A molecular dynamics computer simulation study of room-temperature ionic liquids. II. Equilibrium and nonequilibrium solvation dynamics.

PubMed

Shim, Y; Choi, M Y; Kim, Hyung J

2005-01-22

The molecular dynamics (MD) simulation study of solvation structure and free energetics in 1-ethyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium hexafluorophosphate using a probe solute in the preceding article [Y. Shim, M. Y. Choi and H. J. Kim, J. Chem. Phys. 122, 044510 (2005)] is extended to investigate dynamic properties of these liquids. Solvent fluctuation dynamics near equilibrium are studied via MD and associated time-dependent friction is analyzed via the generalized Langevin equation. Nonequilibrium solvent relaxation following an instantaneous change in the solute charge distribution and accompanying solvent structure reorganization are also investigated. Both equilibrium and nonequilibrium solvation dynamics are characterized by at least two vastly different time scales--a subpicosecond inertial regime followed by a slow diffusive regime. Solvent regions contributing to the subpicosecond nonequilibrium relaxation are found to vary significantly with initial solvation configurations, especially near the solute. If the solvent density near the solute is sufficiently high at the outset of the relaxation, subpicosecond dynamics are mainly governed by the motions of a few ions close to the solute. By contrast, in the case of a low local density, solvent ions located not only close to but also relatively far from the solute participate in the subpicosecond relaxation. Despite this difference, linear response holds reasonably well in both ionic liquids. (c) 2005 American Institute of Physics.

The glassy state of crambin and the THz time scale protein-solvent fluctuations possibly related to protein function

PubMed Central

2014-01-01

Background THz experiments have been used to characterize the picosecond time scale fluctuations taking place in the model, globular protein crambin. Results Using both hydration and temperature as an experimental parameter, we have identified collective fluctuations (<= 200 cm−1) in the protein. Observation of the protein dynamics in the THz spectrum from both below and above the glass transition temperature (Tg) has provided unique insight into the microscopic interactions and modes that permit the solvent to effectively couple to the protein thermal fluctuations. Conclusions Our findings suggest that the solvent dynamics on the picosecond time scale not only contribute to protein flexibility but may also delineate the types of fluctuations that are able to form within the protein structure. PMID:25184036

Simulation of electric double-layer capacitors: evaluation of constant potential method

NASA Astrophysics Data System (ADS)

Wang, Zhenxing; Laird, Brian; Yang, Yang; Olmsted, David; Asta, Mark

2014-03-01

Atomistic simulations can play an important role in understanding electric double-layer capacitors (EDLCs) at a molecular level. In such simulations, typically the electrode surface is modeled using fixed surface charges, which ignores the charge fluctuation induced by local fluctuations in the electrolyte solution. In this work we evaluate an explicit treatment of charges, namely constant potential method (CPM)[1], in which the electrode charges are dynamically updated to maintain constant electrode potential. We employ a model system with a graphite electrode and a LiClO4/acetonitrile electrolyte, examined as a function of electrode potential differences. Using various molecular and macroscopic properties as metrics, we compare CPM simulations on this system to results using fixed surface charges. Specifically, results for predicted capacity, electric potential gradient and solvent density profile are identical between the two methods; However, ion density profiles and solvation structure yield significantly different results.

Stochastic level-set variational implicit-solvent approach to solute-solvent interfacial fluctuations

PubMed Central

Zhou, Shenggao; Sun, Hui; Cheng, Li-Tien; Dzubiella, Joachim; McCammon, J. Andrew

2016-01-01

Recent years have seen the initial success of a variational implicit-solvent model (VISM), implemented with a robust level-set method, in capturing efficiently different hydration states and providing quantitatively good estimation of solvation free energies of biomolecules. The level-set minimization of the VISM solvation free-energy functional of all possible solute-solvent interfaces or dielectric boundaries predicts an equilibrium biomolecular conformation that is often close to an initial guess. In this work, we develop a theory in the form of Langevin geometrical flow to incorporate solute-solvent interfacial fluctuations into the VISM. Such fluctuations are crucial to biomolecular conformational changes and binding process. We also develop a stochastic level-set method to numerically implement such a theory. We describe the interfacial fluctuation through the “normal velocity” that is the solute-solvent interfacial force, derive the corresponding stochastic level-set equation in the sense of Stratonovich so that the surface representation is independent of the choice of implicit function, and develop numerical techniques for solving such an equation and processing the numerical data. We apply our computational method to study the dewetting transition in the system of two hydrophobic plates and a hydrophobic cavity of a synthetic host molecule cucurbit[7]uril. Numerical simulations demonstrate that our approach can describe an underlying system jumping out of a local minimum of the free-energy functional and can capture dewetting transitions of hydrophobic systems. In the case of two hydrophobic plates, we find that the wavelength of interfacial fluctuations has a strong influence to the dewetting transition. In addition, we find that the estimated energy barrier of the dewetting transition scales quadratically with the inter-plate distance, agreeing well with existing studies of molecular dynamics simulations. Our work is a first step toward the inclusion of fluctuations into the VISM and understanding the impact of interfacial fluctuations on biomolecular solvation with an implicit-solvent approach. PMID:27497546

Free energetics of carbon nanotube association in aqueous inorganic NaI salt solutions: Temperature effects using all-atom molecular dynamics simulations.

PubMed

Ou, Shu-Ching; Cui, Di; Wezowicz, Matthew; Taufer, Michela; Patel, Sandeep

2015-06-15

In this study, we examine the temperature dependence of free energetics of nanotube association using graphical processing unit-enabled all-atom molecular dynamics simulations (FEN ZI) with two (10,10) single-walled carbon nanotubes in 3 m NaI aqueous salt solution. Results suggest that the free energy, enthalpy and entropy changes for the association process are all reduced at the high temperature, in agreement with previous investigations using other hydrophobes. Via the decomposition of free energy into individual components, we found that solvent contribution (including water, anion, and cation contributions) is correlated with the spatial distribution of the corresponding species and is influenced distinctly by the temperature. We studied the spatial distribution and the structure of the solvent in different regions: intertube, intratube and the bulk solvent. By calculating the fluctuation of coarse-grained tube-solvent surfaces, we found that tube-water interfacial fluctuation exhibits the strongest temperature dependence. By taking ions to be a solvent-like medium in the absence of water, tube-anion interfacial fluctuation shows similar but weaker dependence on temperature, while tube-cation interfacial fluctuation shows no dependence in general. These characteristics are discussed via the malleability of their corresponding solvation shells relative to the nanotube surface. Hydrogen bonding profiles and tetrahedrality of water arrangement are also computed to compare the structure of solvent in the solvent bulk and intertube region. The hydrophobic confinement induces a relatively lower concentration environment in the intertube region, therefore causing different intertube solvent structures which depend on the tube separation. This study is relevant in the continuing discourse on hydrophobic interactions (as they impact generally a broad class of phenomena in biology, biochemistry, and materials science and soft condensed matter research), and interpretations of hydrophobicity in terms of alternative but parallel signatures such as interfacial fluctuations, dewetting transitions, and enhanced fluctuation probabilities at interfaces. © 2015 Wiley Periodicals, Inc.

Quantitative study of fluctuation effects by fast lattice Monte Carlo simulations: Compression of grafted homopolymers

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

Zhang, Pengfei; Wang, Qiang, E-mail: q.wang@colostate.edu

2014-01-28

Using fast lattice Monte Carlo (FLMC) simulations [Q. Wang, Soft Matter 5, 4564 (2009)] and the corresponding lattice self-consistent field (LSCF) calculations, we studied a model system of grafted homopolymers, in both the brush and mushroom regimes, in an explicit solvent compressed by an impenetrable surface. Direct comparisons between FLMC and LSCF results, both of which are based on the same Hamiltonian (thus without any parameter-fitting between them), unambiguously and quantitatively reveal the fluctuations/correlations neglected by the latter. We studied both the structure (including the canonical-ensemble averages of the height and the mean-square end-to-end distances of grafted polymers) and thermodynamicsmore » (including the ensemble-averaged reduced energy density and the related internal energy per chain, the differences in the Helmholtz free energy and entropy per chain from the uncompressed state, and the pressure due to compression) of the system. In particular, we generalized the method for calculating pressure in lattice Monte Carlo simulations proposed by Dickman [J. Chem. Phys. 87, 2246 (1987)], and combined it with the Wang-Landau–Optimized Ensemble sampling [S. Trebst, D. A. Huse, and M. Troyer, Phys. Rev. E 70, 046701 (2004)] to efficiently and accurately calculate the free energy difference and the pressure due to compression. While we mainly examined the effects of the degree of compression, the distance between the nearest-neighbor grafting points, the reduced number of chains grafted at each grafting point, and the system fluctuations/correlations in an athermal solvent, the θ-solvent is also considered in some cases.« less

Solvent induced conformational fluctuation of alanine dipeptide studied by using vibrational probes

NASA Astrophysics Data System (ADS)

Cai, Kaicong; Du, Fenfen; Liu, Jia; Su, Tingting

2015-02-01

The solvation effect on the three dimensional structure and the vibrational feature of alanine dipeptide (ALAD) was evaluated by applying the implicit solvents from polarizable continuum solvent model (PCM) through ab initio calculations, by using molecular dynamic (MD) simulations with explicit solvents, and by combining these two approaches. The implicit solvent induced potential energy fluctuations of ALAD in CHCl3, DMSO and H2O are revealed by means of ab initio calculations, and a global view of conformational and solvation environmental dependence of amide I frequencies is achieved. The results from MD simulations with explicit solvents show that ALAD trends to form PPII, αL, αR, and C5 in water, PPII and C5 in DMSO, and C5 in CHCl3, ordered by population, and the demonstration of the solvated structure, the solute-solvent interaction and hydrogen bonding is therefore enhanced. Representative ALAD-solvent clusters were sampled from MD trajectories and undergone ab initio calculations. The explicit solvents reveal the hydrogen bonding between ALAD and solvents, and the correlation between amide I frequencies and the Cdbnd O bond length is built. The implicit solvents applied to the ALAD-solvent clusters further compensate the solvation effect from the bulk, and thus enlarge the degree of structural distortion and the amide I frequency red shift. The combination of explicit solvent in the first hydration shell and implicit solvent in the bulk is helpful for our understanding about the conformational fluctuation of solvated polypeptides through vibrational probes.

Concentration Fluctuations and Capacitive Response in Dense Ionic Solutions.

PubMed

Uralcan, Betul; Aksay, Ilhan A; Debenedetti, Pablo G; Limmer, David T

2016-07-07

We use molecular dynamics simulations in a constant potential ensemble to study the effects of solution composition on the electrochemical response of a double layer capacitor. We find that the capacitance first increases with ion concentration following its expected ideal solution behavior but decreases upon approaching a pure ionic liquid in agreement with recent experimental observations. The nonmonotonic behavior of the capacitance as a function of ion concentration results from the competition between the independent motion of solvated ions in the dilute regime and solvation fluctuations in the concentrated regime. Mirroring the capacitance, we find that the characteristic decay length of charge density correlations away from the electrode is also nonmonotonic. The correlation length first decreases with ion concentration as a result of better electrostatic screening but increases with ion concentration as a result of enhanced steric interactions. When charge fluctuations induced by correlated ion-solvent fluctuations are large relative to those induced by the pure ionic liquid, such capacitive behavior is expected to be generic.

Nonisothermal fluctuating hydrodynamics and Brownian motion

NASA Astrophysics Data System (ADS)

Falasco, G.; Kroy, K.

2016-03-01

The classical theory of Brownian dynamics follows from coarse graining the underlying linearized fluctuating hydrodynamics of the solvent. We extend this procedure to globally nonisothermal conditions, requiring only a local thermal equilibration of the solvent. Starting from the conservation laws, we establish the stochastic equations of motion for the fluid momentum fluctuations in the presence of a suspended Brownian particle. These are then contracted to the nonisothermal generalized Langevin description of the suspended particle alone, for which the coupling to stochastic temperature fluctuations is found to be negligible under typical experimental conditions.

Vibrational spectroscopic determination of local solvent electric field, solute-solvent electrostatic interaction energy, and their fluctuation amplitudes.

PubMed

Lee, Hochan; Lee, Gayeon; Jeon, Jonggu; Cho, Minhaeng

2012-01-12

IR probes have been extensively used to monitor local electrostatic and solvation dynamics. Particularly, their vibrational frequencies are highly sensitive to local solvent electric field around an IR probe. Here, we show that the experimentally measured vibrational frequency shifts can be inversely used to determine local electric potential distribution and solute-solvent electrostatic interaction energy. In addition, the upper limits of their fluctuation amplitudes are estimated by using the vibrational bandwidths. Applying this method to fully deuterated N-methylacetamide (NMA) in D(2)O and examining the solvatochromic effects on the amide I' and II' mode frequencies, we found that the solvent electric potential difference between O(═C) and D(-N) atoms of the peptide bond is about 5.4 V, and thus, the approximate solvent electric field produced by surrounding water molecules on the NMA is 172 MV/cm on average if the molecular geometry is taken into account. The solute-solvent electrostatic interaction energy is estimated to be -137 kJ/mol, by considering electric dipole-electric field interaction. Furthermore, their root-mean-square fluctuation amplitudes are as large as 1.6 V, 52 MV/cm, and 41 kJ/mol, respectively. We found that the water electric potential on a peptide bond is spatially nonhomogeneous and that the fluctuation in the electrostatic peptide-water interaction energy is about 10 times larger than the thermal energy at room temperature. This indicates that the peptide-solvent interactions are indeed important for the activation of chemical reactions in aqueous solution.

Degree of polymerization of glucan chains shapes the structure fluctuations and melting thermodynamics of a cellulose microfibril.

PubMed

Chang, Rakwoo; Gross, Adam S; Chu, Jhih-Wei

2012-07-19

A Staggered LATtice (SLAT) model is developed for modeling cellulose microfibrils. The simple representation of molecular packing and interactions employed in SLAT allows simulations of structure fluctuations and phase transition of cellulose microfibrils at sufficiently long and large scales for comparison with experiments. Glucan chains in the microfibril are modeled as connected monomers, each corresponding to a cellobiose subunit, and the surrounding space around the cellulose is composed of solvent cells. Interaction parameters of monomer-monomer interactions were parametrized based on the results of atomistic molecular dynamics simulations. The monomer-solvent interaction was optimized to give a melting temperature of ∼695 K for the 36-glucan chain model cellulose microfibril, which is consistent with the estimation based on experimental data. Monte Carlo simulations of the SLAT model also capture experimentally measured X-ray diffraction patterns of cellulose as a function of temperature, including the region of melting transition, as well as predict the highly flexible regions in the microfibril. Beyond the diameter of ∼3 nm, we found that melting temperature of the cellulose microfibril is not significantly shifted by changing the thickness. On the other hand, a slight decrease in the degree of polymerization of glucan chains is shown to enhance structure fluctuations through the ends of glucan chains, i.e., the defect sites, and thereby significantly reduce the melting temperature. Analysis of the sizes, densities, and lifetimes of defect structures in the microfibril indicates a significant extent of fluctuations on the surfaces even at room temperature and that defect statistics are strong but distinct functions of temperature and solvent quality. The SLAT model is the first of its kind for simulating cellulosic materials, and this work shows that it can be used to incorporate information obtained from atomistic simulations and experimental data to enable the aforementioned findings through computation.

Vibrational spectra from atomic fluctuations in dynamics simulations. II. Solvent-induced frequency fluctuations at femtosecond time resolution

NASA Astrophysics Data System (ADS)

Schmitz, Matthias; Tavan, Paul

2004-12-01

The midinfrared (MIR) spectra of molecules in polar solvents exhibit inhomogeneously broadened bands whose spectral positions are shifted as compared to the gas phase. The shifts are caused by interactions with structured solvation shells and the broadenings by fluctuations of these interactions. The MIR spectra can be calculated from hybrid molecular dynamics (MD) simulations, which treat the solute molecule by density functional theory and the solvent by molecular mechanics by the so-called instantaneous normal mode analysis (INMA) or by Fourier transforming the time correlation function (FTTCF) of the molecular dipole moment. In Paper I of this work [M. Schmitz and P. Tavan, J. Chem. Phys. 121, 12233 (2004)] we explored an alternative method based on generalized virial (GV) frequencies noting, however, that GV systematically underestimates frequencies. As shown by us these artifacts are caused by solvent-induced fluctuations of the (i) equilibrium geometry, (ii) force constants, and (iii) normal mode directions as well as by (iv) diagonal and (v) off-diagonal anharmonicities. Here we now show, by analyzing the time scales of fluctuations and sample MD trajectories of formaldehyde in the gas phase and in water, that all these sources of computational artifacts can be made visible by a Fourier analysis of the normal coordinates. Correspondingly, the error sources (i) and (iii)-(v) can be removed by bandpass filtering, as long as the spectral signatures of the respective effects are well separated from the fundamental band. Furthermore, the artifacts arising from effect (ii) can be strongly diminished by a time-resolved version of the GV approach (TF-GV). The TF-GV method then yields for each mode j a trajectory of the vibrational frequency ωj(t|τ) at a time resolution τ>τj, which is only limited by the corresponding oscillation time τj=2π/ωj and, thus, is in the femtosecond range. A correlation analysis of these trajectories clearly separates the librational motions from the conformational dynamics of the solvation shells and yields the inhomogeneously broadened MIR spectra, if the theory of motional narrowing is properly included. The MIR spectrum of formaldehyde in solution obtained by TF-GV agrees very well with the FTTCF result, if one applies the so-called "harmonic approximation" quantum correction factor and a temperature scaling to the FTTCF intensities. Also for INMA an excellent agreement is achieved if one disregards a slight INMA overestimate of linewidths.

Transitions of tethered chain molecules under tension.

PubMed

Luettmer-Strathmann, Jutta; Binder, Kurt

2014-09-21

An applied tension force changes the equilibrium conformations of a polymer chain tethered to a planar substrate and thus affects the adsorption transition as well as the coil-globule and crystallization transitions. Conversely, solvent quality and surface attraction are reflected in equilibrium force-extension curves that can be measured in experiments. To investigate these effects theoretically, we study tethered chains under tension with Wang-Landau simulations of a bond-fluctuation lattice model. Applying our model to pulling experiments on biological molecules we obtain a good description of experimental data in the intermediate force range, where universal features dominate and finite size effects are small. For tethered chains in poor solvent, we observe the predicted two-phase coexistence at transitions from the globule to stretched conformations and also discover direct transitions from crystalline to stretched conformations. A phase portrait for finite chains constructed by evaluating the density of states for a broad range of solvent conditions and tensions shows how increasing tension leads to a disappearance of the globular phase. For chains in good solvents tethered to hard and attractive surfaces we find the predicted scaling with the chain length in the low-force regime and show that our results are well described by an analytical, independent-bond approximation for the bond-fluctuation model for the highest tensions. Finally, for a hard or slightly attractive surface the stretching of a tethered chain is a conformational change that does not correspond to a phase transition. However, when the surface attraction is sufficient to adsorb a chain it will undergo a desorption transition at a critical value of the applied force. Our results for force-induced desorption show the transition to be discontinuous with partially desorbed conformations in the coexistence region.

Evaluation of the constant potential method in simulating electric double-layer capacitors

NASA Astrophysics Data System (ADS)

Wang, Zhenxing; Yang, Yang; Olmsted, David L.; Asta, Mark; Laird, Brian B.

2014-11-01

A major challenge in the molecular simulation of electric double layer capacitors (EDLCs) is the choice of an appropriate model for the electrode. Typically, in such simulations the electrode surface is modeled using a uniform fixed charge on each of the electrode atoms, which ignores the electrode response to local charge fluctuations in the electrolyte solution. In this work, we evaluate and compare this Fixed Charge Method (FCM) with the more realistic Constant Potential Method (CPM), [S. K. Reed et al., J. Chem. Phys. 126, 084704 (2007)], in which the electrode charges fluctuate in order to maintain constant electric potential in each electrode. For this comparison, we utilize a simplified LiClO4-acetonitrile/graphite EDLC. At low potential difference (ΔΨ ⩽ 2 V), the two methods yield essentially identical results for ion and solvent density profiles; however, significant differences appear at higher ΔΨ. At ΔΨ ⩾ 4 V, the CPM ion density profiles show significant enhancement (over FCM) of "inner-sphere adsorbed" Li+ ions very close to the electrode surface. The ability of the CPM electrode to respond to local charge fluctuations in the electrolyte is seen to significantly lower the energy (and barrier) for the approach of Li+ ions to the electrode surface.

Charge fluctuations in nanoscale capacitors.

PubMed

Limmer, David T; Merlet, Céline; Salanne, Mathieu; Chandler, David; Madden, Paul A; van Roij, René; Rotenberg, Benjamin

2013-09-06

The fluctuations of the charge on an electrode contain information on the microscopic correlations within the adjacent fluid and their effect on the electronic properties of the interface. We investigate these fluctuations using molecular dynamics simulations in a constant-potential ensemble with histogram reweighting techniques. This approach offers, in particular, an efficient, accurate, and physically insightful route to the differential capacitance that is broadly applicable. We demonstrate these methods with three different capacitors: pure water between platinum electrodes and a pure as well as a solvent-based organic electrolyte each between graphite electrodes. The total charge distributions with the pure solvent and solvent-based electrolytes are remarkably Gaussian, while in the pure ionic liquid the total charge distribution displays distinct non-Gaussian features, suggesting significant potential-driven changes in the organization of the interfacial fluid.

Charge Fluctuations in Nanoscale Capacitors

NASA Astrophysics Data System (ADS)

Limmer, David T.; Merlet, Céline; Salanne, Mathieu; Chandler, David; Madden, Paul A.; van Roij, René; Rotenberg, Benjamin

2013-09-01

The fluctuations of the charge on an electrode contain information on the microscopic correlations within the adjacent fluid and their effect on the electronic properties of the interface. We investigate these fluctuations using molecular dynamics simulations in a constant-potential ensemble with histogram reweighting techniques. This approach offers, in particular, an efficient, accurate, and physically insightful route to the differential capacitance that is broadly applicable. We demonstrate these methods with three different capacitors: pure water between platinum electrodes and a pure as well as a solvent-based organic electrolyte each between graphite electrodes. The total charge distributions with the pure solvent and solvent-based electrolytes are remarkably Gaussian, while in the pure ionic liquid the total charge distribution displays distinct non-Gaussian features, suggesting significant potential-driven changes in the organization of the interfacial fluid.

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

Zhou, Shenggao, E-mail: sgzhou@suda.edu.cn, E-mail: bli@math.ucsd.edu; Sun, Hui; Cheng, Li-Tien

Recent years have seen the initial success of a variational implicit-solvent model (VISM), implemented with a robust level-set method, in capturing efficiently different hydration states and providing quantitatively good estimation of solvation free energies of biomolecules. The level-set minimization of the VISM solvation free-energy functional of all possible solute-solvent interfaces or dielectric boundaries predicts an equilibrium biomolecular conformation that is often close to an initial guess. In this work, we develop a theory in the form of Langevin geometrical flow to incorporate solute-solvent interfacial fluctuations into the VISM. Such fluctuations are crucial to biomolecular conformational changes and binding process. Wemore » also develop a stochastic level-set method to numerically implement such a theory. We describe the interfacial fluctuation through the “normal velocity” that is the solute-solvent interfacial force, derive the corresponding stochastic level-set equation in the sense of Stratonovich so that the surface representation is independent of the choice of implicit function, and develop numerical techniques for solving such an equation and processing the numerical data. We apply our computational method to study the dewetting transition in the system of two hydrophobic plates and a hydrophobic cavity of a synthetic host molecule cucurbit[7]uril. Numerical simulations demonstrate that our approach can describe an underlying system jumping out of a local minimum of the free-energy functional and can capture dewetting transitions of hydrophobic systems. In the case of two hydrophobic plates, we find that the wavelength of interfacial fluctuations has a strong influence to the dewetting transition. In addition, we find that the estimated energy barrier of the dewetting transition scales quadratically with the inter-plate distance, agreeing well with existing studies of molecular dynamics simulations. Our work is a first step toward the inclusion of fluctuations into the VISM and understanding the impact of interfacial fluctuations on biomolecular solvation with an implicit-solvent approach.« less

Effects of solvent concentration and composition on protein dynamics: 13C MAS NMR studies of elastin in glycerol-water mixtures.

PubMed

Demuth, Dominik; Haase, Nils; Malzacher, Daniel; Vogel, Michael

2015-08-01

We use (13)C CP MAS NMR to investigate the dependence of elastin dynamics on the concentration and composition of the solvent at various temperatures. For elastin in pure glycerol, line-shape analysis shows that larger-scale fluctuations of the protein backbone require a minimum glycerol concentration of ~0.6 g/g at ambient temperature, while smaller-scale fluctuations are activated at lower solvation levels of ~0.2 g/g. Immersing elastin in various glycerol-water mixtures, we observe at room temperature that the protein mobility is higher for lower glycerol fractions in the solvent and, thus, lower solvent viscosity. When decreasing the temperature, the elastin spectra approach the line shape for the rigid protein at 245 K for all studied samples, indicating that the protein ceases to be mobile on the experimental time scale of ~10(-5) s. Our findings yield evidence for a strong coupling between elastin fluctuations and solvent dynamics and, hence, such interaction is not restricted to the case of protein-water mixtures. Spectral resolution of different carbon species reveals that the protein-solvent couplings can, however, be different for side chain and backbone units. We discuss these results against the background of the slaving model for protein dynamics. Copyright © 2015 Elsevier B.V. All rights reserved.

Dielectric and thermal effects on the optical properties of natural dyes: a case study on solvated cyanin.

PubMed

Malcıoğlu, Osman Bariş; Calzolari, Arrigo; Gebauer, Ralph; Varsano, Daniele; Baroni, Stefano

2011-10-05

The optical properties of the flavylium state of the cyanin dye are simulated numerically by combining Car-Parrinello molecular dynamics and linear-response time-dependent density functional theory calculations. The spectrum of the dye calculated in the gas phase is characterized by two peaks in the yellow and in the blue (green and violet), using a GGA-PBE (hybrid-B3LYP) DFT functional, which would bring about a greenish (bright orange) color incompatible with the dark purple hue observed in nature. Describing the effect of the water solvent through a polarizable continuum model does not modify qualitatively the resulting picture. An explicit simulation of both solvent and thermal effects using ab initio molecular dynamics results instead in a spectrum that is compatible with the observed coloration. This result is analyzed in terms of the spectroscopic effects of the molecular distortions induced by thermal fluctuations.

Brownian motion of a nano-colloidal particle: the role of the solvent.

PubMed

Torres-Carbajal, Alexis; Herrera-Velarde, Salvador; Castañeda-Priego, Ramón

2015-07-15

Brownian motion is a feature of colloidal particles immersed in a liquid-like environment. Usually, it can be described by means of the generalised Langevin equation (GLE) within the framework of the Mori theory. In principle, all quantities that appear in the GLE can be calculated from the molecular information of the whole system, i.e., colloids and solvent molecules. In this work, by means of extensive Molecular Dynamics simulations, we study the effects of the microscopic details and the thermodynamic state of the solvent on the movement of a single nano-colloid. In particular, we consider a two-dimensional model system in which the mass and size of the colloid are two and one orders of magnitude, respectively, larger than the ones associated with the solvent molecules. The latter ones interact via a Lennard-Jones-type potential to tune the nature of the solvent, i.e., it can be either repulsive or attractive. We choose the linear momentum of the Brownian particle as the observable of interest in order to fully describe the Brownian motion within the Mori framework. We particularly focus on the colloid diffusion at different solvent densities and two temperature regimes: high and low (near the critical point) temperatures. To reach our goal, we have rewritten the GLE as a second kind Volterra integral in order to compute the memory kernel in real space. With this kernel, we evaluate the momentum-fluctuating force correlation function, which is of particular relevance since it allows us to establish when the stationarity condition has been reached. Our findings show that even at high temperatures, the details of the attractive interaction potential among solvent molecules induce important changes in the colloid dynamics. Additionally, near the critical point, the dynamical scenario becomes more complex; all the correlation functions decay slowly in an extended time window, however, the memory kernel seems to be only a function of the solvent density. Thus, the explicit inclusion of the solvent in the description of Brownian motion allows us to better understand the behaviour of the memory kernel at those thermodynamic states near the critical region without any further approximation. This information is useful to elaborate more realistic descriptions of Brownian motion that take into account the particular details of the host medium.

Investigation of detection limits for solutes in water measured by laser raman spectrometry

USGS Publications Warehouse

Goldberg, M.C.

1977-01-01

The influence of experimental parameters on detection sensitivity was determined for laser Raman analysis of dissolved solutes in water. Individual solutions of nitrate, sulfate, carbonate, bicarbonate, monohydrogen phosphate, dihydrogen phosphate, acetate ion, and acetic acid were measured. An equation is derived which expresses the signal-to-noise ratio in terms of solute concentration, measurement time, spectral slit width, laser power fluctuations, and solvent background intensity. Laser beam intensity fluctuations at the sample and solvent background intensity are the most important limiting factors.

Flexible chain molecules in the marginal and concentrated regimes: universal static scaling laws and cross-over predictions.

PubMed

Laso, Manuel; Karayiannis, Nikos Ch

2008-05-07

We present predictions for the static scaling exponents and for the cross-over polymer volumetric fractions in the marginal and concentrated solution regimes. Corrections for finite chain length are made. Predictions are based on an analysis of correlated fluctuations in density and chain length, in a semigrand ensemble in which mers and solvent sites exchange identities. Cross-over volumetric fractions are found to be chain length independent to first order, although reciprocal-N corrections are also estimated. Predicted scaling exponents and cross-over regimes are compared with available data from extensive off-lattice Monte Carlo simulations [Karayiannis and Laso, Phys. Rev. Lett. 100, 050602 (2008)] on freely jointed, hard-sphere chains of average lengths from N=12-500 and at packing densities from dilute ones up to the maximally random jammed state.

Blowing bubbles in Lennard-Jonesium along the saturation curve.

PubMed

Ashbaugh, Henry S

2009-05-28

Extensive molecular simulations of the Lennard-Jones fluid have been performed to determine its liquid-vapor coexistence properties and solvent contact densities with cavities up to ten times the diameter of the solvent from the triple point to the critical point. These simulations are analyzed using a revised scaled-particle theory [H. S. Ashbaugh and L. R. Pratt, Rev. Mod. Phys. 78, 159 (2006)] to evaluate the thermodynamics of cavity solvation and curvature dependent interfacial properties along the saturation curve. While the thermodynamic signatures of cavity solvation are distinct from those in water, exhibiting a chemical potential dominated by a large temperature independent enthalpy, the solvent dewets cavities of increasing size similar with water near coexistence. The interfacial tension for forming a liquid-wall interface is found to be consistently greater than the liquid-vapor surface tension of the Lennard-Jones fluid by up to 10% and potentially reflects the suppression of high amplitude fluctuations at the cavity surface. The first-order curvature correction for the surface tension is negative and appears to diverge to negative infinity at temperatures approaching the critical point. Our results point to the success of the revised scaled-particle theory at bridging molecular and macroscopic descriptions of cavity solvation.

