaces has been used for description of the condensate. The intermolecular forces between the solid core and condensate molecules have been taken into account with the help of the Lennard-Jones part of the total molecular potential of the core. The influence of the electric charge of the particle has been considered under assumption of the central Coulomb potential in the medium with dielectric permittivity depending on local condensate density. The condensate density profiles and equimolecular radii for equilibrium droplets at different values of the condensate chemical potential have been computed in the cases of an uncharged solid core with the molecular potential, a charged core without molecular potential, and a core with joint action of the Coulomb and molecular potentials. The appearance of stable equilibrium droplets even in the absence of the electric charge has been commented. As a next step, the capillary, disjoining pressure, and electrostatic contributions to the condensate chemical potential have been considered and compared with the predictions of classical thermodynamics in a wide range of values of the droplet and the particle equimolecular radii. With the help of the found dependence of the condensate chemical potential in droplet on the droplet size, the activation barrier for nucleation on uncharged and charged particles has been computed as a function of the vapor supersaturation. Finally, the work of droplet formation and the work of wetting the particle have been found as functions of the droplet size.

Modelling of hydrogen transport in silicon solar cell structures under equilibrium conditions

NASA Astrophysics Data System (ADS)

Hamer, P.; Hallam, B.; Bonilla, R. S.; Altermatt, P. P.; Wilshaw, P.; Wenham, S.

2018-01-01

This paper presents a model for the introduction and redistribution of hydrogen in silicon solar cells at temperatures between 300 and 700 °C based on a second order backwards difference formula evaluated using a single Newton-Raphson iteration. It includes the transport of hydrogen and interactions with impurities such as ionised dopants. The simulations lead to three primary conclusions: (1) hydrogen transport across an n-type emitter is heavily temperature dependent; (2) under equilibrium conditions, hydrogen is largely driven by its charged species, with the switch from a dominance of negatively charged hydrogen (H-) to positively charged hydrogen (H+) within the emitter region critical to significant transport across the junction; and (3) hydrogen transport across n-type emitters is critically dependent upon the doping profile within the emitter, and, in particular, the peak doping concentration. It is also observed that during thermal processes after an initial high temperature step, hydrogen preferentially migrates to the surface of a phosphorous doped emitter, drawing hydrogen out of the p-type bulk. This may play a role in several effects observed during post-firing anneals in relation to the passivation of recombination active defects and even the elimination of hydrogen-related defects in the bulk of silicon solar cells.

Low Mach number fluctuating hydrodynamics for electrolytes

DOE PAGES

Péraud, Jean-Philippe; Nonaka, Andy; Chaudhri, Anuj; ...

2016-11-18

Here, we formulate and study computationally the low Mach number fluctuating hydrodynamic equations for electrolyte solutions. We are also interested in studying transport in mixtures of charged species at the mesoscale, down to scales below the Debye length, where thermal fluctuations have a significant impact on the dynamics. Continuing our previous work on fluctuating hydrodynamics of multicomponent mixtures of incompressible isothermal miscible liquids (A. Donev, et al., Physics of Fluids, 27, 3, 2015), we now include the effect of charged species using a quasielectrostatic approximation. Localized charges create an electric field, which in turn provides additional forcing in the massmore » and momentum equations. Our low Mach number formulation eliminates sound waves from the fully compressible formulation and leads to a more computationally efficient quasi-incompressible formulation. Furthermore, we demonstrate our ability to model saltwater (NaCl) solutions in both equilibrium and nonequilibrium settings. We show that our algorithm is second-order in the deterministic setting, and for length scales much greater than the Debye length gives results consistent with an electroneutral/ambipolar approximation. In the stochastic setting, our model captures the predicted dynamics of equilibrium and nonequilibrium fluctuations. We also identify and model an instability that appears when diffusive mixing occurs in the presence of an applied electric field.« less

Modeling the Charge Transport in Graphene Nano Ribbon Interfaces for Nano Scale Electronic Devices

NASA Astrophysics Data System (ADS)