Resonances arising from hydrodynamic memory in Brownian motion.

PubMed

Franosch, Thomas; Grimm, Matthias; Belushkin, Maxim; Mor, Flavio M; Foffi, Giuseppe; Forró, László; Jeney, Sylvia

2011-10-05

Observation of the Brownian motion of a small probe interacting with its environment provides one of the main strategies for characterizing soft matter. Essentially, two counteracting forces govern the motion of the Brownian particle. First, the particle is driven by rapid collisions with the surrounding solvent molecules, referred to as thermal noise. Second, the friction between the particle and the viscous solvent damps its motion. Conventionally, the thermal force is assumed to be random and characterized by a Gaussian white noise spectrum. The friction is assumed to be given by the Stokes drag, suggesting that motion is overdamped at long times in particle tracking experiments, when inertia becomes negligible. However, as the particle receives momentum from the fluctuating fluid molecules, it also displaces the fluid in its immediate vicinity. The entrained fluid acts back on the particle and gives rise to long-range correlations. This hydrodynamic 'memory' translates to thermal forces, which have a coloured, that is, non-white, noise spectrum. One hundred years after Perrin's pioneering experiments on Brownian motion, direct experimental observation of this colour is still elusive. Here we measure the spectrum of thermal noise by confining the Brownian fluctuations of a microsphere in a strong optical trap. We show that hydrodynamic correlations result in a resonant peak in the power spectral density of the sphere's positional fluctuations, in strong contrast to overdamped systems. Furthermore, we demonstrate different strategies to achieve peak amplification. By analogy with microcantilever-based sensors, our results reveal that the particle-fluid-trap system can be considered a nanomechanical resonator in which the intrinsic hydrodynamic backflow enhances resonance. Therefore, instead of being treated as a disturbance, details in thermal noise could be exploited for the development of new types of sensor and particle-based assay in lab-on-a-chip applications.

Solvation and thermal effects on the optical properties of naturaldyes: a case study on the flavylium cyanin

NASA Astrophysics Data System (ADS)

Calzolari, Arrigo; Malcioglu, Baris; Gebauer, Ralph; Varsano, Daniele; Baroni, Stefano

2011-03-01

We present a first-principles study of the effects of both hydration and thermal dynamics on the optical properties of a natural anthocyanin dye, namely, cyanin (Cya), in aqueous solution. We combine Car-Parrinello molecular dynamics and time-dependent density functional theory (TDDFT) approaches to simulate the time evolution of UV-vis spectrum of the hydrated Cya molecule at room temperature [2,3]. The spectrum of the dye calculated in the gas phase is characterized by two peaks in the red and in the blue, which would bring about a greenish hue incompatible with the dark purple coloration observed in nature. Describing the effect of the water solvent through a polarizable continuum model does not modify qualitatively the resulting picture. An explicit simulation of both solvent and thermal effects using ab-initio molecular dynamics results instead in a spectrum that is compatible with the observed coloration. This result is analyzed in terms of the spectroscopic effects of molecular distortions, induced by thermal fluctuations.

Simple and exact approach to the electronic polarization effect on the solvation free energy: formulation for quantum-mechanical/molecular-mechanical system and its applications to aqueous solutions.

PubMed

Takahashi, Hideaki; Omi, Atsushi; Morita, Akihiro; Matubayasi, Nobuyuki

2012-06-07

We present a simple and exact numerical approach to compute the free energy contribution δμ in solvation due to the electron density polarization and fluctuation of a quantum-mechanical solute in the quantum-mechanical/molecular-mechanical (QM/MM) simulation combined with the theory of the energy representation (QM/MM-ER). Since the electron density fluctuation is responsible for the many-body QM-MM interactions, the standard version of the energy representation method cannot be applied directly. Instead of decomposing the QM-MM polarization energy into the pairwise additive and non-additive contributions, we take sum of the polarization energies in the QM-MM interaction and adopt it as a new energy coordinate for the method of energy representation. Then, it is demonstrated that the free energy δμ can be exactly formulated in terms of the energy distribution functions for the solution and reference systems with respect to this energy coordinate. The benchmark tests were performed to examine the numerical efficiency of the method with respect to the changes in the individual properties of the solvent and the solute. Explicitly, we computed the solvation free energy of a QM water molecule in ambient and supercritical water, and also the free-energy change associated with the isomerization reaction of glycine from neutral to zwitterionic structure in aqueous solution. In all the systems examined, it was demonstrated that the computed free energy δμ agrees with the experimental value, irrespective of the choice of the reference electron density of the QM solute. The present method was also applied to a prototype reaction of adenosine 5'-triphosphate hydrolysis where the effect of the electron density fluctuation is substantial due to the excess charge. It was demonstrated that the experimental free energy of the reaction has been accurately reproduced with the present approach.

Extended hierarchical solvent perturbations from curved surfaces of mesoporous silica particles in a deep eutectic solvent.

PubMed

Hammons, Joshua A; Zhang, Fan; Ilavsky, Jan

2018-06-15

Many applications of deep eutectic solvents (DES) rely on exploitation of their unique yet complex liquid structures. Due to the ionic nature of the DES components, their diffuse structures are perturbed in the presence of a charged surface. We hypothesize that it is possible to perturb the bulk DES structure far (>100 nm) from a curved, charged surface with mesoscopic dimensions. We performed in situ, synchrotron-based ultra-small angle X-ray scattering (USAXS) experiments to study the solvent distribution near the surface of charged mesoporous silica particles (MPS) (≈0.5 µm in diameter) suspended in both water and a common type of DES (1:2 choline Cl-:ethylene glycol). A careful USAXS analysis reveals that the perturbation of electron density distribution within the DES extends ≈1 μm beyond the particle surface, and that this perturbation can be manipulated by the addition of salt ions (AgCl). The concentration of the pore-filling fluid is greatly reduced in the DES. Notably, we extracted the real-space structures of these fluctuations from the USAXS data using a simulated annealing approach that does not require a priori knowledge about the scattering form factor, and can be generalized to a wide range of complex small-angle scattering problems. Copyright © 2018 Elsevier Inc. All rights reserved.

Predictive Sampling of Rare Conformational Events in Aqueous Solution: Designing a Generalized Orthogonal Space Tempering Method.

PubMed

Lu, Chao; Li, Xubin; Wu, Dongsheng; Zheng, Lianqing; Yang, Wei

2016-01-12

In aqueous solution, solute conformational transitions are governed by intimate interplays of the fluctuations of solute-solute, solute-water, and water-water interactions. To promote molecular fluctuations to enhance sampling of essential conformational changes, a common strategy is to construct an expanded Hamiltonian through a series of Hamiltonian perturbations and thereby broaden the distribution of certain interactions of focus. Due to a lack of active sampling of configuration response to Hamiltonian transitions, it is challenging for common expanded Hamiltonian methods to robustly explore solvent mediated rare conformational events. The orthogonal space sampling (OSS) scheme, as exemplified by the orthogonal space random walk and orthogonal space tempering methods, provides a general framework for synchronous acceleration of slow configuration responses. To more effectively sample conformational transitions in aqueous solution, in this work, we devised a generalized orthogonal space tempering (gOST) algorithm. Specifically, in the Hamiltonian perturbation part, a solvent-accessible-surface-area-dependent term is introduced to implicitly perturb near-solute water-water fluctuations; more importantly in the orthogonal space response part, the generalized force order parameter is generalized as a two-dimension order parameter set, in which essential solute-solvent and solute-solute components are separately treated. The gOST algorithm is evaluated through a molecular dynamics simulation study on the explicitly solvated deca-alanine (Ala10) peptide. On the basis of a fully automated sampling protocol, the gOST simulation enabled repetitive folding and unfolding of the solvated peptide within a single continuous trajectory and allowed for detailed constructions of Ala10 folding/unfolding free energy surfaces. The gOST result reveals that solvent cooperative fluctuations play a pivotal role in Ala10 folding/unfolding transitions. In addition, our assessment analysis suggests that because essential conformational events are mainly driven by the compensating fluctuations of essential solute-solvent and solute-solute interactions, commonly employed "predictive" sampling methods are unlikely to be effective on this seemingly "simple" system. The gOST development presented in this paper illustrates how to employ the OSS scheme for physics-based sampling method designs.

Multi-scale dynamics and relaxation of a tethered membrane in a solvent by Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Pandey, Ras; Anderson, Kelly; Farmer, Barry

2006-03-01

A tethered membrane modeled by a flexible sheet dissipates entropy as it wrinkles and crumples. Nodes of a coarse grained membrane are connected via multiple pathways for dynamical modes to propagate. We consider a sheet with nodes connected by fluctuating bonds on a cubic lattice. The empty lattice sites constitute an effective solvent medium via node-solvent interaction. Each node execute its stochastic motion with the Metropolis algorithm subject to bond fluctuations, excluded volume constraints, and interaction energy. Dynamics and conformation of the sheet are examined at a low and a high temperature with attractive and repulsive node-node interactions for the contrast in an attractive solvent medium. Variations of the mean square displacement of the center node of the sheet and that of its center of mass with the time steps are examined in detail which show different power-law motion from short to long time regimes. Relaxation of the gyration radius and scaling of its asymptotic value with the molecular weight are examined.

Impact of neutral density fluctuations on gas puff imaging diagnostics

NASA Astrophysics Data System (ADS)

Wersal, C.; Ricci, P.

2017-11-01

A three-dimensional turbulence simulation of the SOL and edge regions of a toroidally limited tokamak is carried out. The simulation couples self-consistently the drift-reduced two-fluid Braginskii equations to a kinetic equation for neutral atoms. A diagnostic neutral gas puff on the low-field side midplane is included and the impact of neutral density fluctuations on D_α light emission investigated. We find that neutral density fluctuations affect the D_α emission. In particular, at a radial distance from the gas puff smaller than the neutral mean free path, neutral density fluctuations are anti-correlated with plasma density, electron temperature, and D_α fluctuations. It follows that the neutral fluctuations reduce the D_α emission in most of the observed region and, therefore, have to be taken into account when interpreting the amplitude of the D_α emission. On the other hand, higher order statistical moments (skewness, kurtosis) and turbulence characteristics (such as correlation length, or the autocorrelation time) are not significantly affected by the neutral fluctuations. At distances from the gas puff larger than the neutral mean free path, a non-local shadowing effect influences the neutral density fluctuations. There, the D_α fluctuations are correlated with the neutral density fluctuations, and the high-order statistical moments and measurements of other turbulence properties are strongly affected by the neutral density fluctuations.

Liquid-Vapor Interfacial Properties of Aqueous Solutions of Guanidinium and Methyl Guanidinium Chloride: Influence of Molecular Orientation on Interface Fluctuations

PubMed Central

Ou, Shuching; Cui, Di; Patel, Sandeep

2014-01-01

The guanidinium cation (C(NH2)3+) is a highly stable cation in aqueous solution due to its efficient solvation by water molecules and resonance stabilization of the charge. Its salts increase the solubility of nonpolar molecules (”salting-in”) and decrease the ordering of water. It is one of the strongest denaturants used in biophysical studies of protein folding. We investigate the behavior of guanidinium and its derivative, methyl guanidinium (an amino acid analogue) at the air-water surface, using atomistic molecular dynamics (MD) simulations and calculation of potentials of mean force. Methyl guanidinium cation is less excluded from the air-water surface than guanidinium cation, but both cations show orientational dependence of surface affinity. Parallel orientations of the guanidinium ring (relative to the Gibbs dividing surface) show pronounced free energy minima in the interfacial region, while ring orientations perpendicular to the GDS exhibit no discernible surface stability. Calculations of surface fluctuations demonstrate that near the air-water surface, the parallel-oriented cations generate significantly greater interfacial fluctuations compared to other orientations, which induces more long-ranged perturbations and solvent density redistribution. Our results suggest a strong correlation with induced interfacial fluctuations and ion surface stability. These results have implications for interpreting molecular-level, mechanistic action of this osmolyte’s interaction with hydrophobic interfaces as they impact protein denaturation (solubilization). PMID:23937431

Solvent Electrostatic Response: From Simple Solutes to Proteins

NASA Astrophysics Data System (ADS)

Dinpajooh, Mohammadhasan

How water behaves at interfaces is relevant to many scientific and technological applications; however, many subtle phenomena are unknown in aqueous solutions. In this work, interfacial structural transition in hydration shells of a polarizable solute at critical polarizabilities is discovered. The transition is manifested in maximum water response, the reorientation of the water dipoles at the interface, and an increase in the density of dangling OH bonds. This work also addresses the role of polarizability of the active site of proteins in biological catalytic reactions. For proteins, the hydration shell becomes very heterogeneous and involves a relatively large number of water molecules. The molecular dynamics simulations show that the polarizability, along with the atomic charge distribution, needs to be a part of the picture describing how enzymes work. Non Gaussian dynamics in time-resolved linear and nonlinear (correlation) 2D spectra are also analyzed. Additionally, a theoretical formalism is presented to show that when preferential orientations of water dipoles exist at the interface, electrophoretic charges can be produced without free charge carriers, i.e., neutral solutes can move in a constant electric field due to the divergence of polarization at the interface. Furthermore, the concept of interface susceptibility is introduced. It involves the fluctuations of the surface charge density caused by thermal motion and its correlation over the characteristic correlation length with the fluctuations of the solvent charge density. Solvation free energy and interface dielectric constant are formulated accordingly. Unlike previous approaches, the solvation free energy scales quite well in a broad range of ion sizes, namely in the range of 2-14 A. Interface dielectric constant is defined such that the boundary conditions in the Laplace equation describing a micro- or mesoscopic interface are satisfied. The effective dielectric constant of interfacial water is found to be significantly lower than its bulk value. Molecular dynamics simulation results show that the interface dielectric constant for a TIP3P water model changes from nine to four when the effective solute radius is increased from 5 Ato 18 A. The small value of the interface dielectric constant of water has potentially dramatic consequences for hydration.

Direct observation of two-step crystallization in nanoparticle superlattice formation

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

Park, Jungwon; Zheng, Haimei; Lee, Won Chul

2011-10-06

Direct imaging of nanoparticle solutions by liquid phase transmission electron microscopy has enabled unique in-situ studies of nanoparticle motion and growth. In the present work, we report on real-time formation of two-dimensional nanoparticle arrays in the very low diffusive limit, where nanoparticles are mainly driven by capillary forces and solvent fluctuations. We find that superlattice formation appears to be segregated into multiple regimes. Initially, the solvent front drags the nanoparticles, condensing them into an amorphous agglomerate. Subsequently, the nanoparticle crystallization into an array is driven by local fluctuations. Following the crystallization event, superlattice growth can also occur via the additionmore » of individual nanoparticles drawn from outlying regions by different solvent fronts. The dragging mechanism is consistent with simulations based on a coarse-grained lattice gas model at the same limit.« less

On the role of water density fluctuations in the inhibition of a proton channel

PubMed Central

Gianti, Eleonora; Delemotte, Lucie; Klein, Michael L.; Carnevale, Vincenzo

2016-01-01

Hv1 is a transmembrane four-helix bundle that transports protons in a voltage-controlled manner. Its crucial role in many pathological conditions, including cancer and ischemic brain damage, makes Hv1 a promising drug target. Starting from the recently solved crystal structure of Hv1, we used structural modeling and molecular dynamics simulations to characterize the channel’s most relevant conformations along the activation cycle. We then performed computational docking of known Hv1 inhibitors, 2-guanidinobenzimidazole (2GBI) and analogs. Although salt-bridge patterns and electrostatic potential profiles are well-defined and distinctive features of activated versus nonactivated states, the water distribution along the channel lumen is dynamic and reflects a conformational heterogeneity inherent to each state. In fact, pore waters assemble into intermittent hydrogen-bonded clusters that are replaced by the inhibitor moieties upon ligand binding. The entropic gain resulting from releasing these conformationally restrained waters to the bulk solvent is likely a major contributor to the binding free energy. Accordingly, we mapped the water density fluctuations inside the pore of the channel and identified the regions of maximum fluctuation within putative binding sites. Two sites appear as outstanding: One is the already known binding pocket of 2GBI, which is accessible to ligands from the intracellular side; the other is a site located at the exit of the proton permeation pathway. Our analysis of the waters confined in the hydrophobic cavities of Hv1 suggests a general strategy for drug discovery that can be applied to any ion channel. PMID:27956641

High Energy Density in Azobenzene-based Materials for Photo-Thermal Batteries via Controlled Polymer Architecture and Polymer-Solvent Interactions.

PubMed

Jeong, Seung Pyo; Renna, Lawrence A; Boyle, Connor J; Kwak, Hyunwook S; Harder, Edward; Damm, Wolfgang; Venkataraman, Dhandapani

2017-12-19

Energy densities of ~510 J/g (max: 698 J/g) have been achieved in azobenzene-based syndiotactic-rich poly(methacrylate) polymers. The processing solvent and polymer-solvent interactions are important to achieve morphologically optimal structures for high-energy density materials. This work shows that morphological changes of solid-state syndiotactic polymers, driven by different solvent processings play an important role in controlling the activation energy of Z-E isomerization as well as the shape of the DSC exotherm. Thus, this study shows the crucial role of processing solvents and thin film structure in achieving higher energy densities.

The Transport of Density Fluctuations Throughout the Heliosphere

NASA Technical Reports Server (NTRS)

Zank, G. P.; Jetha, N.; Hu, Q.; Hunana, P.

2012-01-01

The solar wind is recognized as a turbulent magnetofluid, for which the properties of the turbulent velocity and magnetic field fluctuations are often described by the equations of incompressible magnetohydrodynamics (MHD). However, low-frequency density turbulence is also ubiquitous. On the basis of a nearly incompressible formulation of MHD in the expanding inhomogeneous solar wind, we derive the transport equation for the variance of the density fluctuations (Rho(exp 2)). The transport equation shows that density fluctuations behave as a passive scalar in the supersonic solar wind. In the absence of sources of density turbulence, such as within 1AU, the variance (Rho(exp 2)) approximates r(exp -4). In the outer heliosphere beyond 1 AU, the shear between fast and slow streams, the propagation of shocks, and the creation of interstellar pickup ions all act as sources of density turbulence. The model density fluctuation variance evolves with heliocentric distance within approximately 300 AU as (Rho(exp 2)) approximates r(exp -3.3) after which it flattens and then slowly increases. This is precisely the radial profile for the density fluctuation variance observed by Voyager 2. Using a different analysis technique, we confirm the radial profile for Rho(exp 2) of Bellamy, Cairns, & Smith using Voyager 2 data. We conclude that a passive scalar description for density fluctuations in the supersonic solar wind can explain the density fluctuation variance observed in both the inner and the outer heliosphere.

Dendritic brushes under theta and poor solvent conditions

NASA Astrophysics Data System (ADS)

Gergidis, Leonidas N.; Kalogirou, Andreas; Charalambopoulos, Antonios; Vlahos, Costas

2013-07-01

The effects of solvent quality on the internal stratification of polymer brushes formed by dendron polymers up to third generation were studied by means of molecular dynamics simulations with Langevin thermostat. The distributions of polymer units, of the free ends, the radii of gyration, and the back folding probabilities of the dendritic spacers were studied at the macroscopic states of theta and poor solvent. For high grafting densities we observed a small decrease in the height of the brush as the solvent quality decreases. The internal stratification in theta solvent was similar to the one we found in good solvent, with two and in some cases three kinds of populations containing short dendrons with weakly extended spacers, intermediate-height dendrons, and tall dendrons with highly stretched spacers. The differences increase as the grafting density decreases and single dendron populations were evident in theta and poor solvent. In poor solvent at low grafting densities, solvent micelles, polymeric pinned lamellae, spherical and single chain collapsed micelles were observed. The scaling dependence of the height of the dendritic brush at high density brushes for both solvents was found to be in agreement with existing analytical results.

Solvent fluctuations and nuclear quantum effects modulate the molecular hyperpolarizability of water

NASA Astrophysics Data System (ADS)

Liang, Chungwen; Tocci, Gabriele; Wilkins, David M.; Grisafi, Andrea; Roke, Sylvie; Ceriotti, Michele

2017-07-01

Second-harmonic scattering (SHS) experiments provide a unique approach to probe noncentrosymmetric environments in aqueous media, from bulk solutions to interfaces, living cells, and tissue. A central assumption made in analyzing SHS experiments is that each molecule scatters light according to a constant molecular hyperpolarizability tensor β(2 ). Here, we investigate the dependence of the molecular hyperpolarizability of water on its environment and internal geometric distortions, in order to test the hypothesis of constant β(2 ). We use quantum chemistry calculations of the hyperpolarizability of a molecule embedded in point-charge environments obtained from simulations of bulk water. We demonstrate that both the heterogeneity of the solvent configurations and the quantum mechanical fluctuations of the molecular geometry introduce large variations in the nonlinear optical response of water. This finding has the potential to change the way SHS experiments are interpreted: In particular, isotopic differences between H2O and D2O could explain recent SHS observations. Finally, we show that a machine-learning framework can predict accurately the fluctuations of the molecular hyperpolarizability. This model accounts for the microscopic inhomogeneity of the solvent and represents a step towards quantitative modeling of SHS experiments.

Permeability modes in fluctuating lipid membranes with DNA-translocating pores.

PubMed

Moleiro, L H; Mell, M; Bocanegra, R; López-Montero, I; Fouquet, P; Hellweg, Th; Carrascosa, J L; Monroy, F

2017-09-01

Membrane pores can significantly alter not only the permeation dynamics of biological membranes but also their elasticity. Large membrane pores able to transport macromolecular contents represent an interesting model to test theoretical predictions that assign active-like (non-equilibrium) behavior to the permeability contributions to the enhanced membrane fluctuations existing in permeable membranes [Maneville et al. Phys. Rev. Lett. 82, 4356 (1999)]. Such high-amplitude active contributions arise from the forced transport of solvent and solutes through the open pores, which becomes even dominant at large permeability. In this paper, we present a detailed experimental analysis of the active shape fluctuations that appear in highly permeable lipid vesicles with large macromolecular pores inserted in the lipid membrane, which are a consequence of transport permeability events occurred in an osmotic gradient. The experimental results are found in quantitative agreement with theory, showing a remarkable dependence with the density of membrane pores and giving account of mechanical compliances and permeability rates that are compatible with the large size of the membrane pore considered. The presence of individual permeation events has been detected in the fluctuation time-series, from which a stochastic distribution of the permeation events compatible with a shot-noise has been deduced. The non-equilibrium character of the membrane fluctuations in a permeation field, even if the membrane pores are mere passive transporters, is clearly demonstrated. Finally, a bio-nano-technology outlook of the proposed synthetic concept is given on the context of prospective uses as active membrane DNA-pores exploitable in gen-delivery applications based on lipid vesicles. Copyright © 2017 Elsevier B.V. All rights reserved.

An ellipsoid-chain model for conjugated polymer solutions

NASA Astrophysics Data System (ADS)

Lee, Cheng K.; Hua, Chi C.; Chen, Show A.

2012-02-01

We propose an ellipsoid-chain model which may be routinely parameterized to capture large-scale properties of semiflexible, amphiphilic conjugated polymers in various solvent media. The model naturally utilizes the defect locations as pivotal centers connecting adjacent ellipsoids (each currently representing ten monomer units), and a variant umbrella-sampling scheme is employed to construct the potentials of mean force (PMF) for specific solvent media using atomistic dynamics data and simplex optimization. The performances, both efficacy and efficiency, of the model are thoroughly evaluated by comparing the simulation results on long, single-chain (i.e., 300-mer) structures with those from two existing, finer-grained models for a standard conjugated polymer (i.e., poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) or MEH-PPV) in two distinct solvents (i.e., chloroform or toluene) as well as a hybrid, binary-solvent medium (i.e., chloroform/toluene = 1:1 in number density). The coarse-grained Monte Carlo (CGMC) simulation of the ellipsoid-chain model is shown to be the most efficient—about 300 times faster than the coarse-grained molecular dynamics (CGMD) simulation of the finest CG model that employs explicit solvents—in capturing elementary single-chain structures for both single-solvent media, and is a few times faster than the coarse-grained Langevin dynamics (CGLD) simulation of another implicit-solvent polymer model with a slightly greater coarse-graining level than in the CGMD simulation. For the binary-solvent system considered, however, both of the two implicit-solvent schemes (i.e., CGMC and CGLD) fail to capture the effects of conspicuous concentration fluctuations near the polymer-solvent interface, arising from a pronounced coupling between the solvent molecules and different parts of the polymer. Essential physical implications are elaborated on the success as well as the failure of the two implicit-solvent CG schemes under varying solvent conditions. Within the ellipsoid-chain model, the impact of synthesized defects on local segmental ordering as well as bulk chain conformation is also scrutinized, and essential consequences in practical applications discussed. In future perspectives, we remark on strategy that takes advantage of the coordination among various CG models and simulation schemes to warrant computational efficiency and accuracy, with the anticipated capability of simulating larger-scale, many-chain aggregate systems.

2D image of local density and magnetic fluctuations from line-integrated interferometry-polarimetry measurements.

PubMed

Lin, L; Ding, W X; Brower, D L

2014-11-01

Combined polarimetry-interferometry capability permits simultaneous measurement of line-integrated density and Faraday effect with fast time response (∼1 μs) and high sensitivity. Faraday effect fluctuations with phase shift of order 0.05° associated with global tearing modes are resolved with an uncertainty ∼0.01°. For physics investigations, local density fluctuations are obtained by inverting the line-integrated interferometry data. The local magnetic and current density fluctuations are then reconstructed using a parameterized fit of the polarimetry data. Reconstructed 2D images of density and magnetic field fluctuations in a poloidal cross section exhibit significantly different spatial structure. Combined with their relative phase, the magnetic-fluctuation-induced particle transport flux and its spatial distribution are resolved.

2D image of local density and magnetic fluctuations from line-integrated interferometry-polarimetry measurements

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

Lin, L., E-mail: lianglin@ucla.edu; Ding, W. X.; Brower, D. L.

2014-11-15

Combined polarimetry-interferometry capability permits simultaneous measurement of line-integrated density and Faraday effect with fast time response (∼1 μs) and high sensitivity. Faraday effect fluctuations with phase shift of order 0.05° associated with global tearing modes are resolved with an uncertainty ∼0.01°. For physics investigations, local density fluctuations are obtained by inverting the line-integrated interferometry data. The local magnetic and current density fluctuations are then reconstructed using a parameterized fit of the polarimetry data. Reconstructed 2D images of density and magnetic field fluctuations in a poloidal cross section exhibit significantly different spatial structure. Combined with their relative phase, the magnetic-fluctuation-induced particlemore » transport flux and its spatial distribution are resolved.« less

Non-uniform Continuum Model for Solvated Species Based on Frozen-Density Embedding Theory: The Study Case of Solvatochromism of Coumarin 153.

PubMed

Shedge, Sapana V; Zhou, Xiuwen; Wesolowski, Tomasz A

2014-09-01

Recent application of the Frozen-Density Embedding Theory based continuum model of the solvent, which is used for calculating solvatochromic shifts in the UV/Vis range, are reviewed. In this model, the solvent is represented as a non-uniform continuum taking into account both the statistical nature of the solvent and specific solute-solvent interactions. It offers, therefore, a computationally attractive alternative to methods in which the solvent is described at atomistic level. The evaluation of the solvatochromic shift involves only two calculations of excitation energy instead of at least hundreds needed to account for inhomogeneous broadening. The present review provides a detailed graphical analysis of the key quantities of this model: the average charge density of the solvent (<ρB>) and the corresponding Frozen-Density Embedding Theory derived embedding potential for coumarin 153.

On the Roles of Substrate Binding and Hinge Unfolding in Conformational Changes of Adenylate Kinase

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

Brokaw, Jason B.; Chu, Jhih-wei

2010-11-17

We characterized the conformational change of adenylate kinase (AK) between open and closed forms by conducting five all-atom molecular-dynamics simulations, each of 100 ns duration. Different initial structures and substrate binding configurations were used to probe the pathways of AK conformational change in explicit solvent, and no bias potential was applied. A complete closed-to-open and a partial open-to-closed transition were observed, demonstrating the direct impact of substrate-mediated interactions on shifting protein conformation. The sampled configurations suggest two possible pathways for connecting the open and closed structures of AK, affirming the prediction made based on available x-ray structures and earlier worksmore » of coarse-grained modeling. The trajectories of the all-atom molecular-dynamics simulations revealed the complexity of protein dynamics and the coupling between different domains during conformational change. Calculations of solvent density and density fluctuations surrounding AK did not show prominent variation during the transition between closed and open forms. Finally, we characterized the effects of local unfolding of an important hinge near Pro177 on the closed-to-open transition of AK and identified a novel mechanism by which hinge unfolding modulates protein conformational change. The local unfolding of Pro177 hinge induces alternative tertiary contacts that stabilize the closed structure and prevent the opening transition.« less

Preferential binding effects on protein structure and dynamics revealed by coarse-grained Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Pandey, R. B.; Jacobs, D. J.; Farmer, B. L.

2017-05-01

The effect of preferential binding of solute molecules within an aqueous solution on the structure and dynamics of the histone H3.1 protein is examined by a coarse-grained Monte Carlo simulation. The knowledge-based residue-residue and hydropathy-index-based residue-solvent interactions are used as input to analyze a number of local and global physical quantities as a function of the residue-solvent interaction strength (f). Results from simulations that treat the aqueous solution as a homogeneous effective solvent medium are compared to when positional fluctuations of the solute molecules are explicitly considered. While the radius of gyration (Rg) of the protein exhibits a non-monotonic dependence on solvent interaction over a wide range of f within an effective medium, an abrupt collapse in Rg occurs in a narrow range of f when solute molecules rapidly bind to a preferential set of sites on the protein. The structure factor S(q) of the protein with wave vector (q) becomes oscillatory in the collapsed state, which reflects segmental correlations caused by spatial fluctuations in solute-protein binding. Spatial fluctuations in solute binding also modify the effective dimension (D) of the protein in fibrous (D ˜ 1.3), random-coil (D ˜ 1.75), and globular (D ˜ 3) conformational ensembles as the interaction strength increases, which differ from an effective medium with respect to the magnitude of D and the length scale.

Marshall N. Rosenbluth Outstanding Doctoral Thesis Award Talk: Simultaneous Measurement of Electron Temperature and Density Fluctuations in the Core of DIII-D Plasmas

NASA Astrophysics Data System (ADS)

White, A. E.

2009-11-01

Multi-field fluctuation measurements provide opportunities for rigorous comparison between experiment and nonlinear gyrokinetic turbulence simulations. A unique set of diagnostics on DIII-D allows for simultaneous study of local, long-wavelength (0 < kθρs< 0.5) electron temperature and density fluctuations in the core plasma (0.4 < ρ< 0.8). Previous experiments in L-mode indicate that normalized electron temperature fluctuation levels (40 < f < 400,kHz) increase with radius from ˜0.4% at ρ= 0.5 to ˜2% at ρ=0.8, similar to simultaneously measured density fluctuations. Electron cyclotron heating (ECH) is used to increase Te, which increases electron temperature fluctuation levels and electron heat transport in the experiments. In contrast, long wavelength density fluctuation levels change very little. The different responses are consistent with increased TEM drive relative to ITG-mode drive. A new capability at DIII-D is the measurement of phase angle between electron temperature and density fluctuations using coupled correlation electron cyclotron emission radiometer and reflectometer diagnostics. Linear and nonlinear GYRO runs have been used to design validation experiments that focus on measurements of the phase angle. GYRO shows that if Te and ∇Te increase 50% in a beam-heated L-mode plasma (ρ=0.5), then the phase angle between electron temperature and density fluctuations decreases 30%-50% and electron temperature fluctuation levels increase a factor of two more than density fluctuations. Comparisons between these predictions and experimental results will be presented.

Many-body dynamics of chemically propelled nanomotors

NASA Astrophysics Data System (ADS)

Colberg, Peter H.; Kapral, Raymond

2017-08-01

The collective behavior of chemically propelled sphere-dimer motors made from linked catalytic and noncatalytic spheres in a quasi-two-dimensional confined geometry is studied using a coarse-grained microscopic dynamical model. Chemical reactions at the catalytic spheres that convert fuel to product generate forces that couple to solvent degrees of freedom as a consequence of momentum conservation in the microscopic dynamics. The collective behavior of the many-body system is influenced by direct intermolecular interactions among the motors, chemotactic effects due to chemical gradients, hydrodynamic coupling, and thermal noise. Segregation into high and low density phases and globally homogeneous states with strong fluctuations are investigated as functions of the motor characteristics. Factors contributing to this behavior are discussed in the context of active Brownian models.

Role of Dynamically Frustrated Bond Disorder in a Li + Superionic Solid Electrolyte

DOE PAGES

Adelstein, Nicole; Wood, Brandon C.

2016-09-16

Inorganic lithium solid electrolytes are critical components in next-generation solid-state batteries, yet the fundamental nature of the cation-anion interactions and their relevance for ionic conductivity in these materials remains enigmatic. Here, we employ first-principles molecular dynamics simulations to explore the interplay between chemistry, structure, and functionality of a highly conductive Li + solid electrolyte, Li3InBr6. Using local-orbital projections to dynamically track the evolution of the electronic charge density, the simulations reveal rapid, correlated fluctuations between cation-anion interactions with different degrees of directional covalent character. These chemical bond dynamics are shown to correlate with Li + mobility, and are enabled thermallymore » by intrinsic frustration between the preferred geometries of chemical bonding and lattice symmetry. We suggest that the fluctuating chemical environment from the polarizable anions functions similar to a solvent, contributing to the superionic behavior of Li 3InBr 6 by temporarily stabilizing configurations favorable for migrating Li +. The generality of these conclusions for understanding solid electrolytes and key factors governing the superionic phase transition is discussed.« less

Properties of density and magnetic fluctuations occurring in density striations in the new LAPD

NASA Astrophysics Data System (ADS)

Maggs, J. E.; Morales, G. J.

2001-10-01

Previous studies of density striations (long, narrow magnetic-field-aligned density depletions) in the LAPD plasma device at UCLA revealed an eigenmode structure to fluctuations driven by the pressure gradient in the striation wall (Maggs and Morales, Phys. Plasmas, 4, 1997). The nature of these fluctuations depended on the plasma beta external to the striation, with shear Alfvén wave turbulence developing at betas less than the mass ratio and drift-Alfvén waves at betas above the mass ratio. These fluctuations were found to have a direct connection to turbulence observed at the plasma edge. The new LAPD is 18 meters in length with a background field up to twice previously attainable values. We report on the properties of fluctuations associated with density striations in the new device over a wider range of beta, and compare them to previous results. The behavior of fluctuations in density striations created in flared-field and magnetic-mirror geometries will also be presented. Research sponsored by ONR and NSF

Intermittent electron density and temperature fluctuations and associated fluxes in the Alcator C-Mod scrape-off layer

NASA Astrophysics Data System (ADS)

Kube, R.; Garcia, O. E.; Theodorsen, A.; Brunner, D.; Kuang, A. Q.; LaBombard, B.; Terry, J. L.

2018-06-01

The Alcator C-Mod mirror Langmuir probe system has been used to sample data time series of fluctuating plasma parameters in the outboard mid-plane far scrape-off layer. We present a statistical analysis of one second long time series of electron density, temperature, radial electric drift velocity and the corresponding particle and electron heat fluxes. These are sampled during stationary plasma conditions in an ohmically heated, lower single null diverted discharge. The electron density and temperature are strongly correlated and feature fluctuation statistics similar to the ion saturation current. Both electron density and temperature time series are dominated by intermittent, large-amplitude burst with an exponential distribution of both burst amplitudes and waiting times between them. The characteristic time scale of the large-amplitude bursts is approximately 15 μ {{s}}. Large-amplitude velocity fluctuations feature a slightly faster characteristic time scale and appear at a faster rate than electron density and temperature fluctuations. Describing these time series as a superposition of uncorrelated exponential pulses, we find that probability distribution functions, power spectral densities as well as auto-correlation functions of the data time series agree well with predictions from the stochastic model. The electron particle and heat fluxes present large-amplitude fluctuations. For this low-density plasma, the radial electron heat flux is dominated by convection, that is, correlations of fluctuations in the electron density and radial velocity. Hot and dense blobs contribute only a minute fraction of the total fluctuation driven heat flux.

Swelling, Structure, and Phase Stability of Soft, Compressible Microgels

NASA Astrophysics Data System (ADS)

Denton, Alan R.; Urich, Matthew

Microgels are soft colloidal particles that swell when dispersed in a solvent. The equilibrium particle size is governed by a delicate balance of osmotic pressures, which can be tuned by varying single-particle properties and externally controlled conditions, such as temperature, pH, ionic strength, and concentration. Because of their tunable size and ability to encapsulate dye or drug molecules, microgels have practical relevance for biosensing, drug delivery, carbon capture, and filtration. Using Monte Carlo simulation, we model suspensions of microgels that interact via Hertzian elastic interparticle forces and can expand or contract via trial size changes governed by the Flory-Rehner free energy of cross-linked polymer gels. We analyze the influence of particle compressibility and size fluctuations on bulk structural and thermal properties by computing swelling ratios, radial distribution functions, static structure factors, osmotic pressures, and freezing densities. With increasing density, microgels progressively deswell and their intrinsic polydispersity broadens, while compressibility acts to forestall crystallization. This work was supported by the National Science Foundation under Grant No. DMR- 1106331.

Solvent selection in ultrasonic-assisted emulsification microextraction: Comparison between high- and low-density solvents by means of novel type of extraction vessel.

PubMed

Nojavan, Saeed; Gorji, Tayebeh; Davarani, Saied Saeed Hosseiny; Morteza-Najarian, Amin

2014-08-01

There are numerous published reports about dispersive liquid phase microextraction of the wide range of substances, however, till now no broadly accepted systematic and purpose oriented selection of extraction solvent has been proposed. Most works deal with the optimization of available solvents without adequate pre-consideration of properness. In this study, it is tried to compare the performances of low- and high-density solvents at the same conditions by means of novel type of extraction vessel with head and bottom conical shape. Extraction efficiencies of seven basic pharmaceutical compounds using eighteen common organic solvents were studied in this work. It was much easier to work with high-density solvents and they mostly showed better performances. This work shows that although exact predicting the performance of the solvents is multifaceted case but the pre-consideration of initial selection of solvents with attention to the physiochemical properties of the desired analytes is feasible and promising. Finally, the practicality of the method for extraction from urine and plasma samples was investigated. Copyright © 2014 Elsevier B.V. All rights reserved.

Fluctuations and symmetry energy in nuclear fragmentation dynamics.

PubMed

Colonna, M

2013-01-25

Within a dynamical description of nuclear fragmentation, based on the liquid-gas phase transition scenario, we explore the relation between neutron-proton density fluctuations and nuclear symmetry energy. We show that, along the fragmentation path, isovector fluctuations follow the evolution of the local density and approach an equilibrium value connected to the local symmetry energy. Higher-density regions are characterized by smaller average asymmetry and narrower isotopic distributions. This dynamical analysis points out that fragment final state isospin fluctuations can probe the symmetry energy of the density domains from which fragments originate.

Efficient molecular density functional theory using generalized spherical harmonics expansions.

PubMed

Ding, Lu; Levesque, Maximilien; Borgis, Daniel; Belloni, Luc

2017-09-07

We show that generalized spherical harmonics are well suited for representing the space and orientation molecular density in the resolution of the molecular density functional theory. We consider the common system made of a rigid solute of arbitrary complexity immersed in a molecular solvent, both represented by molecules with interacting atomic sites and classical force fields. The molecular solvent density ρ(r,Ω) around the solute is a function of the position r≡(x,y,z) and of the three Euler angles Ω≡(θ,ϕ,ψ) describing the solvent orientation. The standard density functional, equivalent to the hypernetted-chain closure for the solute-solvent correlations in the liquid theory, is minimized with respect to ρ(r,Ω). The up-to-now very expensive angular convolution products are advantageously replaced by simple products between projections onto generalized spherical harmonics. The dramatic gain in speed of resolution enables to explore in a systematic way molecular solutes of up to nanometric sizes in arbitrary solvents and to calculate their solvation free energy and associated microscopic solvent structure in at most a few minutes. We finally illustrate the formalism by tackling the solvation of molecules of various complexities in water.

Direct comparison of Viking 2.3-GHz signal phase fluctuation and columnar electron density between 2 and 160 solar radii

NASA Technical Reports Server (NTRS)

Berman, A. L.; Wackley, J. A.; Hietzke, W. H.

1982-01-01

The relationship between solar wind induced signal phase fluctuation and solar wind columnar electron density has been the subject of intensive analysis during the last two decades. In this article, a sizeable volume of 2.3-GHz signal phase fluctuation and columnar electron density measurements separately and concurrently inferred from Viking spacecraft signals are compared as a function of solar geometry. These data demonstrate that signal phase fluctuation and columnar electron density are proportional over a very wide span of solar elongation angle. A radially dependent electron density model which provides a good fit to the columnar electron density measurements and, when appropriately scaled, to the signal phase fluctuation measurements, is given. This model is also in good agreement with K-coronameter observations at 2 solar radii (2r0), with pulsar time delay measurements at 10r0, and with spacecraft in situ electron density measurements at 1 AU.

Communication: Free-energy analysis of hydration effect on protein with explicit solvent: Equilibrium fluctuation of cytochrome c

NASA Astrophysics Data System (ADS)

Karino, Yasuhito; Matubayasi, Nobuyuki

2011-01-01

The relationship between the protein conformation and the hydration effect is investigated for the equilibrium fluctuation of cytochrome c. To elucidate the hydration effect with explicit solvent, the solvation free energy of the protein immersed in water was calculated using the molecular dynamics simulation coupled with the method of energy representation. The variations of the protein intramolecular energy and the solvation free energy are found to compensate each other in the course of equilibrium structural fluctuation. The roles of the attractive and repulsive components in the protein-water interaction are further examined for the solvation free energy. The attractive component represented as the average sum of protein-water interaction energy is dominated by the electrostatic effect and is correlated to the solvation free energy through the linear-response-type relationship. No correlation with the (total) solvation free energy is seen, on the other hand, for the repulsive component expressed as the excluded-volume effect.

Fluid transition layer between rigid solute and liquid solvent: is there depletion or enrichment?

PubMed

Djikaev, Yuri S; Ruckenstein, Eli

2016-03-21

The fluid layer between solute and liquid solvent is studied by combining the density functional theory with the probabilistic hydrogen bond model. This combination allows one to obtain the equilibrium distribution of fluid molecules, taking into account the hydrogen bond contribution to the external potential whereto they are subjected near the solute. One can find the effective width of the fluid solvent-solute transition layer and fluid average density in that layer, and determine their dependence on temperature, solvent-solute affinity, vicinal hydrogen bond (hb) energy alteration ratio, and solute radius. Numerical calculations are performed for the solvation of a plate and spherical solutes of four different radii in two model solvents (associated liquid and non-associated one) in the temperature range from 293 K to 333 K for various solvent-solute affinities and hydrogen bond energy alteration ratios. The predictions of our model for the effective width and average density of the transition layer are consistent with experiments and simulations. The small-to-large crossover lengthscale for hydrophobic hydration is expected to be about 3-5 nm. Remarkably, characterizing the transition layer with the average density, one can observe that for small hydrophobes, the transition layer becomes enriched with rather than depleted of fluid when the solvent-solute affinity and hb-energy alteration ratio become large enough. The boundary values of solvent-solute affinity and hb-energy alteration ratio, needed for the "depletion-to-enrichment" crossover (in the smoothed density sense), are predicted to decrease with increasing temperature.

Molecular dynamics simulation of solute diffusion in Lennard-Jones fluids

NASA Astrophysics Data System (ADS)

Yamaguchi, T.; Kimura, Y.; Hirota, N.

We performed a molecular dynamics (MD) simulation for a system of 5 solute molecules in 495 solvent molecules interacting through the Lennard-Jones (LJ) 12-6 potential, in order to study solvent density effects on the diffusion coefficients in supercritical fluids. The effects of the size of the solute and the strength of the solute-solvent attractive interaction on the diffusion coefficient of the solute were examined. The diffusion coefficients of the solute molecules were calculated at T = 1.5 (in the LJ reduced unit), slightly above the critical temperature, from rho = 0.1 to rho = 0.95, where rho is the number density in the LJ reduced unit. The memory function in the generalized Langevin equation was calculated, in order to know the molecular origin of the friction on a solute. The memory function is separated into fast and slow components. The former arises from the solute-solvent repulsive interaction, and is interpreted as collisional Enskog-like friction. The interaction strength dependence of the collisional friction is larger in the low- and medium-density regions, which is consistent with the 'clustering' picture, i.e., the local density enhancement due to the solute-solvent attractive interaction. However, the slow component of the memory function suppresses the effect of the local density on the diffusion coefficients, and as a result the effect of the attractive interaction is smaller on the diffusion coefficients than on the local density. Nonetheless, the solvent density dependence of the effect of the attraction on the diffusion coefficient varies with the local density, and it is concluded that the local density is the principal factor that determines the interaction strength dependence of the diffusion coefficient in the low- and medium-density regions (p < 0.6).

Differential interferometry for measurement of density fluctuations and fluctuation-induced transport (invited)

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

Lin, L.; Ding, W. X.; Brower, D. L.

2010-10-15

Differential interferometry employs two parallel laser beams with a small spatial offset (less than beam width) and frequency difference (1-2 MHz) using common optics and a single mixer for a heterodyne detection. The differential approach allows measurement of the electron density gradient, its fluctuations, as well as the equilibrium density distribution. This novel interferometry technique is immune to fringe skip errors and is particularly useful in harsh plasma environments. Accurate calibration of the beam spatial offset, accomplished by use of a rotating dielectric wedge, is required to enable broad application of this approach. Differential interferometry has been successfully used onmore » the Madison Symmetric Torus reversed-field pinch plasma to directly measure fluctuation-induced transport along with equilibrium density profile evolution during pellet injection. In addition, by combining differential and conventional interferometry, both linear and nonlinear terms of the electron density fluctuation energy equation can be determined, thereby allowing quantitative investigation of the origin of the density fluctuations. The concept, calibration, and application of differential interferometry are presented.« less

Effects of concentration, temperature and solvent composition on density and apparent molar volume of the binary mixtures of cationic-anionic surfactants in methanol-water mixed solvent media.

PubMed

Bhattarai, Ajaya; Chatterjee, Sujeet Kumar; Niraula, Tulasi Prasad

2013-01-01

The accurate measurements on density of the binary mixtures of cetyltrimethylammonium bromide and sodium dodecyl sulphate in pure water and in methanol(1) + water (2) mixed solvent media containing (0.10, 0.20, and 0.30) volume fractions of methanol at 308.15, 318.15, and 323.15 K are reported. The concentrations are varied from (0.03 to 0.12) mol.l(-1) of sodium dodecyl sulphate in presence of ~ 5.0×10(-4) mol.l(-1) cetyltrimethylammonium bromide. The results showed almost increase in the densities with increasing surfactant mixture concentration, also the densities are found to decrease with increasing temperature over the entire concentration range, investigated in a given mixed solvent medium and these values are found to decrease with increasing methanol content in the solvent composition. The concentration dependence of the apparent molar volumes appear to be negligible over the entire concentration range, investigated in a given mixed solvent medium and the apparent molar volumes increase with increasing temperature and are found to decrease with increasing methanol content in the solvent composition.

Density fluctuation in HT-6M tokamak by CO2 laser scattering

NASA Astrophysics Data System (ADS)

Zeng, Lei; Cao, Jinxiang; Zhu, Guoliang; Ding, Weixing; Yu, Chang-Xuan; Zhang, Daqing; Li, Youyi

1993-09-01

The small scale density fluctuations in the interior of HT-6M Ohmic plasma have been studied by CO2 laser collective scattering system in deuterium discharges covering a wide range of nqa (chord-average density times safety factor at the limiter) and energy confinement time. The relative density fluctuation level in the interior is inversely proportional to the toroidal magnetic field and average density, and the energy confinement time (tau) E decreases with the fluctuation level increasing in the region where (tau) E linearly increases with nq0.5a and satisfies the Goldston scaling law. It is suggested that the microturbulence in the interior zone is responsible for anomalous transport in tokamaks.

Density Fluctuation in Asymmetric Nozzle Plumes and Correlation with Far Field Noise

NASA Technical Reports Server (NTRS)

Panda, J.; Zaman, K. B. M. Q.

2001-01-01

A comparative experimental study of air density fluctuations in the unheated plumes of a circular, 4-tabbed-circular, chevron-circular and 10-lobed rectangular nozzles was performed at a fixed Mach number of 0.95 using a recently developed Rayleigh scattering based technique. Subsequently, the flow density fluctuations are cross-correlated with the far field sound pressure fluctuations to determine sources for acoustics emission. The nearly identical noise spectra from the baseline circular and the chevron nozzles are found to be in agreement with the similarity in spreading, turbulence fluctuations, and flow-sound correlations measured in the plumes. The lobed nozzle produced the least low frequency noise, in agreement with the weakest overall density fluctuations and flow-sound correlation. The tabbed nozzle took an intermediate position in the hierarchy of noise generation, intensity of turbulent fluctuation and flow-sound correlation. Some of the features in the 4-tabbed nozzle are found to be explainable in terms of splitting of the jet in a central large core and 4 side jetlets.

Density Fluctuations in a Polar Coronal Hole

NASA Astrophysics Data System (ADS)

Hahn, Michael; D’Huys, Elke; Savin, Daniel Wolf

2018-06-01

We have measured the root-mean-square (rms) amplitude of intensity fluctuations, ΔI, in plume and interplume regions of a polar coronal hole. These intensity fluctuations correspond to density fluctuations. Using data from the Sun Watcher using the Active Pixel System detector and Image Processing on the Project for Onboard Autonomy (Proba2), our results extend up to a height of about 1.35 R ⊙. One advantage of the rms analysis is that it does not rely on a detailed evaluation of the power spectrum, which is limited by noise levels to low heights in the corona. The rms approach can be performed up to larger heights where the noise level is greater, provided that the noise itself can be quantified. At low heights, both the absolute ΔI, and the amplitude relative to the mean intensity, ΔI/I, decrease with height. However, starting at about 1.2 R ⊙, ΔI/I increases, reaching 20%–40% by 1.35 R ⊙. This corresponds to density fluctuations of Δn e/n e ≈ 10%–20%. The increasing relative amplitude implies that the density fluctuations are generated in the corona itself. One possibility is that the density fluctuations are generated by an instability of Alfvén waves. This generation mechanism is consistent with some theoretical models and with observations of Alfvén wave amplitudes in coronal holes. Although we find that the energy of the observed density fluctuations is small, these fluctuations are likely to play an important indirect role in coronal heating by promoting the reflection of Alfvén waves and driving turbulence.

The statistics of primordial density fluctuations

NASA Astrophysics Data System (ADS)

Barrow, John D.; Coles, Peter

1990-05-01

The statistical properties of the density fluctuations produced by power-law inflation are investigated. It is found that, even the fluctuations present in the scalar field driving the inflation are Gaussian, the resulting density perturbations need not be, due to stochastic variations in the Hubble parameter. All the moments of the density fluctuations are calculated, and is is argued that, for realistic parameter choices, the departures from Gaussian statistics are small and would have a negligible effect on the large-scale structure produced in the model. On the other hand, the model predicts a power spectrum with n not equal to 1, and this could be good news for large-scale structure.

Observations of density fluctuations in an elongated Bose gas: ideal gas and quasicondensate regimes.

PubMed

Esteve, J; Trebbia, J-B; Schumm, T; Aspect, A; Westbrook, C I; Bouchoule, I

2006-04-07

We report in situ measurements of density fluctuations in a quasi-one-dimensional 87Rb Bose gas at thermal equilibrium in an elongated harmonic trap. We observe an excess of fluctuations compared to the shot-noise level expected for uncorrelated atoms. At low atomic density, the measured excess is in good agreement with the expected "bunching" for an ideal Bose gas. At high density, the measured fluctuations are strongly reduced compared to the ideal gas case. We attribute this reduction to repulsive interatomic interactions. The data are compared with a calculation for an interacting Bose gas in the quasicondensate regime.

2D microwave imaging reflectometer electronics.

PubMed

Spear, A G; Domier, C W; Hu, X; Muscatello, C M; Ren, X; Tobias, B J; Luhmann, N C

2014-11-01

A 2D microwave imaging reflectometer system has been developed to visualize electron density fluctuations on the DIII-D tokamak. Simultaneously illuminated at four probe frequencies, large aperture optics image reflections from four density-dependent cutoff surfaces in the plasma over an extended region of the DIII-D plasma. Localized density fluctuations in the vicinity of the plasma cutoff surfaces modulate the plasma reflections, yielding a 2D image of electron density fluctuations. Details are presented of the receiver down conversion electronics that generate the in-phase (I) and quadrature (Q) reflectometer signals from which 2D density fluctuation data are obtained. Also presented are details on the control system and backplane used to manage the electronics as well as an introduction to the computer based control program.

Residual fluctuations in the matter and radiation distribution after the decoupling epoch. [of early universe

NASA Technical Reports Server (NTRS)

Silk, J.; Wilson, M. L.

1980-01-01

The residual spectra of matter and radiation fluctuations in the early universe are investigated, and the evolution of primordial adiabatic and isothermal fluctuations through the decoupling epoch is studied. Amplification of adiabatic density fluctuations during decoupling, or velocity 'overshoot', is largely suppressed by Compton drag. Consequently, the amplitude of density fluctuations entering the horizon prior to decoupling is larger than hitherto assumed in the adiabatic theory. Damping of primordial adiabatic density fluctuations by an order of magnitude occurs on mass-scales of 3 x 10 to the 13th solar masses (Omega = 1) or 10 to the 14th solar masses (Omega = 0.2). Comparison of the residual radiation fluctuations with observational limits indicates that the adiabatic theory is only acceptable if re-ionization of the intergalactic medium results in additional scattering of the radiation after decoupling. Primordial isothermal fluctuations are found to yield radiation fluctuations which are insensitive to the assumed spectrum and lie a factor of about 5 below current limits

Characterization of edge turbulence in different states of divertor detachment using reflectometry in the ASDEX Upgrade tokamak

NASA Astrophysics Data System (ADS)

Nikolaeva, V.; Guimarais, L.; Manz, P.; Carralero, D.; Manso, M. E.; Stroth, U.; Silva, C.; Conway, G. D.; Seliunin, E.; Vicente, J.; Brida, D.; Aguiam, D.; Santos, J.; Silva, A.; ASDEX Upgrade team; MST1 team

2018-05-01

Transport in the scrape-off layer (SOL) depends on the state of divertor detachment. L-mode discharges were analyzed where the state of divertor detachment is varied through a density ramp-up. By means of reflectometry measurements at the low (LFS) and the high field side (HFS), midplane density fluctuations are studied for the first time in ASDEX Upgrade simultaneously at both sides of the tokamak. Radial density fluctuation profiles (δ {n}e/{n}e) increase with radius in both the HFS and the LFS. It is found that in the SOL density fluctuations at the LFS have about a factor of two larger amplitude than at the HFS in agreement with ballooned transport. Density fluctuations at the LFS show a modest variation with increasing background density resulting mainly from a rise of low frequency components. Experimental results are in good agreement with an enhanced convection of filaments at the LFS at the beginning of outer divertor detachment leading to a flatter SOL density profile. In this phase of the discharge, density fluctuations measured at the HFS far-SOL display a strong increase, which may be associated with the presence of faster filaments originated at the LFS.

Effect of Heating on Turbulent Density Fluctuations and Noise Generation From High Speed Jets

NASA Technical Reports Server (NTRS)

Panda, Jayanta; Seasholtz, Richard G.; Elam, Kristie A.; Mielke, Amy F.; Eck, Dennis G.

2004-01-01

Heated jets in a wide range of temperature ratios (TR), and acoustic Mach numbers (Ma) were investigated experimentally using far field microphones and a molecular Rayleigh scattering technique. The latter provided density fluctuations measurements. Two sets of operating conditions were considered: (1) TR was varied between 0.84 and 2.7 while Ma was fixed at 0.9; (2) Ma was varied between 0.6 and 1.48, while TR was fixed at 2.27. The implementation of the molecular Rayleigh scattering technique required dust removal and usage of a hydrogen combustor to avoid soot particles. Time averaged density measurements in the first set of data showed differences in the peripheral density shear layers between the unheated and heated jets. The nozzle exit shear layer showed increased turbulence level with increased plume temperature. Nevertheless, further downstream the density fluctuations spectra are found to be nearly identical for all Mach number and temperature ratio conditions. To determine noise sources a correlation study between plume density fluctuations and far field sound pressure fluctuations was conducted. For all jets the core region beyond the end of the potential flow was found to be the strongest noise source. Except for an isothermal jet, the correlations did not differ significantly with increasing temperature ratio. The isothermal jet created little density fluctuations. Although the far field noise from this jet did not show any exceptional trend, the flow-sound correlations were very low. This indicated that the density fluctuations only acted as a "tracer parameter" for the noise sources.

Gravity waves

NASA Technical Reports Server (NTRS)

Fritts, David

1987-01-01

Gravity waves contributed to the establishment of the thermal structure, small scale (80 to 100 km) fluctuations in velocity (50 to 80 m/sec) and density (20 to 30%, 0 to peak). Dominant gravity wave spectrum in the middle atmosphere: x-scale, less than 100 km; z-scale, greater than 10 km; t-scale, less than 2 hr. Theorists are beginning to understand middle atmosphere motions. There are two classes: Planetary waves and equatorial motions, gravity waves and tidal motions. The former give rise to variability at large scales, which may alter apparent mean structure. Effects include density and velocity fluctuations, induced mean motions, and stratospheric warmings which lead to the breakup of the polar vortex and cooling of the mesosphere. On this scale are also equatorial quasi-biennial and semi-annual oscillations. Gravity wave and tidal motions produce large rms fluctuations in density and velocity. The magnitude of the density fluctuations compared to the mean density is of the order of the vertical wavelength, which grows with height. Relative density fluctuations are less than, or of the order of 30% below the mesopause. Such motions may cause significant and variable convection, and wind shear. There is a strong seasonal variation in gravity wave amplitude. Additional observations are needed to address and quantify mean and fluctuation statistics of both density and mean velocity, variability of the mean and fluctuations, and to identify dominant gravity wave scales and sources as well as causes of variability, both temporal and geographic.

Investigation of Density Fluctuations in Supersonic Free Jets and Correlation with Generated Noise

NASA Technical Reports Server (NTRS)

Panda, J.; Seasholtz, R. G.

2000-01-01

The air density fluctuations in the plumes of fully-expanded, unheated free jets were investigated experimentally using a Rayleigh scattering based technique. The point measuring technique used a continuous wave laser, fiber-optic transmission and photon counting electronics. The radial and centerline profiles of time-averaged density and root-mean-square density fluctuation provided a comparative description of jet growth. To measure density fluctuation spectra a two-Photomultiplier tube technique was used. Crosscorrelation between the two PMT signals significantly reduced electronic shot noise contribution. Turbulent density fluctuations occurring up to a Strouhal number (Sr) of 2.5 were resolved. A remarkable feature of density spectra, obtained from the same locations of jets in 0.5< M<1.5 range, is a constant Strouhal frequency for peak fluctuations. A detailed survey at Mach numbers M = 0.95, 1.4 and 1.8 showed that, in general, distribution of various Strouhal frequency fluctuations remained similar for the three jets. In spite of the similarity in the flow fluctuation the noise characteristics were found to be significantly different. Spark schlieren photographs and near field microphone measurements confirmed that the eddy Mach wave radiation was present in Mach 1.8 jet, and was absent in Mach 0.95 jet. To measure correlation between the flow and the far field sound pressure fluctuations, a microphone was kept at a distance of 50 diameters, 30 deg. to the flow direction, and the laser probe volume was moved from point to point in the flow. The density fluctuations in the peripheral shear layer of Mach 1.8 jet showed significant correlation up to the measurement limit of Sr = 2.5, while for Mach 0.95 jet no correlation was measured. Along the centerline measurable correlation was found from the end of the potential core and at the low frequency range (Sr less than 0.5). Usually the normalized correlation values increased with an increase of the jet Mach number. The experimental data point out eddy Mach waves as a strong source of sound generation in supersonic jets and fail to locate the primary noise mechanism in subsonic jets.