Kumar, Ravinder; Engles, Derick

2015-05-01

In this research work we have modeled, simulated and compared the electronic charge transport for Metal-Semiconductor-Metal interfaces of Graphene Nano Ribbons (GNR) with different geometries using First-Principle calculations and Non-Equilibrium Green's Function (NEGF) method. We modeled junctions of Armchair GNR strip sandwiched between two Zigzag strips with (Z-A-Z) and Zigzag GNR strip sandwiched between two Armchair strips with (A-Z-A) using semi-empirical Extended Huckle Theory (EHT) within the framework of Non-Equilibrium Green Function (NEGF). I-V characteristics of the interfaces were visualized for various transport parameters. The distinct changes in conductance and I-V curves reported as the Width across layers, Channel length (Central part) was varied at different bias voltages from -1V to 1 V with steps of 0.25 V. From the simulated results we observed that the conductance through A-Z-A graphene junction is in the range of 10-13 Siemens whereas the conductance through Z-A-Z graphene junction is in the range of 10-5 Siemens. These suggested conductance controlled mechanisms for the charge transport in the graphene interfaces with different geometries is important for the design of graphene based nano scale electronic devices like Graphene FETs, Sensors.

The Ligand Trans Influence Governs Conformation in Cobalamin-Dependent Methionine Synthase†

PubMed Central

Fleischhacker, Angela S.; Matthews, Rowena G.

2008-01-01

Cobalamin-dependent methionine synthase (MetH) of Escherichia coli is a large, modular enzyme that uses a cobalamin prosthetic group as a donor or acceptor in three separate methyl transfer reactions. The prosthetic group alternates between methylcobalamin and cob(I)alamin during catalysis as homocysteine is converted to methionine using a methyl group derived from methyltetrahydrofolate. Occasional oxidation of cob(I)alamin to cob(II)alamin inactivates the enzyme. Reductive methylation with flavodoxin and adenosylmethionine returns the enzyme to an active methylcobalamin state. At different points during the reaction cycle, the coordination of the cobalt of the cobalamin changes. The imidazole side chain of His759 coordinates to cobalamin in a “His-on” state and dissociates to produce a “His-off” state. The His-off state has been associated with a conformation of MetH that is poised for reactivation of cobalamin by reductive methylation rather than catalysis. Our studies on cob(III)alamins bound to MetH, specifically aqua-, methyl-, and n-propylcobalamin, show a correlation between the accessibility of the reactivation conformation and the order of the established ligand trans influence. The trans influence also controls the affinity of MetH in the cob(III)alamin form for flavodoxin. Flavodoxin, which acts to shift the conformational equilibrium towards the reactivation conformation, binds less tightly to MetH when the cob(III)alamin has a strong trans ligand and therefore has less positive charge on cobalt. These results are compared to those for cob(II)alamin MetH, illustrating that access to the reactivation conformation is governed by the net charge on the cobalt as well as the trans influence in cob(III)alamins. PMID:17924667

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.

Bilinear magnetoelectric resistance as a probe of three-dimensional spin texture in topological surface states

DOE PAGES

He, Pan; Zhang, Steven S. -L.; Zhu, Dapeng; ...

2018-02-05

Surface states of three-dimensional topological insulators exhibit the phenomenon of spin-momentum locking, whereby the orientation of an electron spin is determined by its momentum. Probing the spin texture of these states is of critical importance for the realization of topological insulator devices, but the main technique currently available is spin-and angle-resolved photoemission spectroscopy. Here in this paper we reveal a close link between the spin texture and a new kind of magnetoresistance, which depends on the relative orientation of the current with respect to the magnetic field as well as the crystallographic axes, and scales linearly with both the appliedmore » electric and magnetic fields. This bilinear magnetoelectric resistance can be used to map the spin texture of topological surface states by simple transport measurements. For a prototypical Bi 2Se 3 single layer, we can map both the in-plane and out-of-plane components of the spin texture (the latter arising from hexagonal warping). Theoretical calculations suggest that the bilinear magnetoelectric resistance originates from conversion of a non-equilibrium spin current into a charge current under application of the external magnetic field.« less