Modeling the color of natural dyes

NASA Astrophysics Data System (ADS)

Ge, Xiaochuan; Calzolari, Arrigo; Binnie, Simon; Baroni, Stefano

2013-03-01

We report on a theoretical study, based on time-dependent density-functional theory, of various factors affecting the optical properties of a few representative anthocyanins, a class of molecules responsible for the color of many fruits, flowers, and leaves, which have also aroused some interest for photovoltaic applications. We first address the influence of substituting different side groups in the phenyl ring of flavylium dyes. We find that these dyes can be classified into three broad classes, according to the number of peaks (1, 2, or 3) featured in the visible range, and give a rationale to this finding. We then examine the effects of solvent-induced thermal fluctuations and dielectric screening, by calculating the spectrum of a representative molecule in solution, for each one these classes. This is achieved by first running an ab initio molecular dynamics simulation of an explicit model for the water-solvated molecule, and then accumulating time averages of the optical spectra calculated on the fly. The effects of thermal fluctuations are shown to overshadow those of dielectric screening, and more dramatic the larger the number of peaks in the gas phase. The effects of different functionals (GGA vs. hybrids) on the calculated spectra are also addressed.

Density and magnetic fluctuations in type III-ELM pedestal evolution in JET: experimental and numerical characterization

NASA Astrophysics Data System (ADS)

De Masi, G.; Predebon, I.; Spagnolo, S.; Meneses, L.; Delabie, E.; Lupelli, I.; Hillesheim, J. C.; Maggi, C.; Contributors, JET

2018-04-01

Density and magnetic fluctuation measurements in low-β type-III ELM discharges are obtained in the Joint European Torus (JET). They are observed during the inter-ELM pedestal evolution, after the LH transition phase, at about 60-70 kHz. Density fluctuations are measured with a correlation reflectometer system installed on the low-field side and they are localized at the pedestal top. Magnetic fluctuations with a spatial scale k_yρ_i˜ 0.1 are measured through a high resolution coil array. The main features and the relations with local plasma parameters are presented. The nature of these fluctuations is discussed along with linear gyrokinetic simulations. Ion temperature gradient (ITG) modes are the dominant instabilities in the frequency range of interest. In terms of radial localization, typical oscillation frequency and qualitative relation with the possible linear drive, ITG modes are consistent with the experimental density fluctuations measurements. Micro-tearing modes (MTMs), found unstable with a lower growth rate, appear a possible explanation for magnetic fluctuations in terms of typical wavenumbers and direction of propagation.

Poynting vector, energy densities, and pressure of collective transverse electromagnetic fluctuations in unmagnetized plasmas

NASA Astrophysics Data System (ADS)

Schlickeiser, R.

2012-01-01

A systematic calculation of the electromagnetic properties (Poynting vector, electromagnetic energy, and pressure) of the collective transverse fluctuations in unmagnetized plasmas with velocity-anisotropic plasma particle distributions functions is presented. Time-averaged electromagnetic properties for monochromatic weakly damped wave-like fluctuations and space-averaged electromagnetic properties for monochromatic weakly propagating and aperiodic fluctuations are calculated. For aperiodic fluctuations, the Poynting vector as well as the sum of the space-averaged electric and magnetic field energy densities vanish. However, aperiodic fluctuations possess a positive pressure given by its magnetic energy density. This finite pressure density pa of aperiodic fluctuations has important consequences for the dynamics of cosmic unmagnetized plasmas such as the intergalactic medium after reionization. Adopting the standard cosmological evolution model, we show that this additional pressure changes the expansion law of the universe leading to further deceleration. Negative vacuum pressure counterbalances this deceleration to an accelerating universe provided that the negative vacuum pressure is greater than 1.5pa, which we estimate to be of the order 2.1 . 10-16 dyn cm-2.

Density dependence in demography and dispersal generates fluctuating invasion speeds

PubMed Central

Li, Bingtuan; Miller, Tom E. X.

2017-01-01

Density dependence plays an important role in population regulation and is known to generate temporal fluctuations in population density. However, the ways in which density dependence affects spatial population processes, such as species invasions, are less understood. Although classical ecological theory suggests that invasions should advance at a constant speed, empirical work is illuminating the highly variable nature of biological invasions, which often exhibit nonconstant spreading speeds, even in simple, controlled settings. Here, we explore endogenous density dependence as a mechanism for inducing variability in biological invasions with a set of population models that incorporate density dependence in demographic and dispersal parameters. We show that density dependence in demography at low population densities—i.e., an Allee effect—combined with spatiotemporal variability in population density behind the invasion front can produce fluctuations in spreading speed. The density fluctuations behind the front can arise from either overcompensatory population growth or density-dependent dispersal, both of which are common in nature. Our results show that simple rules can generate complex spread dynamics and highlight a source of variability in biological invasions that may aid in ecological forecasting. PMID:28442569

Problems with the microbial production of butanol.

PubMed

Zheng, Yan-Ning; Li, Liang-Zhi; Xian, Mo; Ma, Yu-Jiu; Yang, Jian-Ming; Xu, Xin; He, Dong-Zhi

2009-09-01

With the incessant fluctuations in oil prices and increasing stress from environmental pollution, renewed attention is being paid to the microbial production of biofuels from renewable sources. As a gasoline substitute, butanol has advantages over traditional fuel ethanol in terms of energy density and hygroscopicity. A variety of cheap substrates have been successfully applied in the production of biobutanol, highlighting the commercial potential of biobutanol development. In this review, in order to better understand the process of acetone-butanol-ethanol production, traditional clostridia fermentation is discussed. Sporulation is probably induced by solvent formation, and the molecular mechanism leading to the initiation of sporulation and solventogenesis is also investigated. Different strategies are employed in the metabolic engineering of clostridia that aim to enhancing solvent production, improve selectivity for butanol production, and increase the tolerance of clostridia to solvents. However, it will be hard to make breakthroughs in the metabolic engineering of clostridia for butanol production without gaining a deeper understanding of the genetic background of clostridia and developing more efficient genetic tools for clostridia. Therefore, increasing attention has been paid to the metabolic engineering of E. coli for butanol production. The importation and expression of a non-clostridial butanol-producing pathway in E. coli is probably the most promising strategy for butanol biosynthesis. Due to the lower butanol titers in the fermentation broth, simultaneous fermentation and product removal techniques have been developed to reduce the cost of butanol recovery. Gas stripping is the best technique for butanol recovery found so far.

Theoretical study of solvent effects on the coil-globule transition

NASA Astrophysics Data System (ADS)

Polson, James M.; Opps, Sheldon B.; Abou Risk, Nicholas

2009-06-01

The coil-globule transition of a polymer in a solvent has been studied using Monte Carlo simulations of a single chain subject to intramolecular interactions as well as a solvent-mediated effective potential. This solvation potential was calculated using several different theoretical approaches for two simple polymer/solvent models, each employing hard-sphere chains and hard-sphere solvent particles as well as attractive square-well potentials between some interaction sites. For each model, collapse is driven by variation in a parameter which changes the energy mismatch between monomers and solvent particles. The solvation potentials were calculated using two fundamentally different methodologies, each designed to predict the conformational behavior of polymers in solution: (1) the polymer reference interaction site model (PRISM) theory and (2) a many-body solvation potential (MBSP) based on scaled particle theory introduced by Grayce [J. Chem. Phys. 106, 5171 (1997)]. For the PRISM calculations, two well-studied solvation monomer-monomer pair potentials were employed, each distinguished by the closure relation used in its derivation: (i) a hypernetted-chain (HNC)-type potential and (ii) a Percus-Yevick (PY)-type potential. The theoretical predictions were each compared to results obtained from explicit-solvent discontinuous molecular dynamics simulations on the same polymer/solvent model systems [J. Chem. Phys. 125, 194904 (2006)]. In each case, the variation in the coil-globule transition properties with solvent density is mostly qualitatively correct, though the quantitative agreement between the theory and prediction is typically poor. The HNC-type potential yields results that are more qualitatively consistent with simulation. The conformational behavior of the polymer upon collapse predicted by the MBSP approach is quantitatively correct for low and moderate solvent densities but is increasingly less accurate for higher densities. At high solvent densities, the PRISM-HNC and MBSP approaches tend to overestimate, while the PRISM-PY approach underestimates the tendency of the solvent to drive polymer collapse.

Energy gap law of electron transfer in nonpolar solvents.

PubMed

Tachiya, M; Seki, Kazuhiko

2007-09-27

We investigate the energy gap law of electron transfer in nonpolar solvents for charge separation and charge recombination reactions. In polar solvents, the reaction coordinate is given in terms of the electrostatic potentials from solvent permanent dipoles at solutes. In nonpolar solvents, the energy fluctuation due to solvent polarization is absent, but the energy of the ion pair state changes significantly with the distance between the ions as a result of the unscreened strong Coulomb potential. The electron transfer occurs when the final state energy coincides with the initial state energy. For charge separation reactions, the initial state is a neutral pair state, and its energy changes little with the distance between the reactants, whereas the final state is an ion pair state and its energy changes significantly with the mutual distance; for charge recombination reactions, vice versa. We show that the energy gap law of electron-transfer rates in nonpolar solvents significantly depends on the type of electron transfer.

Characterisation of SOL density fluctuations in front of the LHCD PAM launcher in Tore

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

Oosako, T.; Ekedahl, A.; Goniche, M.

2011-12-23

The density fluctuations, modified by Lower Hybrid Wave (LHW), is analyzed in Tore Supra with reference to the injected LHW power, density and the gap between LCFS (Last Closed Flux Surface) and the PAM (passive-active-multijunction) launcher. The density fluctuations are measured with RF probes installed at the PAM launcher front. A density scan at nominal toroidal field (3.8 T) shows that the fluctuations rate stays nearly constant ({approx}50%) for <3.5x10{sup 19}m{sup -3} and with LHW power up to 2MW. However, when increasing the density above <{approx}4.2x10{sup 19}m{sup -3}, using strong gas puffing, the fluctuation rate increases to >70%more » and is characterized by strong negative spikes, with typical frequency >100kHz. These are most likely originating from acceleration of electrons in the LHW near field due to parasitic absorption, as evidenced on the IR images, showing hot spots on the side limiters.« less

Method of filtering a target compound from a first solvent that is above its critical density

DOEpatents

Phelps, Max R [Richland, WA; Yonker, Clement R [Kennewick, WA; Fulton, John L [Richland, WA; Bowman, Lawrence E [Richland, WA

2001-07-24

The present invention is a method of separating a first compound having a macromolecular structure from a mixture. The first solvent is a fluid that is a gas at standard temperature and pressure and is at a density greater than a critical density of the fluid. A macromolecular structure containing a first compound is dissolved therein as a mixture. The mixture is contacted onto a selective barrier and the first solvent passed through the selective barrier thereby retaining the first compound, followed by recovering the first compound. By using a fluid that is a gas at standard temperature and pressure at a density greater than its critical density, separation without depressurization is fast and efficient.

40 CFR 60.433 - Performance test and compliance provisions.

Code of Federal Regulations, 2010 CFR

2010-07-01

.... (6) The density variations with temperature of the raw inks, related coatings, VOC solvents used, and... related coatings measured as used by volume with different amounts of VOC content or different densities... amounts of VOC content or different VOC solvent densities. (2) The total mass of VOC used is determined by...

Molecular dynamics simulations of cis-trans isomerization for a proline-containing tripeptide in solution

NASA Astrophysics Data System (ADS)

Wan, Shun Zhou; Wang, Cun Xin; Xu, Ying Wu; Shi, Yun Yu

1996-11-01

The cis-trans isomerization of X-Pro (X is Pro or any other residue) often plays a rate-limiting role in protein folding. In order to study the dynamic properties of X-Pro in water, we have analyzed the trajectory data obtained from constrained molecular dynamics (MD) simulations of a tripeptide Phe-Pro-Ala in solution. Via calculation of autocorrelation functions and their corresponding spectral densities, we have found that the structural fluctuations of the solute are affected by the motions of various degrees of freedom, and the solvent dynamic behavior is bimodal rather than exponential or Gaussian. In addition, according to the energy and torque analysis, we suggest that both the anti/endo and the syn/endo could be the possible transition state for the cis-trans isomerization of the tripeptide.

Metal-doped organic foam

DOEpatents

Rinde, James A.

1982-01-01

Organic foams having a low density and very small cell size and method for producing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

Method for producing metal oxide aerogels

DOEpatents

Tillotson, Thomas M.; Poco, John F.; Hrubesh, Lawrence W.; Thomas, Ian M.

1995-01-01

A two-step hydrolysis-condensation method was developed to form metal oxide aerogels of any density, including densities of less than 0.003g/cm.sup.3 and greater than 0.27g/cm.sup.3. High purity metal alkoxide is reacted with water, alcohol solvent, and an additive to form a partially condensed metal intermediate. All solvent and reaction-generated alcohol is removed, and the intermediate is diluted with a nonalcoholic solvent. The intermediate can be stored for future use to make aerogels of any density. The aerogels are formed by reacting the intermediate with water, nonalcoholic solvent, and a catalyst, and extracting the nonalcoholic solvent directly. The resulting monolithic aerogels are hydrophobic and stable under atmospheric conditions, and exhibit good optical transparency, high clarity, and homogeneity. The aerogels have high thermal insulation capacity, high porosity, mechanical strength and stability, and require shorter gelation times than aerogels formed by conventional methods.

Method for producing metal oxide aerogels

DOEpatents

Tillotson, T.M.; Poco, J.F.; Hrubesh, L.W.; Thomas, I.M.

1995-04-25

A two-step hydrolysis-condensation method was developed to form metal oxide aerogels of any density, including densities of less than 0.003g/cm{sup 3} and greater than 0.27g/cm{sup 3}. High purity metal alkoxide is reacted with water, alcohol solvent, and an additive to form a partially condensed metal intermediate. All solvent and reaction-generated alcohol is removed, and the intermediate is diluted with a nonalcoholic solvent. The intermediate can be stored for future use to make aerogels of any density. The aerogels are formed by reacting the intermediate with water, nonalcoholic solvent, and a catalyst, and extracting the nonalcoholic solvent directly. The resulting monolithic aerogels are hydrophobic and stable under atmospheric conditions, and exhibit good optical transparency, high clarity, and homogeneity. The aerogels have high thermal insulation capacity, high porosity, mechanical strength and stability, and require shorter gelation times than aerogels formed by conventional methods. 8 figs.

Reconstructing Solvent Density of Myoglobin Unit Cell from Proximal Radial Distribution Functions of Amino Acids

NASA Astrophysics Data System (ADS)

Galbraith, Madeline; Lynch, Gc; Pettitt, Bm

Understanding the solvent density around a protein crystal structure is an important step for refining accurate crystal structures for use in dynamics simulations or in free energy calculations. The free energy of solvation has typically been approximated using an implicit continuum solvent model or an all atom MD simulation, with a trade-off between accuracy and computation time. For proteins, using precomputed proximal radial distribution functions (pRDFs) of the solvent to reconstruct solvent density on a grid is much faster than all atom MD simulations and more accurate than using implicit solvent models. MD simulations were run for the 20 common amino acids and pRDFs were calculated for several atom type data sets with and without hydrogens, using atom types representative of amino acid side chain atoms. Preliminary results from reconstructions suggest using a data set with 15 heavy atoms and 3 hydrogen yields results with the lowest error without a tradeoff on time. The results of using precomputed pRDFs to reconstruct the solvent density of water for the myoglobin (pdb ID 2mgk) unit cell quantifies the accuracy of the method in comparison with the crystallographic data. Funding Acknowledgement: This research was funded by the CPRIT Summer Undergraduate Program in Computational Cancer Biology, training Grant award RP 140113 from the Cancer Prevention & Research Institute of Texas (CPRIT).

Conjugated polymers: Watching polymers dance

NASA Astrophysics Data System (ADS)

Rothberg, Lewis

2011-06-01

Single-molecule spectroscopy allows fluctuations of conjugated polymer conformation to be monitored during solvent vapour annealing. Dramatic changes in fluorescence behaviour are observed and interpreted in terms of transformations between extended and collapsed polymer geometries.

Temperature and density anti-correlations in solar wind fluctuations

NASA Technical Reports Server (NTRS)

Zank, G. P.; Matthaeus, W. H.; Klein, L. W.

1990-01-01

Recent theoretical investigations of low Mach number flows, that describe two distinct approaches by fluids to the incompressible regime are summarized. The first includes the effects of relatively strong density and temperature fluctuations (Type I), while the second places fluctuations in mechanical pressure, density, and temperature on an equal footing (Type II). In the latter case, the relations between density and pressure are recovered, whereas the former case yields departures from incompressible behavior in that density and temperature fluctuations are predicted to be anti-correlated. It is suggested that nearly incompressible fluids can be classified as either Type I or II, and it is shown that the well-known pressure-balanced structures represent a subclass of static solutions within this classification. Two examples from Voyager data illustrate the potential for observing these distinct nearly incompressible dynamical ordering in the solar wind.

Vortex-Density Fluctuations, Energy Spectra, and Vortical Regions in Superfluid Turbulence

NASA Astrophysics Data System (ADS)

Baggaley, Andrew W.; Laurie, Jason; Barenghi, Carlo F.

2012-11-01

Measurements of the energy spectrum and of the vortex-density fluctuation spectrum in superfluid turbulence seem to contradict each other. Using a numerical model, we show that at each instance of time the total vortex line density can be decomposed into two parts: one formed by metastable bundles of coherent vortices, and one in which the vortices are randomly oriented. We show that the former is responsible for the observed Kolmogorov energy spectrum, and the latter for the spectrum of the vortex line density fluctuations.

A phase contrast imaging–interferometer system for detection of multiscale electron density fluctuations on DIII-D

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

Davis, E. M.; Rost, J. C.; Porkolab, M.

2016-11-15

Heterodyne interferometry and phase contrast imaging (PCI) are robust, mature techniques for measuring low-k and high-k electron density fluctuations, respectively. This work describes the first-ever implementation of a combined PCI–interferometer. The combined system uses a single 10.6 μm probe beam, two interference schemes, and two detectors to measure electron density fluctuations at large spatiotemporal bandwidth (10 kHz

Thermal and active fluctuations of a compressible bilayer vesicle

NASA Astrophysics Data System (ADS)

Sachin Krishnan, T. V.; Yasuda, Kento; Okamoto, Ryuichi; Komura, Shigeyuki

2018-05-01

We discuss thermal and active fluctuations of a compressible bilayer vesicle by using the results of hydrodynamic theory for vesicles. Coupled Langevin equations for the membrane deformation and the density fields are employed to calculate the power spectral density matrix of membrane fluctuations. Thermal contribution is obtained by means of the fluctuation dissipation theorem, whereas active contribution is calculated from exponentially decaying time correlation functions of active random forces. We obtain the total power spectral density as a sum of thermal and active contributions. An apparent response function is further calculated in order to compare with the recent microrheology experiment on red blood cells. An enhanced response is predicted in the low-frequency regime for non-thermal active fluctuations.

Traffic jams induced by fluctuation of a leading car.

PubMed

Nagatani, T

2000-04-01

We present a phase diagram of the different kinds of congested traffic triggered by fluctuation of a leading car in an open system without sources and sinks. Traffic states and density waves are investigated numerically by varying the amplitude of fluctuation using a car following model. The phase transitions among the free traffic, oscillatory congested traffic, and homogeneous congested traffic occur by fluctuation of a leading car. With increasing the amplitude of fluctuation, the transition between the free traffic and oscillatory traffic occurs at lower density and the transition between the homogeneous congested traffic and the oscillatory traffic occurs at higher density. The oscillatory congested traffic corresponds to the coexisting phase. Also, the moving localized clusters appear just above the transition lines.

Fluctuation diagrams for hot-wire anemometry in subsonic compressible flows

NASA Technical Reports Server (NTRS)

Stainback, P. C.; Nagabushana, K. A.

1991-01-01

The concept of using 'fluctuation diagrams' for describing basic fluctuations in compressible flows was reported by Kovasznay in the 1950's. The application of this technique, for the most part, was restricted to supersonic flows. Recently, Zinovev and Lebiga published reports where they considered the fluctuation diagrams in subsonic compressible flows. For the above studies, the velocity and density sensitivities of the heated wires were equal. However, there are considerable data, much taken in the 1950's, which indicate that under some conditions the velocity and density sensitivities are not equal in subsonic compressible flows. Therefore, possible fluctuation diagrams are described for the cases where the velocity and density sensitivities are equal and the more general cases where they are unequal.

Effect of magnetic and density fluctuations on the propagation of lower hybrid waves in tokamaks

NASA Astrophysics Data System (ADS)

Vahala, George; Vahala, Linda; Bonoli, Paul T.

1992-12-01

Lower hybrid waves have been used extensively for plasma heating, current drive, and ramp-up as well as sawteeth stabilization. The wave kinetic equation for lower hybrid wave propagation is extended to include the effects of both magnetic and density fluctuations. This integral equation is then solved by Monte Carlo procedures for a toroidal plasma. It is shown that even for magnetic/density fluctuation levels on the order of 10-4, there are significant magnetic fluctuation effects on the wave power deposition into the plasma. This effect is quite pronounced if the magnetic fluctuation spectrum is peaked within the plasma. For Alcator-C-Mod [I. H. Hutchinson and the Alcator Group, Proceedings of the IEEE 13th Symposium on Fusion Engineering (IEEE, New York, 1990), Cat. No. 89CH 2820-9, p. 13] parameters, it seems possible to be able to infer information on internal magnetic fluctuations from hard x-ray data—especially since the effects of fluctuations on electron power density can explain the hard x-ray data from the JT-60 tokamak [H. Kishimoto and JT-60 Team, in Plasma Physics and Controlled Fusion (International Atomic Energy Agency, Vienna, 1989), Vol. I, p. 67].

Brownian Motion with Active Fluctuations

NASA Astrophysics Data System (ADS)

Romanczuk, Pawel; Schimansky-Geier, Lutz

2011-06-01

We study the effect of different types of fluctuation on the motion of self-propelled particles in two spatial dimensions. We distinguish between passive and active fluctuations. Passive fluctuations (e.g., thermal fluctuations) are independent of the orientation of the particle. In contrast, active ones point parallel or perpendicular to the time dependent orientation of the particle. We derive analytical expressions for the speed and velocity probability density for a generic model of active Brownian particles, which yields an increased probability of low speeds in the presence of active fluctuations in comparison to the case of purely passive fluctuations. As a consequence, we predict sharply peaked Cartesian velocity probability densities at the origin. Finally, we show that such a behavior may also occur in non-Gaussian active fluctuations and discuss briefly correlations of the fluctuating stochastic forces.

Compressibility of the protein-water interface

NASA Astrophysics Data System (ADS)

Persson, Filip; Halle, Bertil

2018-06-01

The compressibility of a protein relates to its stability, flexibility, and hydrophobic interactions, but the measurement, interpretation, and computation of this important thermodynamic parameter present technical and conceptual challenges. Here, we present a theoretical analysis of protein compressibility and apply it to molecular dynamics simulations of four globular proteins. Using additively weighted Voronoi tessellation, we decompose the solution compressibility into contributions from the protein and its hydration shells. We find that positively cross-correlated protein-water volume fluctuations account for more than half of the protein compressibility that governs the protein's pressure response, while the self correlations correspond to small (˜0.7%) fluctuations of the protein volume. The self compressibility is nearly the same as for ice, whereas the total protein compressibility, including cross correlations, is ˜45% of the bulk-water value. Taking the inhomogeneous solvent density into account, we decompose the experimentally accessible protein partial compressibility into intrinsic, hydration, and molecular exchange contributions and show how they can be computed with good statistical accuracy despite the dominant bulk-water contribution. The exchange contribution describes how the protein solution responds to an applied pressure by redistributing water molecules from lower to higher density; it is negligibly small for native proteins, but potentially important for non-native states. Because the hydration shell is an open system, the conventional closed-system compressibility definitions yield a pseudo-compressibility. We define an intrinsic shell compressibility, unaffected by occupation number fluctuations, and show that it approaches the bulk-water value exponentially with a decay "length" of one shell, less than the bulk-water compressibility correlation length. In the first hydration shell, the intrinsic compressibility is 25%-30% lower than in bulk water, whereas its self part is 15%-20% lower. These large reductions are caused mainly by the proximity to the more rigid protein and are not a consequence of the perturbed water structure.

Compressibility of the protein-water interface.

PubMed

Persson, Filip; Halle, Bertil

2018-06-07

The compressibility of a protein relates to its stability, flexibility, and hydrophobic interactions, but the measurement, interpretation, and computation of this important thermodynamic parameter present technical and conceptual challenges. Here, we present a theoretical analysis of protein compressibility and apply it to molecular dynamics simulations of four globular proteins. Using additively weighted Voronoi tessellation, we decompose the solution compressibility into contributions from the protein and its hydration shells. We find that positively cross-correlated protein-water volume fluctuations account for more than half of the protein compressibility that governs the protein's pressure response, while the self correlations correspond to small (∼0.7%) fluctuations of the protein volume. The self compressibility is nearly the same as for ice, whereas the total protein compressibility, including cross correlations, is ∼45% of the bulk-water value. Taking the inhomogeneous solvent density into account, we decompose the experimentally accessible protein partial compressibility into intrinsic, hydration, and molecular exchange contributions and show how they can be computed with good statistical accuracy despite the dominant bulk-water contribution. The exchange contribution describes how the protein solution responds to an applied pressure by redistributing water molecules from lower to higher density; it is negligibly small for native proteins, but potentially important for non-native states. Because the hydration shell is an open system, the conventional closed-system compressibility definitions yield a pseudo-compressibility. We define an intrinsic shell compressibility, unaffected by occupation number fluctuations, and show that it approaches the bulk-water value exponentially with a decay "length" of one shell, less than the bulk-water compressibility correlation length. In the first hydration shell, the intrinsic compressibility is 25%-30% lower than in bulk water, whereas its self part is 15%-20% lower. These large reductions are caused mainly by the proximity to the more rigid protein and are not a consequence of the perturbed water structure.

Measurement of Correlation Between Flow Density, Velocity, and Density*velocity(sup 2) with Far Field Noise in High Speed Jets

NASA Technical Reports Server (NTRS)

Panda, Jayanta; Seasholtz, Richard G.; Elam, Kristie A.

2002-01-01

To locate noise sources in high-speed jets, the sound pressure fluctuations p', measured at far field locations, were correlated with each of radial velocity v, density rho, and phov(exp 2) fluctuations measured from various points in jet plumes. The experiments follow the cause-and-effect method of sound source identification, where correlation is related to the first, and correlation to the second source terms of Lighthill's equation. Three fully expanded, unheated plumes of Mach number 0.95, 1.4 and 1.8 were studied for this purpose. The velocity and density fluctuations were measured simultaneously using a recently developed, non-intrusive, point measurement technique based on molecular Rayleigh scattering. It was observed that along the jet centerline the density fluctuation spectra S(sub rho) have different shapes than the radial velocity spectra S(sub v), while data obtained from the peripheral shear layer show similarity between the two spectra. Density fluctuations in the jet showed significantly higher correlation, than either rhov(sub 2) or v fluctuations. It is found that a single point correlation from the peak sound emitting region at the end of the potential core can account for nearly 10% of all noise at 30 to the jet axis. The correlation, representing the effectiveness of a longitudinal quadrupole in generating noise 90 to the jet axis, is found to be zero within experimental uncertainty. In contrast rhov(exp 2) fluctuations were better correlated with sound pressure fluctuation at the 30 location. The strongest source of sound is found to lie at the centerline and beyond the end of potential core.

Reference interaction site model with hydrophobicity induced density inhomogeneity: An analytical theory to compute solvation properties of large hydrophobic solutes in the mixture of polyatomic solvent molecules.

PubMed

Cao, Siqin; Sheong, Fu Kit; Huang, Xuhui

2015-08-07

Reference interaction site model (RISM) has recently become a popular approach in the study of thermodynamical and structural properties of the solvent around macromolecules. On the other hand, it was widely suggested that there exists water density depletion around large hydrophobic solutes (>1 nm), and this may pose a great challenge to the RISM theory. In this paper, we develop a new analytical theory, the Reference Interaction Site Model with Hydrophobicity induced density Inhomogeneity (RISM-HI), to compute solvent radial distribution function (RDF) around large hydrophobic solute in water as well as its mixture with other polyatomic organic solvents. To achieve this, we have explicitly considered the density inhomogeneity at the solute-solvent interface using the framework of the Yvon-Born-Green hierarchy, and the RISM theory is used to obtain the solute-solvent pair correlation. In order to efficiently solve the relevant equations while maintaining reasonable accuracy, we have also developed a new closure called the D2 closure. With this new theory, the solvent RDFs around a large hydrophobic particle in water and different water-acetonitrile mixtures could be computed, which agree well with the results of the molecular dynamics simulations. Furthermore, we show that our RISM-HI theory can also efficiently compute the solvation free energy of solute with a wide range of hydrophobicity in various water-acetonitrile solvent mixtures with a reasonable accuracy. We anticipate that our theory could be widely applied to compute the thermodynamic and structural properties for the solvation of hydrophobic solute.

Effective interactions between nanoparticles: Creating temperature-independent solvation environments for self-assembly

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

Yadav, Hari O. S., E-mail: cyz108802@chemistry.iitd.ac.in, E-mail: hariyadav.iitd@gmail.com; Shrivastav, Gourav; Agarwal, Manish

2016-06-28

The extent to which solvent-mediated effective interactions between nanoparticles can be predicted based on structure and associated thermodynamic estimators for bulk solvents and for solvation of single and pairs of nanoparticles is studied here. As a test of the approach, we analyse the strategy for creating temperature-independent solvent environments using a series of homologous chain fluids as solvents, as suggested by an experimental paper [M. I. Bodnarchuk et al., J. Am. Chem. Soc. 132, 11967 (2010)]. Our conclusions are based on molecular dynamics simulations of Au{sub 140}(SC{sub 10}H{sub 21}){sub 62} nanoparticles in n-alkane solvents, specifically hexane, octane, decane and dodecane,more » using the TraPPE-UA potential to model the alkanes and alkylthiols. The 140-atom gold core of the nanocrystal is held rigid in a truncated octahedral geometry and the gold-thiolate interaction is modeled using a Morse potential. The experimental observation was that the structural and rheological properties of n-alkane solvents are constant over a temperature range determined by equivalent solvent vapour pressures. We show that this is a consequence of the fact that long chain alkane liquids behave to a good approximation as simple liquids formed by packing of monomeric methyl/methylene units. Over the corresponding temperature range (233–361 K), the solvation environment is approximately constant at the single and pair nanoparticle levels under good solvent conditions. However, quantitative variations of the order of 10%–20% do exist in various quantities, such as molar volume of solute at infinite dilution, entropy of solvation, and onset distance for soft repulsions. In the opposite limit of a poor solvent, represented by vacuum in this study, the effective interactions between nanoparticles are no longer temperature-independent with attractive interactions increasing by up to 50% on decreasing the temperature from 361 K to 290 K, accompanied by an increase in emergent anisotropy due to correlation of mass dipoles on the two nanoparticles. One expects therefore that during self-assembly using solvent evaporation, temperature can be used as a structure-directing factor as long as good solvent conditions are maintained. It also suggests that disordered configurations may emerge as solvent quality decreases due to increasing role of short-range attractions and ligand fluctuation-driven anisotropy. The possibilities of using structural estimators of various thermodynamic quantities to analyse the interplay of ligand fluctuations and solvent quality in self-assembly as well as to design solvation environments are discussed.« less

Density-Gradient-Driven trapped-electron-modes in improved-confinement RFP plasmas

NASA Astrophysics Data System (ADS)

Duff, James; Sarff, John; Ding, Weixing; Brower, David; Parke, Eli; Chapman, Brett; Terry, Paul; Pueschel, M. J.; Williams, Zach

2017-10-01

Short wavelength density fluctuations in improved-confinement MST plasmas exhibit multiple features characteristic of the trapped-electron-mode (TEM). Core transport in the RFP is normally governed by magnetic stochasticity stemming from long wavelength tearing modes that arise from current profile peaking, which are suppressed via inductive control for this work. The improved confinement is associated with an increase in the pressure gradient that can destabilize drift waves. The measured density fluctuations have f 50 kHz, kϕρs < 0.14 , and propagate in the electron drift direction. Their spectral emergence coincides with a sharp decrease in global tearing mode associated fluctuations, their amplitude increases with local density gradient, and they exhibit a density-gradient threshold at R /Ln 15 . The GENE code, modified for the RFP, predicts the onset of density-gradient-driven TEM for these strong-gradient plasma conditions. While nonlinear analysis shows a large Dimits shift associated with predicted strong zonal flows, the inclusion of residual magnetic fluctuations, comparable to experimental magnetic fluctuations, causes a collapse of the zonal flows and an increase in the predicted transport to a level close to the experimentally measured heat flux. Work supported by US DOE.

Folding of the four-helix bundle FF domain from a compact on-pathway intermediate state is governed predominantly by water motion.

PubMed

Sekhar, Ashok; Vallurupalli, Pramodh; Kay, Lewis E

2012-11-20

Friction plays a critical role in protein folding. Frictional forces originating from random solvent and protein fluctuations both retard motion along the folding pathway and activate protein molecules to cross free energy barriers. Studies of friction thus may provide insights into the driving forces underlying protein conformational dynamics. However, the molecular origin of friction in protein folding remains poorly understood because, with the exception of the native conformer, there generally is little detailed structural information on the other states participating in the folding process. Here, we study the folding of the four-helix bundle FF domain that proceeds via a transiently formed, sparsely populated compact on-pathway folding intermediate whose structure was elucidated previously. Because the intermediate is stabilized by both native and nonnative interactions, friction in the folding transition between intermediate and folded states is expected to arise from intrachain reorganization in the protein. However, the viscosity dependencies of rates of folding from or unfolding to the intermediate, as established by relaxation dispersion NMR spectroscopy, clearly indicate that contributions from internal friction are small relative to those from solvent, so solvent frictional forces drive the folding process. Our results emphasize the importance of solvent dynamics in mediating the interconversion between protein configurations, even those that are highly compact, and in equilibrium folding/unfolding fluctuations in general.

Regimes of electrostatic collapse of a highly charged polyelectrolyte in a poor solvent.

PubMed

Tom, Anvy Moly; Vemparala, Satyavani; Rajesh, R; Brilliantov, Nikolai V

2017-03-01

We perform extensive molecular dynamics simulations of a highly charged, collapsed, flexible polyelectrolyte chain in a poor solvent for the case when the electrostatic interactions, characterized by the reduced Bjerrum length l B , are strong. We find the existence of several sub-regimes in the dependence of the gyration radius of the chain R g on l B characterized by R g ∼ l. In contrast to a good solvent, the exponent γ for a poor solvent crucially depends on the size and valency of the counterions. To explain the different sub-regimes, we generalize the existing counterion fluctuation theory by including a more complete account of all possible volume interactions in the free energy of the polyelectrolyte chain. We also show that the presence of condensed counterions modifies the effective attraction among the chain monomers and modulates the sign of the second virial coefficient under poor solvent conditions.

Simple liquid models with corrected dielectric constants

PubMed Central

Fennell, Christopher J.; Li, Libo; Dill, Ken A.

2012-01-01

Molecular simulations often use explicit-solvent models. Sometimes explicit-solvent models can give inaccurate values for basic liquid properties, such as the density, heat capacity, and permittivity, as well as inaccurate values for molecular transfer free energies. Such errors have motivated the development of more complex solvents, such as polarizable models. We describe an alternative here. We give new fixed-charge models of solvents for molecular simulations – water, carbon tetrachloride, chloroform and dichloromethane. Normally, such solvent models are parameterized to agree with experimental values of the neat liquid density and enthalpy of vaporization. Here, in addition to those properties, our parameters are chosen to give the correct dielectric constant. We find that these new parameterizations also happen to give better values for other properties, such as the self-diffusion coefficient. We believe that parameterizing fixed-charge solvent models to fit experimental dielectric constants may provide better and more efficient ways to treat solvents in computer simulations. PMID:22397577

On optical imaging through aircraft turbulent boundary layers

NASA Technical Reports Server (NTRS)

Sutton, G. W.

1980-01-01

Optical resolution quality as affected by aircraft turbulent boundary layers is analyzed. Wind-tunnel data was analyzed to obtained the variation of boundary layer turbulence scale length and mass density rms fluctuations with Mach number. The data gave good agreement with a mass density fluctuation turbulence spectrum that is either isotropic of orthogonally anisotropic. The data did not match an isotropic turbulence velocity spectrum which causes an anisotropic non-orthogonal mass density fluctuation spectrum. The results indicate that the average mass density rms fluctuation is about 10% of the maximum mass density across the boundary layer and that the transverse turbulence scale size is about 10% of the boundary layer thickness. The results indicate that the effect of the turbulent boundary layer is large angle scattering which decreases contrast but not resolution. Using extinction as a criteria the range of acceptable aircraft operating conditions are given.

Fluctuations around equilibrium laws in ergodic continuous-time random walks.

PubMed

Schulz, Johannes H P; Barkai, Eli

2015-06-01

We study occupation time statistics in ergodic continuous-time random walks. Under thermal detailed balance conditions, the average occupation time is given by the Boltzmann-Gibbs canonical law. But close to the nonergodic phase, the finite-time fluctuations around this mean are large and nontrivial. They exhibit dual time scaling and distribution laws: the infinite density of large fluctuations complements the Lévy-stable density of bulk fluctuations. Neither of the two should be interpreted as a stand-alone limiting law, as each has its own deficiency: the infinite density has an infinite norm (despite particle conservation), while the stable distribution has an infinite variance (although occupation times are bounded). These unphysical divergences are remedied by consistent use and interpretation of both formulas. Interestingly, while the system's canonical equilibrium laws naturally determine the mean occupation time of the ergodic motion, they also control the infinite and Lévy-stable densities of fluctuations. The duality of stable and infinite densities is in fact ubiquitous for these dynamics, as it concerns the time averages of general physical observables.

Stochastic transport models for mixing in variable-density turbulence

NASA Astrophysics Data System (ADS)

Bakosi, J.; Ristorcelli, J. R.

2011-11-01

In variable-density (VD) turbulent mixing, where very-different- density materials coexist, the density fluctuations can be an order of magnitude larger than their mean. Density fluctuations are non-negligible in the inertia terms of the Navier-Stokes equation which has both quadratic and cubic nonlinearities. Very different mixing rates of different materials give rise to large differential accelerations and some fundamentally new physics that is not seen in constant-density turbulence. In VD flows material mixing is active in a sense far stronger than that applied in the Boussinesq approximation of buoyantly-driven flows: the mass fraction fluctuations are coupled to each other and to the fluid momentum. Statistical modeling of VD mixing requires accounting for basic constraints that are not important in the small-density-fluctuation passive-scalar-mixing approximation: the unit-sum of mass fractions, bounded sample space, and the highly skewed nature of the probability densities become essential. We derive a transport equation for the joint probability of mass fractions, equivalent to a system of stochastic differential equations, that is consistent with VD mixing in multi-component turbulence and consistently reduces to passive scalar mixing in constant-density flows.

Studies on the latitudinal distribution of ground-based geomagnetic pulsations and fluctuations in the interplanetary medium using discrete mathematical analysis methods

NASA Astrophysics Data System (ADS)

Zelinsky, N. R.; Kleimenova, N. G.; Malysheva, L. M.

2014-07-01

Ground-based geomagnetic Pc5 (2-7 mHz) pulsations, caused by the passage of dense transients (density disturbances) in the solar wind, were analyzed. It was shown that intensive bursts can appear in the density of the solar wind and its fluctuations, up to Np ˜ 30-50 cm3, even during the most magnetically calm year in the past decades (2009). The analysis, performed using one of the latest methods of discrete mathematical analysis (DMA), is presented. The energy functional of a time-series fragment (called "anomaly rectification" in DMA terms) of two such events was calculated. It was established that fluctuations in the dynamic pressure (density) of the solar wind (SW) cause the global excitation of Pc5 geomagnetic pulsations in the daytime sector of the Earth's magnetosphere, i.e., from polar to equatorial latitudes. Such pulsations started and ended suddenly and simultaneously at all latitudes. Fluctuations in the interplanetary magnetic field (IMF) have turned up to be less geoeffective in exciting geomagnetic pulsations than fluctuations in the SW density. The pulsation generation mechanisms in various structural regions of the magnetosphere were probably different. It was therefore concluded that the most probable source of ground-based pulsations are fluctuations of the corresponding periods in the SW density.

The solvent component of macromolecular crystals

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

Weichenberger, Christian X.; Afonine, Pavel V.; Kantardjieff, Katherine

2015-04-30

On average, the mother liquor or solvent and its constituents occupy about 50% of a macromolecular crystal. Ordered as well as disordered solvent components need to be accurately accounted for in modelling and refinement, often with considerable complexity. The mother liquor from which a biomolecular crystal is grown will contain water, buffer molecules, native ligands and cofactors, crystallization precipitants and additives, various metal ions, and often small-molecule ligands or inhibitors. On average, about half the volume of a biomolecular crystal consists of this mother liquor, whose components form the disordered bulk solvent. Its scattering contributions can be exploited in initialmore » phasing and must be included in crystal structure refinement as a bulk-solvent model. Concomitantly, distinct electron density originating from ordered solvent components must be correctly identified and represented as part of the atomic crystal structure model. Herein, are reviewed (i) probabilistic bulk-solvent content estimates, (ii) the use of bulk-solvent density modification in phase improvement, (iii) bulk-solvent models and refinement of bulk-solvent contributions and (iv) modelling and validation of ordered solvent constituents. A brief summary is provided of current tools for bulk-solvent analysis and refinement, as well as of modelling, refinement and analysis of ordered solvent components, including small-molecule ligands.« less

Effect of supersonic molecular-beam injection on edge fluctuation and particle transport in Heliotron J

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

Zang, L., E-mail: l-zang@center.iae.kyoto-u.ac.jp; Kasajima, K.; Hashimoto, K.

Edge fluctuation in a supersonic molecular-beam injection (SMBI) fueled plasma has been measured using an electrostatic probe array. After SMBI, the plasma stored energy (W{sub p}) temporarily decreased then started to increase. The local plasma fluctuation and fluctuation induced particle transport before and after SMBI have been analyzed. In a short duration (∼4 ms) just after SMBI, the density fluctuation of broad-band low frequency increased, and the probability density function (PDF) changed from a nearly Gaussian to a positively skewed non-Gaussian one. This suggests that intermittent structures were produced due to SMBI. Also the fluctuation induced particle transport was greatly enhancedmore » during this short duration. About 4 ms after SMBI, the low frequency broad-band density fluctuation decreased, and the PDF returned to a nearly Gaussian shape. Also the fluctuation induced particle transport was reduced. Compared with conventional gas puff, W{sub p} degradation window is very short due to the short injection period of SMBI. After this short degradation window, fluctuation induced particle transport was reduced and W{sub p} started the climbing phase. Therefore, the short period of the influence to the edge fluctuation might be an advantage of this novel fueling technique. On the other hand, although their roles are not identified at present, coherent MHD modes are also suppressed as well by the application of SMBI. These MHD modes are thought to be de-exited due to a sudden change of the edge density and/or excitation conditions.« less

Metal-doped organic foam and method of making same. [Patent application

DOEpatents

Rinde, J.A.

Organic foams having a low density and very small cell size and method for producing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

Method of making metal-doped organic foam products

DOEpatents

Rinde, James A.

1981-01-01

Organic foams having a low density and very small cell size and method for roducing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

Refractometric sensitivity and thermal stabilization of fluorescent core microcapillary sensors: theory and experiment.

PubMed

Lane, S; Marsiglio, F; Zhi, Y; Meldrum, A

2015-02-20

Fluorescent-core microcapillaries (FCMs) present a robust basis for the application of optical whispering gallery modes toward refractometric sensing. An important question concerns whether these devices can be rendered insensitive to local temperature fluctuations, which may otherwise limit their refractometric detection limits, mainly as a result of thermorefractive effects. Here, we first use a standard cylindrical cavity formalism to develop the refractometric and thermally limited detection limits for the FCM structure. We then measure the thermal response of a real device with different analytes in the channel and compare the result to the theory. Good stability against temperature fluctuations was obtained for an ethanol solvent, with a near-zero observed thermal shift for the transverse magnetic modes. Similarly good results could in principle be obtained for any other solvent (e.g., water), if the thickness of the fluorescent layer can be sufficiently well controlled.

Synthetic Microwave Imaging Reflectometry diagnostic using 3D FDTD Simulations

NASA Astrophysics Data System (ADS)

Kruger, Scott; Jenkins, Thomas; Smithe, David; King, Jacob; Nimrod Team Team

2017-10-01

Microwave Imaging Reflectometry (MIR) has become a standard diagnostic for understanding tokamak edge perturbations, including the edge harmonic oscillations in QH mode operation. These long-wavelength perturbations are larger than the normal turbulent fluctuation levels and thus normal analysis of synthetic signals become more difficult. To investigate, we construct a synthetic MIR diagnostic for exploring density fluctuation amplitudes in the tokamak plasma edge by using the three-dimensional, full-wave FDTD code Vorpal. The source microwave beam for the diagnostic is generated and refelected at the cutoff surface that is distorted by 2D density fluctuations in the edge plasma. Synthetic imaging optics at the detector can be used to understand the fluctuation and background density profiles. We apply the diagnostic to understand the fluctuations in edge plasma density during QH-mode activity in the DIII-D tokamak, as modeled by the NIMROD code. This work was funded under DOE Grant Number DE-FC02-08ER54972.

Comparison of polymer induced and solvent induced trypsin denaturation: the role of hydrophobicity.

PubMed

Jasti, Lakshmi S; Fadnavis, Nitin W; Addepally, Uma; Daniels, Siona; Deokar, Sarika; Ponrathnam, Surendra

2014-04-01

Trypsin adsorption from aqueous buffer by various copolymers of allyl glycidyl ether-ethylene glycol dimethacrylate (AGE-EGDM) copolymer with varying crosslink density increases with increasing crosslink density and the effect slowly wears off after reaching a plateau at 50% crosslink density. The copolymer with 25% crosslink density was reacted with different amines with alkyl/aryl side chains to obtain a series of copolymers with 1,2-amino alcohol functional groups and varying hydrophobicity. Trypsin binding capacity again increases with hydrophobicity of the reacting amine and a good correlation between logPoctanol of the amine and protein binding is observed. The bound trypsin is denatured to the extent of 90% in spite of the presence of hydrophilic hydroxyl and amino groups. The behavior was comparable to that in mixtures of aqueous buffer and water-miscible organic co-solvents where the solvent concentration required to deactivate 50% of the enzyme (C50) is dependent on logPoctanol of the co-solvent. Copyright © 2014 Elsevier B.V. All rights reserved.

Low density microcellular carbon foams and method of preparation

DOEpatents

Arnold, C. Jr.; Aubert, J.H.; Clough, R.L.; Rand, P.B.; Sylwester, A.P.

1988-06-20

A low density, open-celled microcellular carbon foam is disclosed which is prepared by dissolving a carbonizable polymer or copolymer in a solvent, pouring the solution into a mold, cooling the solution, removing the solvent, and then carbonizing the polymer or copolymer in a high temperature oven to produce the foam. If desired, an additive can be introduced in order to produce a doped carbon foam, and the foams can be made isotropic by selection of a suitable solvent. The low density, microcellular foams produced by this process are particularly useful in the fabrication of inertial confinement fusion targets, but can also be used as catalysts, absorbents, and electrodes.

Low density microcellular carbon foams and method of preparation

DOEpatents

Arnold, Jr., Charles; Aubert, James H.; Clough, Roger L.; Rand, Peter B.; Sylwester, Alan P.

1989-01-01

A low density, open-celled microcellular carbon foam is disclosed which is prepared by dissolving a carbonizable polymer or copolymer in a solvent, pouring the solution into a mold, cooling the solution, removing the solvent, and then carbonizing the polymer or copolymer in a high temperature oven to produce the foam. If desired, an additive can be introduced in order to produce a doped carbon foam, and the foams can be made isotropic by selection of a suitable solvent. The low density, microcellular foams produced by this process are particularly useful in the fabrication of inertial confinement fusion targets, but can also be used as catalysts, absorbents, and electrodes.

Weighted-density functionals for cavity formation and dispersion energies in continuum solvation models

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

Sundararaman, Ravishankar; Gunceler, Deniz; Arias, T. A.

2014-10-07

Continuum solvation models enable efficient first principles calculations of chemical reactions in solution, but require extensive parametrization and fitting for each solvent and class of solute systems. Here, we examine the assumptions of continuum solvation models in detail and replace empirical terms with physical models in order to construct a minimally-empirical solvation model. Specifically, we derive solvent radii from the nonlocal dielectric response of the solvent from ab initio calculations, construct a closed-form and parameter-free weighted-density approximation for the free energy of the cavity formation, and employ a pair-potential approximation for the dispersion energy. We show that the resulting modelmore » with a single solvent-independent parameter: the electron density threshold (n c), and a single solvent-dependent parameter: the dispersion scale factor (s 6), reproduces solvation energies of organic molecules in water, chloroform, and carbon tetrachloride with RMS errors of 1.1, 0.6 and 0.5 kcal/mol, respectively. We additionally show that fitting the solvent-dependent s 6 parameter to the solvation energy of a single non-polar molecule does not substantially increase these errors. Parametrization of this model for other solvents, therefore, requires minimal effort and is possible without extensive databases of experimental solvation free energies.« less

Weighted-density functionals for cavity formation and dispersion energies in continuum solvation models

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

Sundararaman, Ravishankar; Gunceler, Deniz; Arias, T. A.

2014-10-07

Continuum solvation models enable efficient first principles calculations of chemical reactions in solution, but require extensive parametrization and fitting for each solvent and class of solute systems. Here, we examine the assumptions of continuum solvation models in detail and replace empirical terms with physical models in order to construct a minimally-empirical solvation model. Specifically, we derive solvent radii from the nonlocal dielectric response of the solvent from ab initio calculations, construct a closed-form and parameter-free weighted-density approximation for the free energy of the cavity formation, and employ a pair-potential approximation for the dispersion energy. We show that the resulting modelmore » with a single solvent-independent parameter: the electron density threshold (n{sub c}), and a single solvent-dependent parameter: the dispersion scale factor (s{sub 6}), reproduces solvation energies of organic molecules in water, chloroform, and carbon tetrachloride with RMS errors of 1.1, 0.6 and 0.5 kcal/mol, respectively. We additionally show that fitting the solvent-dependent s{sub 6} parameter to the solvation energy of a single non-polar molecule does not substantially increase these errors. Parametrization of this model for other solvents, therefore, requires minimal effort and is possible without extensive databases of experimental solvation free energies.« less

Joint density-functional theory for energetics and spectroscopy in complex aqueous and nonaqueous solvents

NASA Astrophysics Data System (ADS)

Gunceler, Deniz

Solvents are of great importance in many technological applications, but are difficult to study using standard, off-the-shelf ab initio electronic structure methods. This is because a single configuration of molecular positions in the solvent (a "snapshot" of the fluid) is not necessarily representative of the thermodynamic average. To obtain any thermodynamic averages (e.g. free energies), the phase space of the solvent must be sampled, typically using molecular dynamics. This greatly increases the computational cost involved in studying solvated systems. Joint density-functional theory has made its mark by being a computationally efficient yet rigorous theory by which to study solvation. It replaces the need for thermodynamic sampling with an effective continuum description of the solvent environment that is in-principle exact, computationally efficient and intuitive (easier to interpret). It has been very successful in aqueous systems, with potential applications in (among others) energy materials discovery, catalysis and surface science. In this dissertation, we develop accurate and fast joint density functional theories for complex, non-aqueous solvent enviroments, including organic solvents and room temperature ionic liquids, as well as new methods for calculating electron excitation spectra in such systems. These theories are then applied to a range of physical problems, from dendrite formation in lithium-metal batteries to the optical spectra of solvated ions.

Solvent Reaction Field Potential inside an Uncharged Globular Protein: A Bridge between Implicit and Explicit Solvent Models?

PubMed Central

Baker, Nathan A.; McCammon, J. Andrew

2008-01-01

The solvent reaction field potential of an uncharged protein immersed in Simple Point Charge/Extended (SPC/E) explicit solvent was computed over a series of molecular dynamics trajectories, intotal 1560 ns of simulation time. A finite, positive potential of 13 to 24 kbTec−1 (where T = 300K), dependent on the geometry of the solvent-accessible surface, was observed inside the biomolecule. The primary contribution to this potential arose from a layer of positive charge density 1.0 Å from the solute surface, on average 0.008 ec/Å3, which we found to be the product of a highly ordered first solvation shell. Significant second solvation shell effects, including additional layers of charge density and a slight decrease in the short-range solvent-solvent interaction strength, were also observed. The impact of these findings on implicit solvent models was assessed by running similar explicit-solvent simulations on the fully charged protein system. When the energy due to the solvent reaction field in the uncharged system is accounted for, correlation between per-atom electrostatic energies for the explicit solvent model and a simple implicit (Poisson) calculation is 0.97, and correlation between per-atom energies for the explicit solvent model and a previously published, optimized Poisson model is 0.99. PMID:17949217

Solvent reaction field potential inside an uncharged globular protein: A bridge between implicit and explicit solvent models?

NASA Astrophysics Data System (ADS)

Cerutti, David S.; Baker, Nathan A.; McCammon, J. Andrew

2007-10-01

The solvent reaction field potential of an uncharged protein immersed in simple point charge/extended explicit solvent was computed over a series of molecular dynamics trajectories, in total 1560ns of simulation time. A finite, positive potential of 13-24 kbTec-1 (where T =300K), dependent on the geometry of the solvent-accessible surface, was observed inside the biomolecule. The primary contribution to this potential arose from a layer of positive charge density 1.0Å from the solute surface, on average 0.008ec/Å3, which we found to be the product of a highly ordered first solvation shell. Significant second solvation shell effects, including additional layers of charge density and a slight decrease in the short-range solvent-solvent interaction strength, were also observed. The impact of these findings on implicit solvent models was assessed by running similar explicit solvent simulations on the fully charged protein system. When the energy due to the solvent reaction field in the uncharged system is accounted for, correlation between per-atom electrostatic energies for the explicit solvent model and a simple implicit (Poisson) calculation is 0.97, and correlation between per-atom energies for the explicit solvent model and a previously published, optimized Poisson model is 0.99.

Quasi-linear theory of electron density and temperature fluctuations with application to MHD generators and MPD arc thrusters

NASA Technical Reports Server (NTRS)

Smith, M.

1972-01-01

Fluctuations in electron density and temperature coupled through Ohm's law are studied for an ionizable medium. The nonlinear effects are considered in the limit of a third order quasi-linear treatment. Equations are derived for the amplitude of the fluctuation. Conditions under which a steady state can exist in the presence of the fluctuation are examined and effective transport properties are determined. A comparison is made to previously considered second order theory. The effect of third order terms indicates the possibility of fluctuations existing in regions predicted stable by previous analysis.

Size-dependent error of the density functional theory ionization potential in vacuum and solution

DOE PAGES

Sosa Vazquez, Xochitl A.; Isborn, Christine M.

2015-12-22

Density functional theory is often the method of choice for modeling the energetics of large molecules and including explicit solvation effects. It is preferable to use a method that treats systems of different sizes and with different amounts of explicit solvent on equal footing. However, recent work suggests that approximate density functional theory has a size-dependent error in the computation of the ionization potential. We here investigate the lack of size-intensivity of the ionization potential computed with approximate density functionals in vacuum and solution. We show that local and semi-local approximations to exchange do not yield a constant ionization potentialmore » for an increasing number of identical isolated molecules in vacuum. Instead, as the number of molecules increases, the total energy required to ionize the system decreases. Rather surprisingly, we find that this is still the case in solution, whether using a polarizable continuum model or with explicit solvent that breaks the degeneracy of each solute, and we find that explicit solvent in the calculation can exacerbate the size-dependent delocalization error. We demonstrate that increasing the amount of exact exchange changes the character of the polarization of the solvent molecules; for small amounts of exact exchange the solvent molecules contribute a fraction of their electron density to the ionized electron, but for larger amounts of exact exchange they properly polarize in response to the cationic solute. As a result, in vacuum and explicit solvent, the ionization potential can be made size-intensive by optimally tuning a long-range corrected hybrid functional.« less

Size-dependent error of the density functional theory ionization potential in vacuum and solution

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

Sosa Vazquez, Xochitl A.; Isborn, Christine M., E-mail: cisborn@ucmerced.edu

2015-12-28

Density functional theory is often the method of choice for modeling the energetics of large molecules and including explicit solvation effects. It is preferable to use a method that treats systems of different sizes and with different amounts of explicit solvent on equal footing. However, recent work suggests that approximate density functional theory has a size-dependent error in the computation of the ionization potential. We here investigate the lack of size-intensivity of the ionization potential computed with approximate density functionals in vacuum and solution. We show that local and semi-local approximations to exchange do not yield a constant ionization potentialmore » for an increasing number of identical isolated molecules in vacuum. Instead, as the number of molecules increases, the total energy required to ionize the system decreases. Rather surprisingly, we find that this is still the case in solution, whether using a polarizable continuum model or with explicit solvent that breaks the degeneracy of each solute, and we find that explicit solvent in the calculation can exacerbate the size-dependent delocalization error. We demonstrate that increasing the amount of exact exchange changes the character of the polarization of the solvent molecules; for small amounts of exact exchange the solvent molecules contribute a fraction of their electron density to the ionized electron, but for larger amounts of exact exchange they properly polarize in response to the cationic solute. In vacuum and explicit solvent, the ionization potential can be made size-intensive by optimally tuning a long-range corrected hybrid functional.« less

Electrostatic and magnetic measurements of turbulence and transport in Extrap T2

NASA Astrophysics Data System (ADS)

Möller, Anders; Sallander, Eva

1999-10-01

Langmuir probe and magnetic pick-up coil measurements are used to study edge turbulence in the Extrap T2 reversed field pinch. Magnetic fluctuations resonant outside the toroidal field reversal surface are observed where previously only fluctuations in the spectra of potential and electron density and temperature have been measured. Results are presented which imply that these fluctuations are coupled to and also correlated to the internally resonant tearing mode fluctuations. Evidence of coupling between low-frequency (<100 kHz) and high-frequency fluctuations is also presented. The normalized floating potential fluctuations are seen to increase with the edge electron temperature. This causes an increase of the potential and density fluctuation driven transport with the temperature which is faster than linear. These results, in combination, are consistent with a picture where internally resonant fluctuations couple to edge fluctuations through radial heat conduction from the stochastic core to the edge.

Alfven resonance mode conversion in the Phaedrus-T current drive experiments: Modelling and density fluctuations measurements

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

Vukovic, M.; Harper, M.; Breun, R.

1995-12-31

Current drive experiments on the Phaedrus-T tokamak performed with a low field side two-strap fast wave antenna at frequencies below {omega}{sub cH} show loop volt drops of up to 30% with strap phasing (0, {pi}/2). RF induced density fluctuations in the plasma core have also been observed with a microwave reflectometer. It is believed that they are caused by kinetic Alfven waves generated by mode conversion of fast waves at the Alfven resonance. Correlation of the observed density fluctuations with the magnitude of the {Delta}V{sub loop} suggest that the {Delta}V{sub loop} is attributable to current drive/heating due to mode convertedmore » kinetic Alfven waves. The toroidal cold plasma wave code LION is used to model the Alfven resonance mode conversion surfaces in the experiments while the cylindrical hot plasma kinetic wave code ISMENE is used to model the behavior of kinetic Alfven waves at the Alfven resonance location. Initial results obtained from limited density, magnetic field, antenna phase, and impurity scans show good agreement between the RF induced density fluctuations and the predicted behavior of the kinetic Alfven waves. Detailed comparisons between the density fluctuations and the code predictions are presented.« less

A molecular Rayleigh scattering setup to measure density fluctuations in thermal boundary layers

NASA Astrophysics Data System (ADS)

Panda, J.

2016-12-01

A Rayleigh scattering-based density fluctuation measurement system was set up inside a low-speed wind tunnel of NASA Ames Research Center. The immediate goal was to study the thermal boundary layer on a heated flat plate. A large number of obstacles had to be overcome to set up the system, such as the removal of dust particles using air filters, the use of photoelectron counting electronics to measure low intensity light, an optical layout to minimize stray light contamination, the reduction in tunnel vibration, and an expanded calibration process to relate photoelectron arrival rate to air density close to the plate surface. To measure spectra of turbulent density fluctuations, a two-PMT cross-correlation system was used to minimize the shot noise floor. To validate the Rayleigh measurements, temperature fluctuations spectra were calculated from density spectra and then compared with temperature spectra measured with a cold-wire probe operated in constant current mode. The spectra from the downstream half of the plate were found to be in good agreement with cold-wire probe, whereas spectra from the leading edge differed. Various lessons learnt are discussed. It is believed that the present effort is the first measurement of density fluctuations spectra in a boundary layer flow.