Bilinear magnetoelectric resistance as a probe of three-dimensional spin texture in topological surface states

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

He, Pan; Zhang, Steven S. -L.; Zhu, Dapeng

Surface states of three-dimensional topological insulators exhibit the phenomenon of spin-momentum locking, whereby the orientation of an electron spin is determined by its momentum. Probing the spin texture of these states is of critical importance for the realization of topological insulator devices, but the main technique currently available is spin-and angle-resolved photoemission spectroscopy. Here in this paper we reveal a close link between the spin texture and a new kind of magnetoresistance, which depends on the relative orientation of the current with respect to the magnetic field as well as the crystallographic axes, and scales linearly with both the appliedmore » electric and magnetic fields. This bilinear magnetoelectric resistance can be used to map the spin texture of topological surface states by simple transport measurements. For a prototypical Bi 2Se 3 single layer, we can map both the in-plane and out-of-plane components of the spin texture (the latter arising from hexagonal warping). Theoretical calculations suggest that the bilinear magnetoelectric resistance originates from conversion of a non-equilibrium spin current into a charge current under application of the external magnetic field.« less

Nonlinear ballooning modes in tokamaks: stability and saturation

NASA Astrophysics Data System (ADS)

Ham, C. J.; Cowley, S. C.; Brochard, G.; Wilson, H. R.

2018-07-01

The nonlinear dynamics of magneto-hydrodynamic ballooning mode perturbations is conjectured to be characterised by the motion of isolated elliptical flux tubes. The theory of stability, dynamics and saturation of such tubes in tokamaks is developed using a generalised Archimedes’ principle. The equation of motion for a tube moving against a drag force in a general axisymmetric equilibrium is derived and then applied to a simplified ‘s–α’ equilibrium. The perturbed nonlinear tube equilibrium (saturated) states are investigated in an ‘s–α’ equilibrium with specific pressure and magnetic shear profiles. The energy of these nonlinear (ballooning) saturated states is calculated. In some cases, particularly at low magnetic shear, these finitely displaced states can have a lower energy than the equilibrium state even if the profile is linearly stable to ballooning modes (infinitesimal tube displacements) at all radii. Thus nonlinear ballooning modes can be metastable. The amplitude of the saturated tube displacement in such cases can be as large as the pressure gradient scale length. We conjecture that triggering a transition into these filamentary states can lead to hard instability limits. A short survey of different pressure profiles is presented to illustrate the variety of behaviour of perturbed elliptical flux tubes.

An Electronic Structure Approach to Charge Transfer and Transport in Molecular Building Blocks for Organic Optoelectronics

NASA Astrophysics Data System (ADS)

Hendrickson, Heidi Phillips

A fundamental understanding of charge separation in organic materials is necessary for the rational design of optoelectronic devices suited for renewable energy applications and requires a combination of theoretical, computational, and experimental methods. Density functional theory (DFT) and time-dependent (TD)DFT are cost effective ab-initio approaches for calculating fundamental properties of large molecular systems, however conventional DFT methods have been known to fail in accurately characterizing frontier orbital gaps and charge transfer states in molecular systems. In this dissertation, these shortcomings are addressed by implementing an optimally-tuned range-separated hybrid (OT-RSH) functional approach within DFT and TDDFT. The first part of this thesis presents the way in which RSH-DFT addresses the shortcomings in conventional DFT. Environmentally-corrected RSH-DFT frontier orbital energies are shown to correspond to thin film measurements for a set of organic semiconducting molecules. Likewise, the improved RSH-TDDFT description of charge transfer excitations is benchmarked using a model ethene dimer and silsesquioxane molecules. In the second part of this thesis, RSH-DFT is applied to chromophore-functionalized silsesquioxanes, which are currently investigated as candidates for building blocks in optoelectronic applications. RSH-DFT provides insight into the nature of absorptive and emissive states in silsesquioxanes. While absorption primarily involves transitions localized on one chromophore, charge transfer between chromophores and between chromophore and silsesquioxane cage have been identified. The RSH-DFT approach, including a protocol accounting for complex environmental effects on charge transfer energies, was tested and validated against experimental measurements. The third part of this thesis addresses quantum transport through nano-scale junctions. The ability to quantify a molecular junction via spectroscopic methods is crucial to their technological design and development. Time dependent perturbation theory, employed by non-equilibrium Green's function formalism, is utilized to study the effect of quantum coherences on electron transport and the effect of symmetry breaking on the electronic spectra of model molecular junctions. The fourth part of this thesis presents the design of a physical chemistry course based on a pedagogical approach called Writing-to-Teach. The nature of inaccuracies expressed in student-generated explanations of quantum chemistry topics, and the ability of a peer review process to engage these inaccuracies, is explored within this context.