Molecular Rayleigh Scattering Diagnostic for Dynamic Temperature, Velocity, and Density Measurements

NASA Technical Reports Server (NTRS)

Mielke, Amy R.; Elam, Kristie A.; Sung, Chi-Jen

2006-01-01

A molecular Rayleigh scattering technique is developed to measure dynamic gas temperature, velocity, and density in unseeded turbulent flows at sampling rates up to 16 kHz. A high power CW laser beam is focused at a point in an air jet plume and Rayleigh scattered light is collected and spectrally resolved. The spectrum of the light, which contains information about the temperature and velocity of the flow, is analyzed using a Fabry-Perot interferometer. The circular interference fringe pattern is divided into four concentric regions and sampled at 1 and 16 kHz using photon counting electronics. Monitoring the relative change in intensity within each region allows for measurement of gas temperature and velocity. Independently monitoring the total scattered light intensity provides a measure of gas density. A low speed heated jet is used to validate the measurement of temperature fluctuations and an acoustically excited nozzle flow is studied to validate velocity fluctuation measurements. Power spectral density calculations of the property fluctuations, as well as mean and fluctuating quantities are presented. Temperature fluctuation results are compared with constant current anemometry measurements and velocity fluctuation results are compared with constant temperature anemometry measurements at the same locations.

Microturbulence in HT-6M Tokamak

NASA Astrophysics Data System (ADS)

Zeng, Lei; Yu, Changxuan; Cao, Jinxiang; Zhu, Guoliang; Zhang, Daqing; Li, Youyi

1993-08-01

The small scale density fluctuations in the interior of HT-6M Ohmic plasma have been studied by CO2 laser collective scattering system in deuterium discharges covering a range of bar neqa (chord-average density times safety factor at the limiter) and energy confinement time. The relative density fluctuation level in the interior is inversely proportional to the toroidal magnetic field and average density, and the energy confinement time τE decreases with the fluctuation level increasing in the region where τE linearly increases with bar neqa and statisfies the Goldston scaling law. It is suggested that the microturbulence in the interior zone is responsible for anomalous transport in tokamaks.

Wearing surface testing and screening : Yukon River Bridge.

DOT National Transportation Integrated Search

2015-09-01

There is a demand and a need for cheaper and alternative surface coverings in environments with high temperature fluctuations. Our : design for an alternative surface covering involves a basic two-part component epoxy with the addition of a solvent. ...

Origin of density fluctuations in extended inflation

NASA Technical Reports Server (NTRS)

Kolb, Edward W.; Salopek, David S.; Turner, Michael S.

1990-01-01

The density fluctuations (both curvature and isocurvature) that arise due to quantum fluctuations in a simple model of extended inflation based upon the Jordan-Brans-Dicke theory are calculated. Curvature fluctuations arise due to quantum fluctuations in the Brans-Dicke field, in general have a nonscale-invariant spectrum, and can have an amplitude that is cosmologically acceptable and interesting without having to tune any coupling constant to a very small value. The density perturbations that arise due to the inflation field are subdominant. If there are other massless fields in the theory, e.g., an axion or an ilion, then isocurvature fluctuations arise in these fields too. Production of gravitational waves and the massless particles associated with excitations of the Brans-Dicke field are also discussed. Several attempts at more realistic models of extended inflation are also analyzed. The importance of the Einstein conformal frame in calculating curvature fluctuations is emphasized. When viewed in this frame, extended inflation closely resembles slow-rollover inflation with an exponential potential and the usual formula for the amplitude of curvature perturbations applies.

Universal calculational recipe for solvent-mediated potential: based on a combination of integral equation theory and density functional theory

NASA Astrophysics Data System (ADS)

Zhou, Shiqi

2004-07-01

A universal formalism, which enables calculation of solvent-mediated potential (SMP) between two equal or non-equal solute particles with any shape immersed in solvent reservior consisting of atomic particle and/or polymer chain or their mixture, is proposed by importing a density functional theory externally into OZ equation systems. Only if size asymmetry of the solvent bath components is moderate, the present formalism can calculate the SMP in any complex fluids at the present development stage of statistical mechanics, and therefore avoids all of limitations of previous approaches for SMP. Preliminary calculation indicates the reliability of the present formalism.

Dynamics of Large-Scale Fluctuations in Native Proteins.

NASA Astrophysics Data System (ADS)

Erman, Burak; Erkip, Albert

2003-03-01

The fluctuations of residues of proteins about their equilibrium configurations are analyzed by Langevin dynamics. Residue pairs that are within a given cutoff distance of each other are assumed to be connected by linear springs. The action of the solvent and intramolecular interactions on each residue are treated as random noise. The correlations of fluctuations resulting from the solution of the Langevin equation are observed to be identical to those obtained by the Gaussian Network Model based on equilibrium statistical mechanics. The time delayed correlations of fluctuations, and the response of the protein to a given frequency and to a window of frequencies are determined. The fluctuations of the residues resulting from a given fixed externally applied frequency are evaluated for different modes of the system. Synchronous and asynchronous components of correlations for different modes are formulated. The results of the present study are applied to study the fluctuation dynamics of the 241 residue protein S. marcescens endonuclease (1QL0).

Density Fluctuations in the Solar Wind Driven by Alfvén Wave Parametric Decay

NASA Astrophysics Data System (ADS)

Bowen, Trevor A.; Badman, Samuel; Hellinger, Petr; Bale, Stuart D.

2018-02-01

Measurements and simulations of inertial compressive turbulence in the solar wind are characterized by anti-correlated magnetic fluctuations parallel to the mean field and density structures. This signature has been interpreted as observational evidence for non-propagating pressure balanced structures, kinetic ion-acoustic waves, as well as the MHD slow-mode. Given the high damping rates of parallel propagating compressive fluctuations, their ubiquity in satellite observations is surprising and suggestive of a local driving process. One possible candidate for the generation of compressive fluctuations in the solar wind is the Alfvén wave parametric instability. Here, we test the parametric decay process as a source of compressive waves in the solar wind by comparing the collisionless damping rates of compressive fluctuations with growth rates of the parametric decay instability daughter waves. Our results suggest that generation of compressive waves through parametric decay is overdamped at 1 au, but that the presence of slow-mode-like density fluctuations is correlated with the parametric decay of Alfvén waves.

3DRISM-HI-D2MSA: an improved analytic theory to compute solvent structure around hydrophobic solutes with proper treatment of solute–solvent electrostatic interactions

NASA Astrophysics Data System (ADS)

Cao, Siqin; Zhu, Lizhe; Huang, Xuhui

2018-04-01

The 3D reference interaction site model (3DRISM) is a powerful tool to study the thermodynamic and structural properties of liquids. However, for hydrophobic solutes, the inhomogeneity of the solvent density around them poses a great challenge to the 3DRISM theory. To address this issue, we have previously introduced the hydrophobic-induced density inhomogeneity theory (HI) for purely hydrophobic solutes. To further consider the complex hydrophobic solutes containing partial charges, here we propose the D2MSA closure to incorporate the short-range and long-range interactions with the D2 closure and the mean spherical approximation, respectively. We demonstrate that our new theory can compute the solvent distributions around real hydrophobic solutes in water and complex organic solvents that agree well with the explicit solvent molecular dynamics simulations.

Absorption Spectra and Photoreactivity of p-Aminobenzophenone by Time-dependent Density Functional Theory

NASA Astrophysics Data System (ADS)

Cheng, Xue-mei; Huang, Yao; Ma, Jian-yi; Li, Xiang-yuan

2007-06-01

The absorption spectral properties of para-aminobenzophenone (p-ABP) were investigated in gas phase and in solution by time-dependent density functional theory. Calculations suggest that the singlet states vary greatly with the solvent polarities. In various polar solvents, including acetonitrile, methanol, ethanol, dimethyl sulfoxide, and dimethyl formamide, the excited S1 states with charge transfer character result from π → π* transitions. However, in nonpolar solvents, cyclohexane, and benzene, the S1 states are the result of n → π* transitions related to local excitation in the carbonyl group. The excited T1 states were calculated to have ππ* character in various solvents. From the variation of the calculated excited states, the band due to π → π* transition undergoes a redshift with an increase in solvent polarity, while the band due to n → π* transition undergoes a blueshift with an increase in solvent polarity. In addition, the triplet yields and the photoreactivities of p-ABP in various solvents are discussed.

A salient effect of density on the dynamics of nonaqueous electrolytes.

PubMed

Han, Sungho

2017-04-24

The mobility and solvation of lithium ions in electrolytes are crucial for the performance and safety of lithium ion batteries. It has been known that a single type of solvent cannot satisfy the requirements of both mobility and solvation simultaneously for electrolytes. Therefore, complex solvent mixtures have been used to optimize both properties. Here we present the effects of density on the dynamics and solvation of organic liquid electrolytes via extensive molecular dynamics simulations. Our study finds that a small variation in density can induce a significant effect on the mobility of electrolytes but does not influence the solvation structure of a lithium ion. It turns out that an adjustment of the density of electrolytes could provide a more effective way to enhance mobility than a control of the solvent mixture ratio of electrolytes. Our study reveals that the density change of electrolytes mainly affects the residence time of solvents in the first solvation shell of a lithium ion rather than the structural change of the solvation sheath. Finally, our results suggest an intriguing point for understanding and designing electrolytes of lithium ion batteries for better performance and safety.

A salient effect of density on the dynamics of nonaqueous electrolytes

NASA Astrophysics Data System (ADS)

Han, Sungho

2017-04-01

The mobility and solvation of lithium ions in electrolytes are crucial for the performance and safety of lithium ion batteries. It has been known that a single type of solvent cannot satisfy the requirements of both mobility and solvation simultaneously for electrolytes. Therefore, complex solvent mixtures have been used to optimize both properties. Here we present the effects of density on the dynamics and solvation of organic liquid electrolytes via extensive molecular dynamics simulations. Our study finds that a small variation in density can induce a significant effect on the mobility of electrolytes but does not influence the solvation structure of a lithium ion. It turns out that an adjustment of the density of electrolytes could provide a more effective way to enhance mobility than a control of the solvent mixture ratio of electrolytes. Our study reveals that the density change of electrolytes mainly affects the residence time of solvents in the first solvation shell of a lithium ion rather than the structural change of the solvation sheath. Finally, our results suggest an intriguing point for understanding and designing electrolytes of lithium ion batteries for better performance and safety.

Constraints for proton structure fluctuations from exclusive scattering

NASA Astrophysics Data System (ADS)

Mäntysaari, H.; Schenke, B.

2017-08-01

We constrain the average density profile of the proton and the amount of event-by-event fluctuations by simultaneously calculating the coherent and incoherent exclusive diffractive vector meson production cross section in deep inelastic scattering. Working within the Color Glass Condensate picture, we find that the gluonic density of the proton must have large geometric fluctuations in order to describe the experimentally measured large incoherent cross section.

Radiative transfer in scattering stochastic atmospheres

NASA Astrophysics Data System (ADS)

Silant'ev, N. A.; Alekseeva, G. A.; Novikov, V. V.

2017-12-01

Many stars, active galactic nuclei, accretion discs etc. are affected by the stochastic variations of temperature, turbulent gas motions, magnetic fields, number densities of atoms and dust grains. These stochastic variations influence on the extinction factors, Doppler widths of lines and so on. The presence of many reasons for fluctuations gives rise to Gaussian distribution of fluctuations. The usual models leave out of account the fluctuations. In many cases the consideration of fluctuations improves the coincidence of theoretical values with the observed data. The objective of this paper is the investigation of the influence of the number density fluctuations on the form of radiative transfer equations. We consider non-magnetized atmosphere in continuum.

Two Point Space-Time Correlation of Density Fluctuations Measured in High Velocity Free Jets

NASA Technical Reports Server (NTRS)

Panda, Jayanta

2006-01-01

Two-point space-time correlations of air density fluctuations in unheated, fully-expanded free jets at Mach numbers M(sub j) = 0.95, 1.4, and 1.8 were measured using a Rayleigh scattering based diagnostic technique. The molecular scattered light from two small probe volumes of 1.03 mm length was measured for a completely non-intrusive means of determining the turbulent density fluctuations. The time series of density fluctuations were analyzed to estimate the integral length scale L in a moving frame of reference and the convective Mach number M(sub c) at different narrow Strouhal frequency (St) bands. It was observed that M(sub c) and the normalized moving frame length scale L*St/D, where D is the jet diameter, increased with Strouhal frequency before leveling off at the highest resolved frequency. Significant differences were observed between data obtained from the lip shear layer and the centerline of the jet. The wave number frequency transform of the correlation data demonstrated progressive increase in the radiative part of turbulence fluctuations with increasing jet Mach number.

Initial solubility & density evaluation of Non-Aqueous system of amino acid salts for CO2 capture: potassium prolinate blended with ethanol and ethylene glycol

NASA Astrophysics Data System (ADS)

Murshid, Ghulam; Garg, Sahil

2018-05-01

Amine scrubbing is the state of the art technology for CO2 capture, and solvent selection can significantly reduce the capital and energy cost of the process. Higher energy requirement for aqueous amine based CO2 removal process is still a most important downside preventive its industrial deployment. Therefore, in this study, novel non-aqueous based amino acid salt system consisting of potassium prolinate, ethanol and ethylene glycol has been studied. This work presents initial CO2 solubility study and important physical properties i.e. density of the studied solvent system. Previous work showed that non-aqueous system of potassium prolinate and ethanol has good absorption rates and requires lower energy for solvent regeneration. However, during regeneration, solvent loss issues were found due to lower boiling point of the ethanol. Therefore, ethylene glycol was added into current studied system for enhancing the overall boiling point of the system. The good initial CO2 solubility and low density of studied solvent system offers several advantages as compared to conventional amine solutions.

Density functional theory of freezing of a system of highly elongated ellipsoidal oligomer solutions

NASA Astrophysics Data System (ADS)

Dwivedi, Shikha; Mishra, Pankaj

2017-05-01

We have used the density functional theory of freezing to study the liquid crystalline phase behavior of a system of highly elongated ellipsoidal conjugated oligomers dispersed in three different solvents namely chloroform, toluene and their equimolar mixture. The molecules are assumed to interact via solvent-implicit coarse-grained Gay-Berne potential. Pair correlation functions needed as input in the density functional theory have been calculated using the Percus-Yevick (PY) integral equation theory. Considering the isotropic and nematic phases, we have calculated the isotropic-nematic phase transition parameters and presented the temperature-density and pressure-temperature phase diagrams. Different solvent conditions are found not only to affect the transition parameters but also determine the capability of oligomers to form nematic phase in various thermodynamic conditions. In principle, our results are verifiable through computer simulations.

Effects of solvent density on retention in gas-liquid chromatography. I. Alkanes solutes in polyethylene glycol stationary phases.

PubMed

González, F R; Pérez-Parajón, J; García-Domínguez, J A

2002-04-12

Gas-liquid chromatographic columns were prepared coating silica capillaries with poly(oxyethylene) polymers of different molecular mass distributions, in the range of low number-average molar masses, where the density still varies significantly. A novel, high-temperature, rapid evaporation method was developed and applied to the static coating of the low-molecular-mass stationary phases. The analysis of alkanes retention data from these columns reveals that the dependence of the partition coefficient with the solvent macroscopic density is mainly due to a variation of entropy. Enthalpies of solute transfer contribute poorly to the observed variations of retention. Since the alkanes solubility diminishes with the increasing solvent density, and this variation is weakly dependent with temperature, it is concluded that the decrease of free-volume in the liquid is responsible for this behavior.

40 CFR 63.5749 - How do I calculate the organic HAP content of aluminum wipedown solvents?

Code of Federal Regulations, 2011 CFR

2011-07-01

... the past 12 months, liters. Dj= density of aluminum wipedown solvent j, kilograms per liter. Wj= mass fraction of organic HAP in aluminum wipedown solvent j. m = number of different aluminum surface coatings...

Fluctuations and intermittent poloidal transport in a simple toroidal plasma

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

Goud, T. S.; Ganesh, R.; Saxena, Y. C.

In a simple magnetized toroidal plasma, fluctuation induced poloidal flux is found to be significant in magnitude. The probability distribution function of the fluctuation induced poloidal flux is observed to be strongly non-Gaussian in nature; however, in some cases, the distribution shows good agreement with the analytical form [Carreras et al., Phys. Plasmas 3, 2664 (1996)], assuming a coupling between the near Gaussian density and poloidal velocity fluctuations. The observed non-Gaussian nature of the fluctuation induced poloidal flux and other plasma parameters such as density and fluctuating poloidal velocity in this device is due to intermittent and bursty nature ofmore » poloidal transport. In the simple magnetized torus used here, such an intermittent fluctuation induced poloidal flux is found to play a crucial role in generating the poloidal flow.« less

Super-resolution study of polymer mobility fluctuations near c*.

PubMed

King, John T; Yu, Changqian; Wilson, William L; Granick, Steve

2014-09-23

Nanoscale dynamic heterogeneities in synthetic polymer solutions are detected using super-resolution optical microscopy. To this end, we map concentration fluctuations in polystyrene-toluene solutions with spatial resolution below the diffraction limit, focusing on critical fluctuations near the polymer overlap concentration, c*. Two-photon super-resolution microscopy was adapted to be applicable in an organic solvent, and a home-built STED-FCS system with stimulated emission depletion (STED) was used to perform fluorescence correlation spectroscopy (FCS). The polystyrene serving as the tracer probe (670 kg mol(-1), radius of gyration RG ≈ 35 nm, end-labeled with a bodipy derivative chromophore) was dissolved in toluene at room temperature (good solvent) and mixed with matrix polystyrene (3,840 kg mol(-1), RG ≈ 97 nm, Mw/Mn = 1.04) whose concentration was varied from dilute to more than 10c*. Whereas for dilute solutions the intensity-intensity correlation function follows a single diffusion process, it splits starting at c* to imply an additional relaxation process provided that the experimental focal area does not greatly exceed the polymer blob size. We identify the slower mode as self-diffusion and the increasingly rapid mode as correlated segment fluctuations that reflect the cooperative diffusion coefficient, Dcoop. These real-space measurements find quantitative agreement between correlation lengths inferred from dynamic measurements and those from determining the limit below which diffusion coefficients are independent of spot size. This study is considered to illustrate the potential of importing into polymer science the techniques of super-resolution imaging.

Effective size of density-dependent two-sex populations: the effect of mating systems.

PubMed

Myhre, A M; Engen, S; SAEther, B-E

2017-08-01

Density dependence in vital rates is a key feature affecting temporal fluctuations of natural populations. This has important implications for the rate of random genetic drift. Mating systems also greatly affect effective population sizes, but knowledge of how mating system and density regulation interact to affect random genetic drift is poor. Using theoretical models and simulations, we compare N e in short-lived, density-dependent animal populations with different mating systems. We study the impact of a fluctuating, density-dependent sex ratio and consider both a stable and a fluctuating environment. We find a negative relationship between annual N e /N and adult population size N due to density dependence, suggesting that loss of genetic variation is reduced at small densities. The magnitude of this decrease was affected by mating system and life history. A male-biased, density-dependent sex ratio reduces the rate of genetic drift compared to an equal, density-independent sex ratio, but a stochastic change towards male bias reduces the N e /N ratio. Environmental stochasticity amplifies temporal fluctuations in population size and is thus vital to consider in estimation of effective population sizes over longer time periods. Our results on the reduced loss of genetic variation at small densities, particularly in polygamous populations, indicate that density regulation may facilitate adaptive evolution at small population sizes. © 2017 European Society For Evolutionary Biology. Journal of Evolutionary Biology © 2017 European Society For Evolutionary Biology.

Interplanetary Type III Bursts and Electron Density Fluctuations in the Solar Wind

NASA Astrophysics Data System (ADS)

Krupar, V.; Maksimovic, M.; Kontar, E. P.; Zaslavsky, A.; Santolik, O.; Soucek, J.; Kruparova, O.; Eastwood, J. P.; Szabo, A.

2018-04-01

Type III bursts are generated by fast electron beams originated from magnetic reconnection sites of solar flares. As propagation of radio waves in the interplanetary medium is strongly affected by random electron density fluctuations, type III bursts provide us with a unique diagnostic tool for solar wind remote plasma measurements. Here, we performed a statistical survey of 152 simple and isolated type III bursts observed by the twin-spacecraft Solar TErrestrial RElations Observatory mission. We investigated their time–frequency profiles in order to retrieve decay times as a function of frequency. Next, we performed Monte Carlo simulations to study the role of scattering due to random electron density fluctuations on time–frequency profiles of radio emissions generated in the interplanetary medium. For simplification, we assumed the presence of isotropic electron density fluctuations described by a power law with the Kolmogorov spectral index. Decay times obtained from observations and simulations were compared. We found that the characteristic exponential decay profile of type III bursts can be explained by the scattering of the fundamental component between the source and the observer despite restrictive assumptions included in the Monte Carlo simulation algorithm. Our results suggest that relative electron density fluctuations < δ {n}{{e}}> /{n}{{e}} in the solar wind are 0.06–0.07 over wide range of heliospheric distances.

DIFFUSED SOLUTE-SOLVENT INTERFACE WITH POISSON-BOLTZMANN ELECTROSTATICS: FREE-ENERGY VARIATION AND SHARP-INTERFACE LIMIT.

PubMed

Li, B O; Liu, Yuan

A phase-field free-energy functional for the solvation of charged molecules (e.g., proteins) in aqueous solvent (i.e., water or salted water) is constructed. The functional consists of the solute volumetric and solute-solvent interfacial energies, the solute-solvent van der Waals interaction energy, and the continuum electrostatic free energy described by the Poisson-Boltzmann theory. All these are expressed in terms of phase fields that, for low free-energy conformations, are close to one value in the solute phase and another in the solvent phase. A key property of the model is that the phase-field interpolation of dielectric coefficient has the vanishing derivative at both solute and solvent phases. The first variation of such an effective free-energy functional is derived. Matched asymptotic analysis is carried out for the resulting relaxation dynamics of the diffused solute-solvent interface. It is shown that the sharp-interface limit is exactly the variational implicit-solvent model that has successfully captured capillary evaporation in hydrophobic confinement and corresponding multiple equilibrium states of underlying biomolecular systems as found in experiment and molecular dynamics simulations. Our phase-field approach and analysis can be used to possibly couple the description of interfacial fluctuations for efficient numerical computations of biomolecular interactions.

High-Beta Electromagnetic Turbulence in LAPD Plasmas

NASA Astrophysics Data System (ADS)

Rossi, G.; Carter, T. A.; Pueschel, M. J.; Jenko, F.; Told, D.; Terry, P. W.

2015-11-01

The introduction of a new LaB6 cathode plasma source in the Large Plasma Device has enabled the study of pressure-gradient-driven turbulence and transport variations at significantly higher plasma β. Density fluctuations are observed to decrease with increasing β while magnetic fluctuations increase. Furthermore, the perpendicular magnetic fluctuations are seen to saturate while parallel (compressional) magnetic fluctuations increase continuously with β. These observations are compared to linear and nonlinear simulations with the GENE code. The results are consistent with the linear excitation of a Gradient-driven Drift Coupling mode (GDC) which relies on grad-B drift due to parallel magnetic fluctuations and can be driven by density or temperature gradients.

Method of altering the effective bulk density of solid material and the resulting product

DOEpatents

Kool, Lawrence B.; Nolen, Robert L.; Solomon, David E.

1983-01-01

A method of adjustably tailoring the effective bulk density of a solid material in which a mixture comprising the solid material, a film-forming polymer and a volatile solvent are sprayed into a drying chamber such that the solvent evaporates and the polymer dries into hollow shells having the solid material captured within the shell walls. Shell density may be varied as a function of solid/polymer concentration, droplet size and drying temperature.

Ion-mediated interactions in suspensions of oppositely charged nanoparticles

NASA Astrophysics Data System (ADS)

Dahirel, Vincent; Hansen, Jean Pierre

2009-08-01

The structure of oppositely charged spherical nanoparticles (polyions), dispersed in ionic solutions with continuous solvent (primitive model), is investigated by Monte Carlo (MC) simulations, within explicit and implicit microion representations, over a range of polyion valences and densities, and microion concentrations. Systems with explicit microions are explored by semigrand canonical MC simulations, and allow density-dependent effective polyion pair potentials vαβeff(r ) to be extracted from measured partial pair distribution functions. Implicit microion MC simulations are based on pair potentials of mean force vαβ(2)(r ) computed by explicit microion simulations of two charged polyions, in the low density limit. In the vicinity of the liquid-gas separation expected for oppositely charged polyions, the implicit microion representation leads to an instability against density fluctuations for polyion valences |Z| significantly below those at which the instability sets in within the exact explicit microion representation. Far from this instability region, the vαβ(2)(r ) are found to be fairly close to but consistently more repulsive than the effective pair potentials vαβeff(r ). This is corroborated by additional calculations of three-body forces between polyion triplets, which are repulsive when one polyion is of opposite charge to the other two. The explicit microion MC data were exploited to determine the ratio of salt concentrations c and co within the dispersion and the reservoir (Donnan effect). c /co is found to first increase before finally decreasing as a function of the polyion packing fraction.

Extended MHD modeling of tearing-driven magnetic relaxation

NASA Astrophysics Data System (ADS)

Sauppe, J. P.; Sovinec, C. R.

2017-05-01

Discrete relaxation events in reversed-field pinch relevant configurations are investigated numerically with nonlinear extended magnetohydrodynamic (MHD) modeling, including the Hall term in Ohm's law and first-order ion finite Larmor radius effects. Results show variability among relaxation events, where the Hall dynamo effect may help or impede the MHD dynamo effect in relaxing the parallel current density profile. The competitive behavior arises from multi-helicity conditions where the dominant magnetic fluctuation is relatively small. The resulting changes in parallel current density and parallel flow are aligned in the core, consistent with experimental observations. The analysis of simulation results also confirms that the force density from fluctuation-induced Reynolds stress arises subsequent to the drive from the fluctuation-induced Lorentz force density. Transport of the momentum density is found to be dominated by the fluctuation-induced Maxwell stress over most of the cross section with viscous and gyroviscous contributions being large in the edge region. The findings resolve a discrepancy with respect to the relative orientation of current density and flow relaxation, which had not been realized or investigated in King et al. [Phys. Plasmas 19, 055905 (2012)], where only the magnitude of flow relaxation is actually consistent with experimental results.

Environment of Submillimeter Galaxies

NASA Astrophysics Data System (ADS)

Hou, K.-c.; Chen, L.-w.

2013-10-01

To study the environment of high-redshift star-forming galaxies — submillimeter galaxies (SMGs) — and their role during large-scale structure formation, we have estimated the galaxy number density fluctuations around SMGs, and analyzed their cross correlation functions with Lyman alpha emitters (LAEs), and optical-selected galaxies with photometric redshift in the COSMOS and ECDFS fields. Only a marginal cross-correlation between SMGs and optical-selected galaxies at most redshifts intervals is found in our results, except a relatively strong correlation detected in the cases of AzTEC-detected SMGs with galaxies at z ˜2.6 and 3.6. The density fluctuations around SMGs with redshift estimated show most SMGs located in a high-density region. There is no correlation signal between LAEs and SMGs, and the galaxy density fluctuations indicate a slightly anti-correlation on a scale smaller than 2 Mpc. Furthermore, we also investigate the density fluctuations of passive and starforming galaxies selected by optical and near infrared colors at similar redshift around SMGs. Finally the implication from our results to the interconnection between high-redshift galaxy populations is discussed.

Intramolecular and intermolecular vibrational energy relaxation of CH 2I 2 dissolved in supercritical fluid

NASA Astrophysics Data System (ADS)

Sekiguchi, K.; Shimojima, A.; Kajimoto, O.

2002-04-01

A pump-probe experiment was performed to examine vibrational population relaxation of diiodomethane (CH 2I 2) molecule dissolved in supercritical CO 2. Using an apparatus with femtosecond time resolution, we observed the contributions of intramolecular vibrational energy redistribution (IVR) and intermolecular vibrational energy transfer (VET) separately. IVR and VET rates were measured with varying solvent densities at a constant temperature. It is shown that the IVR rate is not density dependent while the VET rate increases with increasing density from 0.4 to 0.8 g cm-3. This observation suggests that the rate of the VET process is determined by solute-solvent collisions whereas the IVR rate is not much affected by solute-solvent interaction.

Large-Scale Structure and Hyperuniformity of Amorphous Ices

NASA Astrophysics Data System (ADS)

Martelli, Fausto; Torquato, Salvatore; Giovambattista, Nicolas; Car, Roberto

2017-09-01

We investigate the large-scale structure of amorphous ices and transitions between their different forms by quantifying their large-scale density fluctuations. Specifically, we simulate the isothermal compression of low-density amorphous ice (LDA) and hexagonal ice to produce high-density amorphous ice (HDA). Both HDA and LDA are nearly hyperuniform; i.e., they are characterized by an anomalous suppression of large-scale density fluctuations. By contrast, in correspondence with the nonequilibrium phase transitions to HDA, the presence of structural heterogeneities strongly suppresses the hyperuniformity and the system becomes hyposurficial (devoid of "surface-area fluctuations"). Our investigation challenges the largely accepted "frozen-liquid" picture, which views glasses as structurally arrested liquids. Beyond implications for water, our findings enrich our understanding of pressure-induced structural transformations in glasses.

General framework for fluctuating dynamic density functional theory

NASA Astrophysics Data System (ADS)

Durán-Olivencia, Miguel A.; Yatsyshin, Peter; Goddard, Benjamin D.; Kalliadasis, Serafim

2017-12-01

We introduce a versatile bottom-up derivation of a formal theoretical framework to describe (passive) soft-matter systems out of equilibrium subject to fluctuations. We provide a unique connection between the constituent-particle dynamics of real systems and the time evolution equation of their measurable (coarse-grained) quantities, such as local density and velocity. The starting point is the full Hamiltonian description of a system of colloidal particles immersed in a fluid of identical bath particles. Then, we average out the bath via Zwanzig’s projection-operator techniques and obtain the stochastic Langevin equations governing the colloidal-particle dynamics. Introducing the appropriate definition of the local number and momentum density fields yields a generalisation of the Dean-Kawasaki (DK) model, which resembles the stochastic Navier-Stokes description of a fluid. Nevertheless, the DK equation still contains all the microscopic information and, for that reason, does not represent the dynamical law of observable quantities. We address this controversial feature of the DK description by carrying out a nonequilibrium ensemble average. Adopting a natural decomposition into local-equilibrium and nonequilibrium contribution, where the former is related to a generalised version of the canonical distribution, we finally obtain the fluctuating-hydrodynamic equation governing the time-evolution of the mesoscopic density and momentum fields. Along the way, we outline the connection between the ad hoc energy functional introduced in previous DK derivations and the free-energy functional from classical density-functional theory. The resultant equation has the structure of a dynamical density-functional theory (DDFT) with an additional fluctuating force coming from the random interactions with the bath. We show that our fluctuating DDFT formalism corresponds to a particular version of the fluctuating Navier-Stokes equations, originally derived by Landau and Lifshitz. Our framework thus provides the formal apparatus for ab initio derivations of fluctuating DDFT equations capable of describing the dynamics of soft-matter systems in and out of equilibrium.

Isocurvature fluctuations through axion trapping by cosmic string wakes

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

Layek, Biswanath

2005-03-15

We consider wakelike density fluctuations produced by cosmic strings at the quark-hadron transition in the early universe. We show that low momentum axions which are produced through the radiation from the axionic string at an earlier stage, may get trapped inside these wakes due to delayed hadronization in these overdense regions. As the interfaces, bordering the wakes, collapse, the axions pick-up momentum from the walls and finally leave the wake regions. These axions thus can produce large scale isocurvature fluctuations. We have calculated the detailed profile of these axionic density fluctuations and discuss its astrophysical consequences.

Electromotive force in strongly compressible magnetohydrodynamic turbulence

NASA Astrophysics Data System (ADS)

Yokoi, N.

2017-12-01

Variable density fluid turbulence is ubiquitous in geo-fluids, not to mention in astrophysics. Depending on the source of density variation, variable density fluid turbulence may be divided into two categories: the weak compressible (entropy mode) turbulence for slow flow and the strong compressible (acoustic mode) turbulence for fast flow. In the strong compressible turbulence, the pressure fluctuation induces a strong density fluctuation ρ ', which is represented by the density variance <ρ'2> (<·> denotes the ensemble average). The turbulent effect on the large-scale magnetic-field B induction is represented by the turbulent electromotive force (EMF) (u': velocity fluctuation, b': magnetic-field fluctuation). In the usual treatment in the dynamo theory, the expression for the EMF has been obtained in the framework of incompressible or weak compressible turbulence, where only the variation of the mean density <ρ>, if any, is taken into account. We see from the equation of the density fluctuation ρ', the density variance <ρ'2> is generated by the large mean density variation ∂<ρ> coupled with the turbulent mass flux <ρ'u'>. This means that in the region where the mean density steeply changes, the density variance effect becomes relevant for the magnetic field evolution. This situation is typically the case for phenomena associated with shocks and compositional discontinuities. With the aid of the analytical theory of inhomogeneous compressible magnetohydrodynamic (MHD) turbulence, the expression for the turbulent electromotive force is investigated. It is shown that, among others, an obliqueness (misalignment) between the mean density gradient ∂<ρ> and the mean magnetic field B may contribute to the EMF as ≈χ B×∂<ρ> with the turbulent transport coefficient χ proportional to the density variance (χ <ρ'2>). This density variance effect is expected to strongly affect the EMF near the interface, and changes the transport properties of turbulence. In the case of an interface under the MHD slow shock, the magnetic reconnection rate may be enhanced by this effect. Physical origin of this effect is discussed in some possible geophysical applications.

Direct 1H NMR evidence of spin-rotation coupling as a source of para → ortho-H2 conversion in diamagnetic solvents.

PubMed

Terenzi, Camilla; Bouguet-Bonnet, Sabine; Canet, Daniel

2017-04-21

At ambient temperature, conversion from 100% enriched para-hydrogen (p-H 2 ; singlet state) to ortho-hydrogen (o-H 2 ; triplet state) leads necessarily to the thermodynamic equilibrium proportions: 75% of o-H 2 and 25% of p-H 2 . When p-H 2 is dissolved in a diamagnetic organic solvent, conversion is very slow and can be considered as arising from nuclear spin relaxation phenomena. A first relaxation mechanism, specific to the singlet state and involving a combination of auto-correlation and cross correlation spectral densities, can be retained: randomly fluctuating magnetic fields due to inter-molecular dipolar interactions. We demonstrate here that (i) this dipolar mechanism is not sufficient for accounting for the para→ortho conversion rate, (ii) spin-rotation interaction, an intra-molecular mechanism, behaves similarly to random-field interaction and, thus, may be involved in the singlet relaxation rate. Also, as the para→ortho conversion is monitored by proton nuclear magnetic resonance (NMR) of dissolved o-H 2 (p-H 2 is NMR-silent), one has to account for H 2 exchange between the liquid phase and the gas phase within the NMR tube, as well as for dissolution effects. Experimental evidence of the above statements is brought here in the case of two organic solvents: acetone-d 6 and carbon disulfide. The observed temperature dependence of the para→ortho conversion rate shows that spin-rotation can be the dominant contribution to the p-H 2 relaxation rate in the absence of tangible dipolar interactions. Our findings shed new light on the "mysterious" mechanism of the para→ortho conversion which has been searched for several decades.

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

Cao, Siqin; Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon; Sheong, Fu Kit

Reference interaction site model (RISM) has recently become a popular approach in the study of thermodynamical and structural properties of the solvent around macromolecules. On the other hand, it was widely suggested that there exists water density depletion around large hydrophobic solutes (>1 nm), and this may pose a great challenge to the RISM theory. In this paper, we develop a new analytical theory, the Reference Interaction Site Model with Hydrophobicity induced density Inhomogeneity (RISM-HI), to compute solvent radial distribution function (RDF) around large hydrophobic solute in water as well as its mixture with other polyatomic organic solvents. To achievemore » this, we have explicitly considered the density inhomogeneity at the solute-solvent interface using the framework of the Yvon-Born-Green hierarchy, and the RISM theory is used to obtain the solute-solvent pair correlation. In order to efficiently solve the relevant equations while maintaining reasonable accuracy, we have also developed a new closure called the D2 closure. With this new theory, the solvent RDFs around a large hydrophobic particle in water and different water-acetonitrile mixtures could be computed, which agree well with the results of the molecular dynamics simulations. Furthermore, we show that our RISM-HI theory can also efficiently compute the solvation free energy of solute with a wide range of hydrophobicity in various water-acetonitrile solvent mixtures with a reasonable accuracy. We anticipate that our theory could be widely applied to compute the thermodynamic and structural properties for the solvation of hydrophobic solute.« less

High power fast wave experiments in LAPD: interaction with density fluctuations and status/plans for ICRH

NASA Astrophysics Data System (ADS)

Carter, Troy; Martin, Michael; van Compernolle, Bart; Gekelman, Walter; Pribyl, Pat; Vincena, Stephen; Tripathi, Shreekrishna; van Eester, Dirk; Crombe, Kristel

2016-10-01

The LArge Plasma Device (LAPD) at UCLA is a 17 m long, up to 60 cm diameter magnetized plasma column with typical plasma parameters ne 1012 -1013 cm-3, Te 1 - 10 eV, and B 1 kG. A new high-power ( 200 kW) RF system and antenna has been developed for LAPD, enabling the generation of large amplitude fast waves in LAPD. Interaction between the fast waves and density fluctuations is observed, resulting in modulation of the coupled RF power. Two classes of RF-induced density fluctuations are observed. First, a coherent (10 kHz) oscillation is observed spatially near the antenna in response to the initial RF turn-on transient. Second, broadband density fluctuations are enhanced when the RF power is above a threshold a threshold. Strong modulation of the fast wave magnetic fluctuations is observed along with broadening of the primary RF spectral line. Ultimately, high power fast waves will be used for ion heating in LAPD through minority species fundamental heating or second harmonic minority or majority heating. Initial experimental results from heating experiments will be presented along with a discussion of future plans. BaPSF supported by NSF and DOE.

INTERPRETATION OF THE STRUCTURE FUNCTION OF ROTATION MEASURE IN THE INTERSTELLAR MEDIUM

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

Xu, Siyao; Zhang, Bing, E-mail: syxu@pku.edu.cn, E-mail: zhang@physics.unlv.edu

2016-06-20

The observed structure function (SF) of rotation measure (RM) varies as a broken power-law function of angular scales. The systematic shallowness of its spectral slope is inconsistent with the standard Kolmogorov scaling. This motivates us to examine the statistical analysis on RM fluctuations. The correlations of RM constructed by Lazarian and Pogosyan are demonstrated to be adequate in explaining the observed features of RM SFs through a direct comparison between the theoretically obtained and observationally measured SF results. By segregating the density and magnetic field fluctuations and adopting arbitrary indices for their respective power spectra, we find that when themore » SFs of RM and emission measure have a similar form over the same range of angular scales, the statistics of the RM fluctuations reflect the properties of density fluctuations. RM SFs can be used to evaluate the mean magnetic field along the line of sight, but cannot serve as an informative source on the properties of turbulent magnetic field in the interstellar medium. We identify the spectral break of RM SFs as the inner scale of a shallow spectrum of electron density fluctuations, which characterizes the typical size of discrete electron density structures in the observed region.« less

Massive superclusters as a probe of the nature and amplitude of primordial density fluctuations

NASA Technical Reports Server (NTRS)

Kaiser, N.; Davis, M.

1985-01-01

It is pointed out that correlation studies of galaxy positions have been widely used in the search for information about the large-scale matter distribution. The study of rare condensations on large scales provides an approach to extend the existing knowledge of large-scale structure into the weakly clustered regime. Shane (1975) provides a description of several apparent massive condensations within the Shane-Wirtanen catalog, taking into account the Serpens-Virgo cloud and the Corona cloud. In the present study, a description is given of a model for estimating the frequency of condensations which evolve from initially Gaussian fluctuations. This model is applied to the Corona cloud to estimate its 'rareness' and thereby estimate the rms density contrast on this mass scale. An attempt is made to find a conflict between the density fluctuations derived from the Corona cloud and independent constraints. A comparison is conducted of the estimate and the density fluctuations predicted to arise in a universe dominated by cold dark matter.

Spherical harmonics analysis of surface density fluctuations of spherical ionic SDS and nonionic C12E8 micelles: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Yoshii, Noriyuki; Nimura, Yuki; Fujimoto, Kazushi; Okazaki, Susumu

2017-07-01

The surface structure and its fluctuation of spherical micelles were investigated using a series of density correlation functions newly defined by spherical harmonics and Legendre polynomials based on the molecular dynamics calculations. To investigate the influence of head-group charges on the micelle surface structure, ionic sodium dodecyl sulfate and nonionic octaethyleneglycol monododecylether (C12E8) micelles were investigated as model systems. Large-scale density fluctuations were observed for both micelles in the calculated surface static structure factor. The area compressibility of the micelle surface evaluated by the surface static structure factor was tens-of-times larger than a typical value of a lipid membrane surface. The structural relaxation time, which was evaluated from the surface intermediate scattering function, indicates that the relaxation mechanism of the long-range surface structure can be well described by the hydrostatic approximation. The density fluctuation on the two-dimensional micelle surface has similar characteristics to that of three-dimensional fluids near the critical point.

Spherical harmonics analysis of surface density fluctuations of spherical ionic SDS and nonionic C12E8 micelles: A molecular dynamics study.

PubMed

Yoshii, Noriyuki; Nimura, Yuki; Fujimoto, Kazushi; Okazaki, Susumu

2017-07-21

The surface structure and its fluctuation of spherical micelles were investigated using a series of density correlation functions newly defined by spherical harmonics and Legendre polynomials based on the molecular dynamics calculations. To investigate the influence of head-group charges on the micelle surface structure, ionic sodium dodecyl sulfate and nonionic octaethyleneglycol monododecylether (C 12 E 8 ) micelles were investigated as model systems. Large-scale density fluctuations were observed for both micelles in the calculated surface static structure factor. The area compressibility of the micelle surface evaluated by the surface static structure factor was tens-of-times larger than a typical value of a lipid membrane surface. The structural relaxation time, which was evaluated from the surface intermediate scattering function, indicates that the relaxation mechanism of the long-range surface structure can be well described by the hydrostatic approximation. The density fluctuation on the two-dimensional micelle surface has similar characteristics to that of three-dimensional fluids near the critical point.

Quasi-Lagrangian measurements of density surface fluctuations and power spectra in the stratosphere

NASA Technical Reports Server (NTRS)

Quinn, Elizabeth P.; Holzworth, Robert H.

1987-01-01

Pressure and temperature data from eight superpressure balloon flights at 26 km in the southern hemisphere stratosphere are analyzed. The balloons, which float on a constant density surface, travel steadily westward during summer and eastward during winter, as expected from local climatology. Two types of fluctuations are observed: neutral buoyancy oscillations (NBO) of around 4 min, and 0.1- to 1-hour oscillations that are characterized as small-amplitude density surface fluctuations. Lapse rates and densities are calculated and found to agree well with the expected values. Examples of wave damping and simultaneous fluctuation at two nearby balloons are presented. Spectral analysis is performed clearly showing the NBO and that the majority of the power is in the mesoscale range. Spectral slopes of power versus frequency are measured to be on the average -2.18 + or - 0.24 for pressure and -1.72 + or - 0.24 for temperature. These slopes are compared to the predictions of turbulence theories and the theory of a universal gravity wave spectrum.

Edge resonant fluctuations and particle transport in a reversed-field pinch

NASA Astrophysics Data System (ADS)

Möller, A.

1998-12-01

Electrostatic fluctuations are measured in the Extrap T2 reversed-field pinch [J. R. Drake et al., in Plasma Physics and Controlled Nuclear Fusion Research 1996 (International Atomic Energy Agency, Vienna, 1997), Vol. 2, pp. 193-199] using a Langmuir probe array. The electrostatic fluctuation, driven particle transport ΓnΦ is derived and found to constitute a large fraction of the total particle transport. The spectral density of all measured quantities exhibits a peak in the frequency range 100-250 kHz, which originates from fluctuations that are resonant close to the edge [n=-(40-80)]. This peak contains only about 10-20% of the total fluctuation power, but is shown to dominate ΓnΦ. The main reason for this is the high toroidal mode number as compared with internally resonant magnetohydrodynamic fluctuations. The edge resonant fluctuations also features a higher coherence (γ=0.5) and close to 90° phase shift between density and potential fluctuations.

Dynamic Responses in a Plant-Insect System to Fertilization by Cormorant Feces

PubMed Central

Kolb, Gundula; Hambäck, Peter A.

2015-01-01

Theoretical arguments suggest that increased plant productivity may not only increase consumer densities but also their fluctuations. While increased consumer densities are commonly observed in fertilization experiments, experiments are seldom performed at a spatial and temporal scale where effects on population fluctuations may be observed. In this study we used a natural gradient in soil fertility caused by cormorant nesting. Cormorants feed on fish but defecate on their nesting islands. On these islands we studied soil nutrient availability, plant nutrient content and the density of Galerucella beetles, main herbivores feeding on Lythrum salicaria. In a common garden experiment, we followed larval development on fertilized plants and estimated larval stoichiometry. Soil nutrient availability varied among islands, and several cormorant islands had very high N and P soil content. Plant nutrient content, however, did not vary among islands, and there was no correlation between soil and plant nutrient contents. Beetle densities increased with plant nutrient content in the field study. However, there was either no effect on temporal fluctuations in beetle density or that temporal fluctuations decreased (at high P). In the common garden experiment, we found limited responses in either larval survival or pupal weights to fertilization. A possible mechanism for the limited effect of fertilization on density fluctuations may be that the distribution of L. salicaria on nesting islands was restricted to sites with a lower N and P content, presumably because high N loads are toxic. PMID:26463193

Experimental study of a free turbulent shear flow at Mach 19 with electron-beam and conventional probes. [flow measurement

NASA Technical Reports Server (NTRS)

Harvey, W. P.; Hunter, W. D., Jr.

1975-01-01

An experimental study of the initial development region of a hypersonic turbulent free mixing layer was made. Data were obtained at three stations downstream of a M = 19 nozzle over a Reynolds range of 1.3 million to 3.3 million per meter and at a total temperature of about 1670 K. In general, good agreement was obtained between electron-beam and conventional probe measurements of local mean flow parameters. Measurements of fluctuating density indicated that peak root-mean-square (rms) levels are higher in the turbulent free mixing layer than in boundary layers for Mach numbers less than 9. The intensity of rms density fluctuations in the free stream is similar in magnitude to pressure fluctuations in high Mach number flows. Spectrum analyses of the measured fluctuating density through the shear layer indicate significant fluctuation energy at the lower frequencies (0.2 to 5 kHZ) which correspond to large-scale disturbances in the high-velocity region of the shear layer.

Electric Field Fluctuations in Water

NASA Astrophysics Data System (ADS)

Thorpe, Dayton; Limmer, David; Chandler, David

2013-03-01

Charge transfer in solution, such as autoionization and ion pair dissociation in water, is governed by rare electric field fluctuations of the solvent. Knowing the statistics of such fluctuations can help explain the dynamics of these rare events. Trajectories short enough to be tractable by computer simulation are virtually certain not to sample the large fluctuations that promote rare events. Here, we employ importance sampling techniques with classical molecular dynamics simulations of liquid water to study statistics of electric field fluctuations far from their means. We find that the distributions of electric fields located on individual water molecules are not in general gaussian. Near the mean this non-gaussianity is due to the internal charge distribution of the water molecule. Further from the mean, however, there is a previously unreported Bjerrum-like defect that stabilizes certain large fluctuations out of equilibrium. As expected, differences in electric fields acting between molecules are gaussian to a remarkable degree. By studying these differences, though, we are able to determine what configurations result not only in large electric fields, but also in electric fields with long spatial correlations that may be needed to promote charge separation.

Proton transfer in a short hydrogen bond caused by solvation shell fluctuations: an ab initio MD and NMR/UV study of an (OHO)(-) bonded system.

PubMed

Pylaeva, Svetlana; Allolio, Christoph; Koeppe, Benjamin; Denisov, Gleb S; Limbach, Hans-Heinrich; Sebastiani, Daniel; Tolstoy, Peter M

2015-02-14

We present a joint experimental and quantum chemical study on the influence of solvent dynamics on the protonation equilibrium in a strongly hydrogen bonded phenol-acetate complex in CD2Cl2. Particular attention is given to the correlation of the proton position distribution with the internal conformation of the complex itself and with fluctuations of the aprotic solvent. Specifically, we have focused on a complex formed by 4-nitrophenol and tetraalkylammonium-acetate in CD2Cl2. Experimentally we have used combined low-temperature (1)H and (13)C NMR and UV-vis spectroscopy and showed that a very strong OHO hydrogen bond is formed with proton tautomerism (PhOH···(-)OAc and PhO(-)···HOAc forms, both strongly hydrogen bonded). Computationally, we have employed ab initio molecular dynamics (70 and 71 solvent molecules, with and without the presence of a counter-cation, respectively). We demonstrate that the relative motion of the counter-cation and the "free" carbonyl group of the acid plays the major role in the OHO bond geometry and causes proton "jumps", i.e. interconversion of PhOH···(-)OAc and PhO(-)···HOAc tautomers. Weak H-bonds between CH(CD) groups of the solvent and the oxygen atom of carbonyl stabilize the PhOH···(-)OAc type of structures. Breaking of CH···O bonds shifts the equilibrium towards PhO(-)···HOAc form.

Homogeneous buoyancy-generated turbulence

NASA Technical Reports Server (NTRS)

Batchelor, G. K.; Canuto, V. M.; Chasnov, J. R.

1992-01-01

Using a theoretical analysis of fundamental equations and a numerical simulation of the flow field, the statistically homogeneous motion that is generated by buoyancy forces after the creation of homogeneous random fluctuations in the density of infinite fluid at an initial instant is examined. It is shown that analytical results together with numerical results provide a comprehensive description of the 'birth, life, and death' of buoyancy-generated turbulence. Results of numerical simulations yielded the mean-square density mean-square velocity fluctuations and the associated spectra as functions of time for various initial conditions, and the time required for the mean-square density fluctuation to fall to a specified small value was estimated.

Microwave beam broadening due to turbulent plasma density fluctuations within the limit of the Born approximation and beyond

NASA Astrophysics Data System (ADS)

Köhn, A.; Guidi, L.; Holzhauer, E.; Maj, O.; Poli, E.; Snicker, A.; Weber, H.

2018-07-01

Plasma turbulence, and edge density fluctuations in particular, can under certain conditions broaden the cross-section of injected microwave beams significantly. This can be a severe problem for applications relying on well-localized deposition of the microwave power, like the control of MHD instabilities. Here we investigate this broadening mechanism as a function of fluctuation level, background density and propagation length in a fusion-relevant scenario using two numerical codes, the full-wave code IPF-FDMC and the novel wave kinetic equation solver WKBeam. The latter treats the effects of fluctuations using a statistical approach, based on an iterative solution of the scattering problem (Born approximation). The full-wave simulations are used to benchmark this approach. The Born approximation is shown to be valid over a large parameter range, including ITER-relevant scenarios.

Local fluctuations of the signed traded volumes and the dependencies of demands: a copula analysis

NASA Astrophysics Data System (ADS)

Wang, Shanshan; Guhr, Thomas

2018-03-01

We investigate how the local fluctuations of the signed traded volumes affect the dependence of demands between stocks. We analyze the empirical dependence of demands using copulas and show that they are well described by a bivariate K copula density function. We find that large local fluctuations strongly increase the positive dependence but lower slightly the negative one in the copula density. This interesting feature is due to cross-correlations of volume imbalances between stocks. Also, we explore the asymmetries of tail dependencies of the copula density, which are moderate for the negative dependencies but strong for the positive ones. For the latter, we reveal that large local fluctuations of the signed traded volumes trigger stronger dependencies of demands than of supplies, probably indicating a bull market with persistent raising of prices.

Solvent evaporation induced graphene powder with high volumetric capacitance and outstanding rate capability for supercapacitors

NASA Astrophysics Data System (ADS)

Zhang, Xiaozhe; Raj, Devaraj Vasanth; Zhou, Xufeng; Liu, Zhaoping

2018-04-01

Graphene-based electrode materials for supercapacitors usually suffer from poor volumetric performance due to the low density. The enhancement of volumetric capacitance by densification of graphene materials, however, is usually accompanied by deterioration of rate capability, as the huge contraction of pore size hinders rapid diffusion of electrolytes. Thus, it is important to develop suitable pore size in graphene materials, which can sustain fast ion diffusion and avoid excessive voids to acquire high density simultaneously for supercapacitor applications. Accordingly, we propose a simple solvent evaporation method to control the pore size of graphene powders by adjusting the surface tension of solvents. Ethanol is used instead of water to reduce the shrinkage degree of graphene powder during solvent evaporation process, due to its lower surface tension comparing with water. Followed by the assistance of mechanical compression, graphene powder having high compaction density of 1.30 g cm-3 and a large proportion of mesopores in the pore size range of 2-30 nm is obtained, which delivers high volumetric capacitance of 162 F cm-3 and exhibits outstanding rate performance of 76% capacity retention at a high current density of 100 A g-1 simultaneously.

Seahorse (Hippocampinae) population fluctuations in the Ria Formosa Lagoon, south Portugal.

PubMed

Correia, M; Caldwell, I R; Koldewey, H J; Andrade, J P; Palma, J

2015-09-01

Comparisons of three sets of surveys in the Ria Formosa Lagoon, Portugal, over a 13 year period (2001-2002, 2008-2009 and 2010-2013) revealed significant population fluctuations in at least one of the two seahorse (Hippocampinae) species living there, and that those fluctuations were potentially associated with habitat changes in the lagoon. After a significant decline between the first two survey periods (2001-2002 v. 2008-2009), long-snouted seahorse Hippocampus guttulatus populations increased significantly between 2008-2009 surveys and new 2010-2013 surveys. There were no significant differences in H. guttulatus populations between the 2001-2002 and 2010-2013 surveys. In contrast, there were no significant differences in short-snouted seahorse Hippocampus hippocampus densities among the 16 sites surveyed throughout the three sampling periods, although the ability to detect any change was hampered by the low densities of this species in all time periods. Fluctuations in H. guttulatus densities were positively correlated with the percentage of holdfast coverage, but with none of the other environmental variables tested. These results highlight the importance of holdfast availability in maintaining stable seahorse populations. While population fluctuations are certainly more promising than a consistent downward decline, such extreme fluctuations observed for seahorses in the Ria Formosa Lagoon could still leave these two species vulnerable to any additional stressors, particularly during low density periods. © 2015 The Fisheries Society of the British Isles.

Density fluctuations from strings and galaxy formation

NASA Technical Reports Server (NTRS)

Vilenkin, A.; Shafi, Q.

1983-01-01

The spectra of density fluctuations caused by strings in a universe dominated either by baryons, neutrinos, or axions are presented. Realistic scenarios for galaxy formation seem possible in all three cases. Examples of grand unified theories which lead to strings with the desired mass scales are given.

Advanced separators based on aromatic polymer for high energy density lithium batteries

DOEpatents

Zhang, Zhengcheng; Woo, Jung-Je; Amine, Khalil

2017-03-21

A process includes casting a solution including poly(phenylene oxide), inorganic nanoparticles, a solvent, and a non-solvent on a substrate; and removing the solvent to form a porous film; wherein: the porous film is configured for use as a porous separator for a lithium ion battery.

New detection system and signal processing for the tokamak ISTTOK heavy ion beam diagnostic.

PubMed

Henriques, R B; Nedzelskiy, I S; Malaquias, A; Fernandes, H

2012-10-01

The tokamak ISTTOK havy ion beam diagnostic (HIBD) operates with a multiple cell array detector (MCAD) that allows for the plasma density and the plasma density fluctuations measurements simultaneously at different sampling volumes across the plasma. To improve the capability of the plasma density fluctuations investigations, a new detection system and new signal conditioning amplifier have been designed and tested. The improvements in MCAD design are presented which allow for nearly complete suppression of the spurious plasma background signal by applying a biasing potential onto special electrodes incorporated into MCAD. The new low cost and small size transimpedance amplifiers are described with the parameters of 400 kHz, 10(7) V/A, 0.4 nA of RMS noise, adequate for the plasma density fluctuations measurements.

Fluctuation-Noise Model for PEM Fuel Cell

NASA Astrophysics Data System (ADS)

Denisov, E. S.; Salakhova, A. Sh.; Adiutantov, N. A.; Evdokimov, Yu. K.

2017-08-01

The fluctuation-noise model is presented. This model allows to describe the power spectral density of PEM fuel cell electrical fluctuation. The proposed model can be used for diagnostics of PEM fuel cell state of health.

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

Mukherji, Debashish; Stuehn, Torsten; Kremer, Kurt

Smart polymers are a modern class of polymeric materials that often exhibit unpredictable behavior in mixtures of solvents. One such phenomenon is co-non-solvency. Co-non-solvency occurs when two (perfectly) miscible and competing good solvents, for a given polymer, are mixed together. As a result, the same polymer collapses into a compact globule within intermediate mixing ratios. More interestingly, polymer collapses when the solvent quality remains good and even gets increasingly better by the addition of the better cosolvent. This is a puzzling phenomenon that is driven by strong local concentration fluctuations. Because of the discrete particle based nature of the interactions,more » Flory-Huggins type mean field arguments become unsuitable. In this work, we extend the analysis of the co-non-solvency effect presented earlier [D. Mukherji et al., Nat. Commun. 5, 4882 (2014)]. We explain why co-non-solvency is a generic phenomenon, which can only be understood by the thermodynamic treatment of the competitive displacement of (co)solvent components. This competition can result in a polymer collapse upon improvement of the solvent quality. Specific chemical details are not required to understand these complex conformational transitions. Therefore, a broad range of polymers are expected to exhibit similar reentrant coil-globule-coil transitions in competing good solvents.« less

Measurement of Initial Conditions at Nozzle Exit of High Speed Jets

NASA Technical Reports Server (NTRS)

Panda, J.; Zaman, K. B. M. Q.; Seasholtz, R. G.

2004-01-01

The time averaged and unsteady density fields close to the nozzle exit (0.1 less than or = x/D less than or = 2, x: downstream distance, D: jet diameter) of unheated free jets at Mach numbers of 0.95, 1.4, and 1.8 were measured using a molecular Rayleigh scattering based technique. The initial thickness of shear layer and its linear growth rate were determined from time-averaged density survey and a modeling process, which utilized the Crocco-Busemann equation to relate density profiles to velocity profiles. The model also corrected for the smearing effect caused by a relatively long probe length in the measured density data. The calculated shear layer thickness was further verified from a limited hot-wire measurement. Density fluctuations spectra, measured using a two-Photomultiplier-tube technique, were used to determine evolution of turbulent fluctuations in various Strouhal frequency bands. For this purpose spectra were obtained from a large number of points inside the flow; and at every axial station spectral data from all radial positions were integrated. The radially-integrated fluctuation data show an exponential growth with downstream distance and an eventual saturation in all Strouhal frequency bands. The initial level of density fluctuations was calculated by extrapolation to nozzle exit.

Large-scale structure of randomly jammed spheres

NASA Astrophysics Data System (ADS)

Ikeda, Atsushi; Berthier, Ludovic; Parisi, Giorgio

2017-05-01

We numerically analyze the density field of three-dimensional randomly jammed packings of monodisperse soft frictionless spherical particles, paying special attention to fluctuations occurring at large length scales. We study in detail the two-point static structure factor at low wave vectors in Fourier space. We also analyze the nature of the density field in real space by studying the large-distance behavior of the two-point pair correlation function, of density fluctuations in subsystems of increasing sizes, and of the direct correlation function. We show that such real space analysis can be greatly improved by introducing a coarse-grained density field to disentangle genuine large-scale correlations from purely local effects. Our results confirm that both Fourier and real space signatures of vanishing density fluctuations at large scale are absent, indicating that randomly jammed packings are not hyperuniform. In addition, we establish that the pair correlation function displays a surprisingly complex structure at large distances, which is however not compatible with the long-range negative correlation of hyperuniform systems but fully compatible with an analytic form for the structure factor. This implies that the direct correlation function is short ranged, as we also demonstrate directly. Our results reveal that density fluctuations in jammed packings do not follow the behavior expected for random hyperuniform materials, but display instead a more complex behavior.

Electromagnetic turbulence and transport in increased β LAPD Plasmas

NASA Astrophysics Data System (ADS)

Rossi, Giovanni; Carter, Troy; Pueschel, Mj; Jenko, Frank; Terry, Paul; Told, Daniel

2016-10-01

The new LaB6 plasma source in LAPD has enabled the production of magnetized, increased β plasmas (up to 15%). We report on the modifications of pressure-gradient-driven turbulence and transport with increased plasma β. Density fluctuations decrease with increasing β while magnetic fluctuations increase. B ⊥ fluctuations saturate while parallel (compressional) magnetic fluctuations increase continuously with β. At the highest β values Î δ ||/ δ B ⊥ 2 and δ B/B 1%. The measurements are consistent with the excitation of the Gradient-driven Drift Coupling (GDC). This instability prefers k|| = 0 and grows in finite β plasmas due to density and temperature gradients through the production of parallel magnetic field fluctuations and resulting ⊥ B|| drifts. Comparisons between experimental measurements and theoretical predictions for the GDC will be shown. Direct measurements of electrostatic particle flux have been performed and show a strong reduction with increasing β. No evidence is found (e.g. density profile shape) of enhanced confinement, suggesting that other transport mechanisms are active. Preliminary measurements indicate that electromagnetic transport due to parallel magnetic field fluctuations at first increases with β but is subsequently suppressed at higher β values.