Chemical bonding and the equilibrium composition of Grignard reagents in ethereal solutions.

PubMed

Henriques, André M; Barbosa, André G H

2011-11-10

A thorough analysis of the electronic structure and thermodynamic aspects of Grignard reagents and its associated equilibrium composition in ethereal solutions is performed. Considering methylmagnesium halides containing fluorine, chlorine, and bromine, we studied the neutral, charged, and radical species associated with their chemical equilibrium in solution. The ethereal solvents considered, tetrahydrofuran (THF) and ethyl ether (Et(2)O), were modeled using the polarizable continuum model (PCM) and also by explicit coordination to the Mg atoms in a cluster. The chemical bonding of the species that constitute the Grignard reagent is analyzed in detail with generalized valence bond (GVB) wave functions. Equilibrium constants were calculated with the DFT/M06 functional and GVB wave functions, yielding similar results. According to our calculations and existing kinetic and electrochemical evidence, the species R(•), R(-), (•)MgX, and RMgX(2)(-) must be present in low concentration in the equilibrium. We conclude that depending on the halogen, a different route must be followed to produce the relevant equilibrium species in each case. Chloride and bromide must preferably follow a "radical-based" pathway, and fluoride must follow a "carbanionic-based" pathway. These different mechanisms are contrasted against the available experimental results and are proven to be consistent with the existing thermodynamic data on the Grignard reagent equilibria.

Diffuse charge and Faradaic reactions in porous electrodes

NASA Astrophysics Data System (ADS)

Biesheuvel, P. M.; Fu, Yeqing; Bazant, Martin Z.

2011-06-01

Porous electrodes instead of flat electrodes are widely used in electrochemical systems to boost storage capacities for ions and electrons, to improve the transport of mass and charge, and to enhance reaction rates. Existing porous electrode theories make a number of simplifying assumptions: (i) The charge-transfer rate is assumed to depend only on the local electrostatic potential difference between the electrode matrix and the pore solution, without considering the structure of the double layer (DL) formed in between; (ii) the charge-transfer rate is generally equated with the salt-transfer rate not only at the nanoscale of the matrix-pore interface, but also at the macroscopic scale of transport through the electrode pores. In this paper, we extend porous electrode theory by including the generalized Frumkin-Butler-Volmer model of Faradaic reaction kinetics, which postulates charge transfer across the molecular Stern layer located in between the electron-conducting matrix phase and the plane of closest approach for the ions in the diffuse part of the DL. This is an elegant and purely local description of the charge-transfer rate, which self-consistently determines the surface charge and does not require consideration of reference electrodes or comparison with a global equilibrium. For the description of the DLs, we consider the two natural limits: (i) the classical Gouy-Chapman-Stern model for thin DLs compared to the macroscopic pore dimensions, e.g., for high-porosity metallic foams (macropores >50 nm) and (ii) a modified Donnan model for strongly overlapping DLs, e.g., for porous activated carbon particles (micropores <2 nm). Our theory is valid for electrolytes where both ions are mobile, and it accounts for voltage and concentration differences not only on the macroscopic scale of the full electrode, but also on the local scale of the DL. The model is simple enough to allow us to derive analytical approximations for the steady-state and early transients. We also present numerical solutions to validate the analysis and to illustrate the evolution of ion densities, pore potential, surface charge, and reaction rates in response to an applied voltage.