Low Density ITB Studies Using the Upgraded C-Mod Reflectometry System

NASA Astrophysics Data System (ADS)

Dominguez, A.; Edlund, E.; Fiore, C. L.; Lin, L.; Marmar, E. S.; Snipes, J. A.; Porkolab, M.; Kramer, G. J.; Rowan, W. L.

2007-11-01

The Alcator C-Mod reflectometry system was recently upgraded in two ways: The low frequency channels were changed from amplitude modulation - in which two microwave signals, slightly separated in frequency, are injected into the plasma - to baseband, where a single frequency is used, in order to improve density fluctuation measurements. The second change, a variable frequency channel operating over the range from 122GHz to 140GHz (with corresponding density cutoffs of 1.84-2.43x10^20m-3) has been installed in collaboration with PPPL. Initial results from the upgraded system are presented, including the study of low density Internal Transport Barriers. Using O-mode waves, the reflectometry system is able to radially localize density fluctuations on the low field side along the tokamak midplane. It can, therefore, be used to probe the foot of low density ITBs. The corresponding reflectometry data will be compared to those of other fluctuation diagnostics, including Phase Contrast Imaging and magnetic pick-up coils.

Development of multicomponent hybrid density functional theory with polarizable continuum model for the analysis of nuclear quantum effect and solvent effect on NMR chemical shift.

PubMed

Kanematsu, Yusuke; Tachikawa, Masanori

2014-04-28

We have developed the multicomponent hybrid density functional theory [MC_(HF+DFT)] method with polarizable continuum model (PCM) for the analysis of molecular properties including both nuclear quantum effect and solvent effect. The chemical shifts and H/D isotope shifts of the picolinic acid N-oxide (PANO) molecule in chloroform and acetonitrile solvents are applied by B3LYP electron exchange-correlation functional for our MC_(HF+DFT) method with PCM (MC_B3LYP/PCM). Our MC_B3LYP/PCM results for PANO are in reasonable agreement with the corresponding experimental chemical shifts and isotope shifts. We further investigated the applicability of our method for acetylacetone in several solvents.

Observation of the electron density fluctuations by using the O-mode Microwave Imaging Reflectometry in LHD

NASA Astrophysics Data System (ADS)

Nagayama, Yoshio; Yamaguchi, Soichiro; Tsuchiya, Hayato; Kuwahara, Daisuke; LHD Experimental Team

2016-10-01

Visualization of local electron density fluctuations will be very useful to study the physics of confinement and instabilities in fusion plasma. In the Large Helical Device (LHD), the O-mode microwave imaging reflectometry (O-MIR) has been intensively developed in order to visualize the electron density fluctuations. The frequency is 26 - 34 GHz. This corresponds to the electron density of 0.8 - 1.5 × 1019 m-3. The plasma is illuminated by the Gaussian beam with four frequencies. The imaging optics make a plasma image onto the newly developed 2D (8 × 8) Horn-antenna Millimeter-wave Imaging Device (HMID). In HMID, the signal wave that is accumulated by the horn antenna is transduced to the micro-strip line by using the finline transducer. The signal wave is mixed by the double balanced mixer with the local wave that is delivered by cables. By using O-MIR, electron density fluctuations are measured at the H-mode edge and the ITB layer in LHD. This work is supported by NIFS/NINS under the project of Formation of International Scientific Base and Network, by the NIFS LHD project, by KAKENHI, and by IMS.

Density-Gradient-Driven trapped-electron-modes in improved-confinement RFP plasmas

NASA Astrophysics Data System (ADS)

Duff, James

2016-10-01

Short wavelength density fluctuations in improved-confinement MST plasmas exhibit multiple features characteristic of the trapped-electron-mode (TEM), strong evidence that drift wave turbulence emerges in RFP plasmas when transport associated with MHD tearing is reduced. Core transport in the RFP is normally governed by magnetic stochasticity stemming from long wavelength tearing modes that arise from current profile peaking. Using inductive control, the tearing modes are reduced and global confinement is increased to values expected for a comparable tokamak plasma. The improved confinement is associated with a large increase in the pressure gradient that can destabilize drift waves. The measured density fluctuations have frequencies >50 kHz, wavenumbers k_phi*rho_s<0.14, and propagate in the electron drift direction. Their spectral emergence coincides with a sharp decrease in fluctuations associated with global tearing modes. Their amplitude increases with the local density gradient, and they exhibit a density-gradient threshold at R/L_n 15, higher than in tokamak plasmas by R/a. the GENE code, modified for RFP equilibria, predicts the onset of microinstability for these strong-gradient plasma conditions. The density-gradient-driven TEM is the dominant instability in the region where the measured density fluctuations are largest, and the experimental threshold-gradient is close to the predicted critical gradient for linear stability. While nonlinear analysis shows a large Dimits shift associated with predicted strong zonal flows, the inclusion of residual magnetic fluctuations causes a collapse of the zonal flows and an increase in the predicted transport to a level close to the experimentally measured heat flux. Similar circumstances could occur in the edge region of tokamak plasmas when resonant magnetic perturbations are applied for the control of ELMs. Work supported by US DOE.

Tailoring the Variational Implicit Solvent Method for New Challenges: Biomolecular Recognition and Assembly

PubMed Central

Ricci, Clarisse Gravina; Li, Bo; Cheng, Li-Tien; Dzubiella, Joachim; McCammon, J. Andrew

2018-01-01

Predicting solvation free energies and describing the complex water behavior that plays an important role in essentially all biological processes is a major challenge from the computational standpoint. While an atomistic, explicit description of the solvent can turn out to be too expensive in large biomolecular systems, most implicit solvent methods fail to capture “dewetting” effects and heterogeneous hydration by relying on a pre-established (i.e., guessed) solvation interface. Here we focus on the Variational Implicit Solvent Method, an implicit solvent method that adds water “plasticity” back to the picture by formulating the solvation free energy as a functional of all possible solvation interfaces. We survey VISM's applications to the problem of molecular recognition and report some of the most recent efforts to tailor VISM for more challenging scenarios, with the ultimate goal of including thermal fluctuations into the framework. The advances reported herein pave the way to make VISM a uniquely successful approach to characterize complex solvation properties in the recognition and binding of large-scale biomolecular complexes. PMID:29484300

Extreme fluctuations in stochastic network coordination with time delays

NASA Astrophysics Data System (ADS)

Hunt, D.; Molnár, F.; Szymanski, B. K.; Korniss, G.

2015-12-01

We study the effects of uniform time delays on the extreme fluctuations in stochastic synchronization and coordination problems with linear couplings in complex networks. We obtain the average size of the fluctuations at the nodes from the behavior of the underlying modes of the network. We then obtain the scaling behavior of the extreme fluctuations with system size, as well as the distribution of the extremes on complex networks, and compare them to those on regular one-dimensional lattices. For large complex networks, when the delay is not too close to the critical one, fluctuations at the nodes effectively decouple, and the limit distributions converge to the Fisher-Tippett-Gumbel density. In contrast, fluctuations in low-dimensional spatial graphs are strongly correlated, and the limit distribution of the extremes is the Airy density. Finally, we also explore the effects of nonlinear couplings on the stability and on the extremes of the synchronization landscapes.

Response of the Equatorial Ionosphere to the Geomagnetic DP 2 Current System

NASA Technical Reports Server (NTRS)

Yizengaw, E.; Moldwin, M. B.; Zesta, E.; Magoun, M.; Pradipta, R.; Biouele, C. M.; Rabiu, A. B.; Obrou, O. K.; Bamba, Z.; Paula, E. R. De

2016-01-01

The response of equatorial ionosphere to the magnetospheric origin DP 2 current system fluctuations is examined using ground-based multiinstrument observations. The interaction between the solar wind and fluctuations of the interplanetary magnetic field (IMF) Bz, penetrates nearly instantaneously to the dayside equatorial region at all longitudes and modulates the electrodynamics that governs the equatorial density distributions. In this paper, using magnetometers at high and equatorial latitudes, we demonstrate that the quasiperiodic DP 2 current system penetrates to the equator and causes the dayside equatorial electrojet (EEJ) and the independently measured ionospheric drift velocity to fluctuate coherently with the high-latitude DP 2 current as well as with the IMF Bz component. At the same time, radar observations show that the ionospheric density layers move up and down, causing the density to fluctuate up and down coherently with the EEJ and IMF Bz.

Microscopic Phase-Space Exploration Modeling of ^{258}Fm Spontaneous Fission.

PubMed

Tanimura, Yusuke; Lacroix, Denis; Ayik, Sakir

2017-04-14

We show that the total kinetic energy (TKE) of nuclei after the spontaneous fission of ^{258}Fm can be well reproduced using simple assumptions on the quantum collective phase space explored by the nucleus after passing the fission barrier. Assuming energy conservation and phase-space exploration according to the stochastic mean-field approach, a set of initial densities is generated. Each density is then evolved in time using the nuclear time-dependent density-functional theory with pairing. This approach goes beyond the mean-field theory by allowing spontaneous symmetry breaking as well as a wider dynamical phase-space exploration leading to larger fluctuations in collective space. The total kinetic energy and mass distributions are calculated. New information on the fission process: fluctuations in scission time, strong correlation between TKE and collective deformation, as well as prescission particle emission, are obtained. We conclude that fluctuations of the TKE and mass are triggered by quantum fluctuations.

Axial distribution of plasma fluctuations, plasma parameters, deposition rate and grain size during copper deposition

NASA Astrophysics Data System (ADS)

Gopikishan, S.; Banerjee, I.; Pathak, Anand; Mahapatra, S. K.

2017-08-01

Floating potential fluctuations, plasma parameters and deposition rate have been investigated as a function of axial distance during deposition of copper in direct current (DC) magnetron sputtering system. Fluctuations were analyzed using phase space, power spectra and amplitude bifurcation plots. It has been observed that the fluctuations are modified from chaotic to ordered state with increase in the axial distance from cathode. Plasma parameters such as electron density (ne), electron temperature (Te) and deposition rate (Dr) were measured and correlated with plasma fluctuations. It was found that more the deposition rate, greater the grain size, higher the electron density, higher the electron temperature and more chaotic the oscillations near the cathode. This observation could be helpful to the thin film technology industry to optimize the required film.

Kinetic-scale fluctuations resolved with the Fast Plasma Investigation on NASA's Magnetospheric Multiscale mission.

NASA Astrophysics Data System (ADS)

Gershman, D. J.; Figueroa-Vinas, A.; Dorelli, J.; Goldstein, M. L.; Shuster, J. R.; Avanov, L. A.; Boardsen, S. A.; Stawarz, J. E.; Schwartz, S. J.; Schiff, C.; Lavraud, B.; Saito, Y.; Paterson, W. R.; Giles, B. L.; Pollock, C. J.; Strangeway, R. J.; Russell, C. T.; Torbert, R. B.; Moore, T. E.; Burch, J. L.

2017-12-01

Measurements from the Fast Plasma Investigation (FPI) on NASA's Magnetospheric Multiscale (MMS) mission have enabled unprecedented analyses of kinetic-scale plasma physics. FPI regularly provides estimates of current density and pressure gradients of sufficient accuracy to evaluate the relative contribution of terms in plasma equations of motion. In addition, high-resolution three-dimensional velocity distribution functions of both ions and electrons provide new insights into kinetic-scale processes. As an example, for a monochromatic kinetic Alfven wave (KAW) we find non-zero, but out-of-phase parallel current density and electric field fluctuations, providing direct confirmation of the conservative energy exchange between the wave field and particles. In addition, we use fluctuations in current density and magnetic field to calculate the perpendicular and parallel wavelengths of the KAW. Furthermore, examination of the electron velocity distribution inside the KAW reveals a population of electrons non-linearly trapped in the kinetic-scale magnetic mirror formed between successive wave peaks. These electrons not only contribute to the wave's parallel electric field but also account for over half of the density fluctuations within the wave, supplying an unexpected mechanism for maintaining quasi-neutrality in a KAW. Finally, we demonstrate that the employed wave vector determination technique is also applicable to broadband fluctuations found in Earth's turbulent magnetosheath.

Plasma Turbulence Imaging via Beam Emission Spectroscopy in the Core of the DIII-D Tokamak

NASA Astrophysics Data System (ADS)

McKee, George R.; Fonck, Raymond J.; Gupta, Deepak K.; Schlossberg, David J.; Shafer, Morgan W.; Boivin, Réjean L.; Solomon, Wayne

Beam Emission Spectroscopy (BES), a high-sensitivity, good spatial resolution imaging diagnostic system, has been deployed and recently upgraded and expanded at the DIII-D tokamak to better understand density fluctuations arising from plasma turbulence. The currently deployed system images density fluctuations over an approximately 5 × 7 cm region at the plasma mid-plane (radially scannable over 0.2 < r/a ≤ 1) with a 5 × 6 (radial × poloidal) grid of rectangular detection channels, with one microsecond time resolution. BES observes collisionally-induced, Doppler-shifted Dα fluorescence (λ = 652-655 nm) of injected deuterium neutral beam atoms. The diagnostic wavenumber sensitivity is approximately k⊥ < 2.5 cm-1, allowing measurement of longwavelength (k⊥ρI < 1) density fluctuations. The recent upgrade includes expanded fiber optics bundles, customdesigned high-transmission, sharp-edge interference filters, ultra fast collection optics, and enlarged photodiode detectors that together provide nearly an order of magnitude increase in sensitivity relative to an earlier generation BES system. The high sensitivity allows visualization of turbulence at normalized density fluctuation amplitudes of ‾n/n < 1%, typical of fluctuation levels in the core region. The imaging array allows for sampling over 2-3 turbulent eddy scale lengths, which captures the essential dynamics of eddy evolution, interaction and shearing.

Calculation of the Intensity of Physical Time Fluctuations Using the Standard Solar Model and its Comparison with the Results of Experimental Measurements

NASA Astrophysics Data System (ADS)

Morozov, A. N.

2017-11-01

The article reviews the possibility of describing physical time as a random Poisson process. An equation allowing the intensity of physical time fluctuations to be calculated depending on the entropy production density within irreversible natural processes has been proposed. Based on the standard solar model the work calculates the entropy production density inside the Sun and the dependence of the intensity of physical time fluctuations on the distance to the centre of the Sun. A free model parameter has been established, and the method of its evaluation has been suggested. The calculations of the entropy production density inside the Sun showed that it differs by 2-3 orders of magnitude in different parts of the Sun. The intensity of physical time fluctuations on the Earth's surface depending on the entropy production density during the sunlight-to-Earth's thermal radiation conversion has been theoretically predicted. A method of evaluation of the Kullback's measure of voltage fluctuations in small amounts of electrolyte has been proposed. Using a simple model of the Earth's surface heat transfer to the upper atmosphere, the effective Earth's thermal radiation temperature has been determined. A comparison between the theoretical values of the Kullback's measure derived from the fluctuating physical time model and the experimentally measured values of this measure for two independent electrolytic cells showed a good qualitative and quantitative concurrence of predictions of both theoretical model and experimental data.

LETTER TO THE EDITOR: The quasi-coherent signature of enhanced Dα H-mode in Alcator C-Mod

NASA Astrophysics Data System (ADS)

Snipes, J. A.; La Bombard, B.; Greenwald, M.; Hutchinson, I. H.; Irby, J.; Lin, Y.; Mazurenko, A.; Porkolab, M.

2001-04-01

The steady-state H-mode regime found at moderate to high density in Alcator C-Mod, known as enhanced Dα (EDA) H-mode, appears to be maintained by a continuous quasi-coherent (QC) mode in the steep edge gradient region. Large amplitude density and magnetic fluctuations with typical frequencies of about 100 kHz are driven by the QC mode. These fluctuations are measured in the steep edge gradient region by inserting a fast-scanning probe containing two poloidally separated Langmuir probes and a poloidal field pick-up coil. As the probe approaches the plasma edge, clear magnetic fluctuations were measured within about 2 cm of the last-closed flux surface (LCFS). The mode amplitude falls off rapidly with distance from the plasma centre with an exponential decay length of kr≈1.5 cm-1, measured 10 cm above the outboard midplane. The root-mean-square amplitude of the fluctuation extrapolated to the LCFS was θ≈5 G. The density fluctuations, on the other hand, were visible on the Langmuir probe only when it was within a few millimetres of the LCFS. The potential and density fluctuations were sufficiently in phase to enhance particle transport at the QC mode frequency. These results show that the QC signature of the EDA H-mode is an electromagnetic mode that appears to be responsible for the enhanced particle transport in the plasma edge.

Interaction between the lower hybrid wave and density fluctuations in the scrape-off layer

NASA Astrophysics Data System (ADS)

Peysson, Y.; Madi, M.; Decker, J.; Kabalan, K.

2015-12-01

In the present paper, the perturbation of the launched power spectrum of the Lower Hybrid wave at the separatrix by electron density fluctuations in the scrape-off layer is investigated. Considering a slab geometry with magnetic field lines parallel to the toroidal direction, the full wave equation is solved using Comsol Multiphysics® for a fully active multi-junction like LH antenna made of two modules. When electron density fluctuations are incorporated in the dielectric tensor over a thin perturbed layer in front of the grill, it is shown that the power spectrum may be strongly modified from the antenna mouth to the plasma separatrix as the wave propagates. The diffraction effect leads to the appearance of multiple satellite lobes with randomly varying positions, a feature consistent with the recently developed model that has been applied successfully to high density discharges on the Tokamak Tore Supra corresponding to the large spectral gap regime [Decker J. et al. Phys. Plasma 21 (2014) 092504]. The perturbation is found to be maximum for the Fourier components of the fluctuating spectrum in the vicinity of the launched LH wavelength.

Effect of the collective motions of molecules inside a condensed phase on fluctuations in the density of small bodies

NASA Astrophysics Data System (ADS)

Tovbin, Yu. K.

2017-11-01

An approach to calculating the effects of fluctuations in density that considers the collective motions of molecules in small condensed phases (e.g., droplets, microcrystals, adsorption at microcrystal faces) is proposed. Statistical sums of the vibrational, rotational, and translational motions of molecules are of a collective character expressed in the dependences of these statistical sums on the local configurations of neighboring molecules. This changes their individual contributions to the free energy and modifies fluctuations in density in the inner homogeneous regions of small bodies. Interactions between nearest neighbors are considered in a quasi-chemical approximation that reflects the effects of short-range direct correlations. Expressions for isotherms relating the densities of mixture components to the chemical potentials in a thermostat are obtained, along with equations for pair distribution functions.

Stochastic modelling of intermittent fluctuations in the scrape-off layer: Correlations, distributions, level crossings, and moment estimation

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

Garcia, O. E., E-mail: odd.erik.garcia@uit.no; Kube, R.; Theodorsen, A.

A stochastic model is presented for intermittent fluctuations in the scrape-off layer of magnetically confined plasmas. The fluctuations in the plasma density are modeled by a super-position of uncorrelated pulses with fixed shape and duration, describing radial motion of blob-like structures. In the case of an exponential pulse shape and exponentially distributed pulse amplitudes, predictions are given for the lowest order moments, probability density function, auto-correlation function, level crossings, and average times for periods spent above and below a given threshold level. Also, the mean squared errors on estimators of sample mean and variance for realizations of the process bymore » finite time series are obtained. These results are discussed in the context of single-point measurements of fluctuations in the scrape-off layer, broad density profiles, and implications for plasma–wall interactions due to the transient transport events in fusion grade plasmas. The results may also have wide applications for modelling fluctuations in other magnetized plasmas such as basic laboratory experiments and ionospheric irregularities.« less

Incoherent scatter radar observations of the ionosphere

NASA Technical Reports Server (NTRS)

Hagfors, Tor

1989-01-01

Incoherent scatter radar (ISR) has become the most powerful means of studying the ionosphere from the ground. Many of the ideas and methods underlying the troposphere and stratosphere (ST) radars have been taken over from ISR. Whereas the theory of refractive index fluctuations in the lower atmosphere, depending as it does on turbulence, is poorly understood, the theory of the refractivity fluctuations in the ionosphere, which depend on thermal fluctuations, is known in great detail. The underlying theory is one of the most successful theories in plasma physics, and allows for many detailed investigations of a number of parameters such as electron density, electron temperature, ion temperature, electron mean velocity, and ion mean velocity as well as parameters pertaining to composition, neutral density and others. Here, the author reviews the fundamental processes involved in the scattering from a plasma undergoing thermal or near thermal fluctuations in density. The fundamental scattering properties of the plasma to the physical parameters characterizing them from first principles. He does not discuss the observation process itself, as the observational principles are quite similar whether they are applied to a neutral gas or a fluctuating plasma.

Experimental studies of toroidal correlations of plasma density fluctuations along the magnetic field lines in the T-10 tokamak and first results of numerical modeling

NASA Astrophysics Data System (ADS)

Buldakov, M. A.; Vershkov, V. A.; Isaev, M. Yu; Shelukhin, D. A.

2017-10-01

The antenna system of reflectometry diagnostics at the T-10 tokamak allows to study long-range toroidal correlations of plasma density fluctuations along the magnetic field lines. The antenna systems are installed in two poloidal cross-sections of the vacuum chamber separated by a 90° angle in the toroidal direction. The experiments, which were conducted at the low field side, showed that the high level of toroidal correlations is observed only for quasi-coherent fluctuations. However, broadband and stochastic low frequency fluctuations are not correlated. Numerical modeling of the plasma turbulence structure in the T-10 tokamak was conducted to interpret the experimental results and take into account non-locality of reflectometry measurements. In the model used, it was assumed that the magnitudes of density fluctuations are constant along the magnetic field lines. The 2D full-wave Tamic-RTH code was used to model the reflectometry signals. High level of correlations for quasi-coherent fluctuations was obtained during the modeling, which agrees with the experimental observations. However, the performed modeling also predicts high level of correlations for broadband fluctuations, which contradicts the experimental data. The modeling showed that the effective reflection radius, from which the information on quasi-coherent plasma turbulence is obtained, is shifted outwards from the reflection radius by approximately 7 mm.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery

PubMed Central

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-01-01

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level. PMID:28272396

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery

NASA Astrophysics Data System (ADS)

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-03-01

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion...carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery.

PubMed

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-03-08

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level.

The radio-frequency fluctuation effect on the floating harmonic method

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

Lee, Jaewon; Kim, Kyung-Hyun; Kim, Dong-Hwan

2016-08-15

The radio-frequency (RF) plasma diagnostics with an electrical probe facing a challenge, because the RF fluctuation oscillates the plasma potential and distorts the current-voltage (I-V) curve. As Langmuir probe is widely used in plasma diagnostics, many researchers have been studying the effect of RF fluctuation on probe and compensation methods. On the other hand, there have not been enough studies on the fluctuation effect on the floating harmonic method. Therefore, we investigated the impact of RF fluctuation on the floating harmonic method theoretically and experimentally. When the electrons are in ideal Maxwellian distribution, the floating potential is negatively shifted bymore » the RF fluctuation, but the fluctuation does not distort I-V curve around the floating potential. However, in practical plasmas, the I-V curve and their harmonic components are distorted. This RF fluctuation effect becomes more significant in a low density plasma with a high impedance sheath. The second harmonic current decreases with the RF fluctuation while the first harmonic current is merely affected. Therefore, the electron temperatures measured with the floating harmonic method under low density plasma with uncompensated probe are overestimated than the results obtained with the compensated probe.« less

Interaction of the electron density fluctuations with electron cyclotron waves from the equatorial launcher in ITER

NASA Astrophysics Data System (ADS)

Snicker, A.; Poli, E.; Maj, O.; Guidi, L.; Köhn, A.; Weber, H.; Conway, G. D.; Henderson, M.; Saibene, G.

2018-01-01

We present a numerical investigation of electron cyclotron beams interacting with electron density fluctuations in the ITER 15 MA H-mode scenario. In particular, here we study how the beam from the equatorial launcher, which shall be utilized to influence the sawtooth instability, is affected by the fluctuations. Moreover, we present the theory and first estimates of the power that is scattered from the injected O-mode to a secondary X-mode in the presence of the fluctuations. It is shown that for ITER parameters the scattered power stays within acceptable limits and broadening of the equatorial beams is less than those from the upper launcher.

Ultrasonic studies of intermolecular interactions in binary mixtures of 4-methoxy benzoin with various solvents: Excess molar functions of ultrasonic parameters at different concentrations and in different solvents.

PubMed

Thanuja, B; Nithya, G; Kanagam, Charles C

2012-11-01

Density (ρ), ultrasonic velocity (U), for the binary mixtures of 4-methoxy benzoin (4MB) with ethanol, chloroform, acetonitrile, benzene, and di-oxane were measured at 298K. The solute-solvent interactions and the effect of the polarity of the solvent on the type of intermolecular interactions are discussed here. From the above data, adiabatic compressibility (β), intermolecular free length (L(f)), acoustic impedance (Z), apparent molar volume (Ø), relative association (RA) have been calculated. Other useful parameters such as excess density, excess velocity and excess adiabatic compressibility have also been calculated. These parameters were used to study the nature and extent of intermolecular interactions between component molecules in the binary mixtures. Copyright © 2012 Elsevier B.V. All rights reserved.

End-anchored polymers in good solvents from the single chain limit to high anchoring densities.

PubMed

Whitmore, Mark D; Grest, Gary S; Douglas, Jack F; Kent, Michael S; Suo, Tongchuan

2016-11-07

An increasing number of applications utilize grafted polymer layers to alter the interfacial properties of solid substrates, motivating refinement in our theoretical understanding of such layers. To assess existing theoretical models of them, we have investigated end-anchored polymer layers over a wide range of grafting densities, σ, ranging from a single chain to high anchoring density limits, chain lengths ranging over two orders of magnitude, for very good and marginally good solvent conditions. We compare Monte Carlo and molecular dynamics simulations, numerical self-consistent field calculations, and experimental measurements of the average layer thickness, h, with renormalization group theory, the Alexander-de Gennes mushroom theory, and the classical brush theory. Our simulations clearly indicate that appreciable inter-chain interactions exist at all simulated areal anchoring densities so that there is no mushroom regime in which the layer thickness is independent of σ. Moreover, we find that there is no high coverage regime in which h follows the predicted scaling, h ∼ Nσ 1/3 , for classical polymer brushes either. Given that no completely adequate analytic theory seems to exist that spans wide ranges of N and σ, we applied scaling arguments for h as a function of a suitably defined reduced anchoring density, defined in terms of the solution radius of gyration of the polymer chains and N. We find that such a scaling approach enables a smooth, unified description of h in very good solvents over the full range of anchoring density and chain lengths, although this type of data reduction does not apply to marginal solvent quality conditions.

[Supercritical and near-critical fluid solvents assisted reaction and separation processes].

PubMed

Song, R; Zeng, J; Zhong, B

2001-11-01

The tunability of supercritical and near-critical fluid (S/NCF) solvents offers environmental improvements and economic advantages from improved performances and flexibility for separation and reaction processes through density changes or cosolvents. The paper reviews the sustainable reaction and separation processes in S/NCF solvents such as supercritical carbon dioxide and near-critical water.

Solvent Effects on the Conductance of 1,4-benzenediamine

NASA Astrophysics Data System (ADS)

Fatemi, Valla; Kamenetska, Maria; Neaton, Jeffrey; Venkataraman, Latha

2010-03-01

We measured the conductance of 1,4-benzenediamine (BDA) by mechanically forming and breaking Au point contacts with a modified STM in a solution of molecules in ambient conditions, using a variety of solvents. Here, we present reliable experimental results which show that the conductance of BDA can be increased by over 50% when dissolved in aromatic organic solvents solely by varying halogen groups on the solvent molecule. The trends in conductance do not correlate with the solvent dielectric constant, dipole moment, or direct solvent-BDA interactions. First-principles density functional theory calculations of solvent molecule binding to gold surfaces are used to discuss mechanisms behind the conductance shift of the BDA molecule.

Observations of fine scale structure in the mesosphere and lower thermosphere

NASA Astrophysics Data System (ADS)

Thrane, E. V.; Grandal, B.

1980-06-01

An electrostatic probe designed to measure ion density with high time resolution and accuracy was flown on a Nike-Apache rocket from Andoeya Rocket Range on March 1 1978. Spectra of the spatial density fluctuations were derived in one kilometer height intervals from 65 to 127 km. Below 95 km the power spectra had a slope of about -5/3, as expected for isotropic turbulence. Above 95 km the fluctuations were stronger and showed a white noise power spectrum. These fluctuations are most likely due to plasma instabilities.

Solvent effects on polysulfide redox kinetics and ionic conductivity in lithium-sulfur batteries

DOE PAGES

Fan, Frank Y.; Pan, Menghsuan Sam; Lau, Kah Chun; ...

2016-11-25

Lithium-sulfur (Li-S) batteries have high theoretical energy density and low raw materials cost compared to present lithium-ion batteries and are thus promising for use in electric transportation and other applications. A major obstacle for Li-S batteries is low rate capability, especially at the low electrolyte/sulfur (E/S) ratios required for high energy density. Herein, we investigate several potentially rate-limiting factors for Li-S batteries. We study the ionic conductivity of lithium polysulfide solutions of varying concentration and in different ether-based solvents and their exchange current density on glassy carbon working electrodes. We believe this is the first such investigation of exchange currentmore » density for lithium polysulfide in solution. Exchange current densities are measured using both electrochemical impedance spectroscopy and steady-state galvanostatic polarization. In the range of interest (1-8 M [S]), the ionic conductivity monotonically decreases with increasing sulfur concentration while exchange current density shows a more complicated relationship to sulfur concentration. The electrolyte solvent dramatically affects ionic conductivity and exchange current density. Finally, the measured ionic conductivities and exchange current densities are also used to interpret the overpotential and rate capability of polysulfide-nanocarbon suspensions; this analysis demonstrates that ionic conductivity is the rate-limiting property in the solution regime (i.e. between Li 2S 8 and Li 2S 4).« less

Millimeter-wave reflectometry for electron density profile and fluctuation measurements on NSTX

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

Kubota, S.; Nguyen, X. V.; Peebles, W. A.

2001-01-01

A millimeter-wave reflectometry system for electron density profile and fluctuation measurements is being developed and installed on the National Spherical Torus Experiment. The initial frequency coverage will be in the bands 12--18, 20--32, and 33--50 GHz, provided by frequency-tunable solid-state sources. These frequencies correspond to O-mode cutoff densities ranging from 1.8x10{sup 12} to 3.1x10{sup 13}cm{sup -3}, which will span both the plasma core ({rho}=r/a<0.8) and edge ({rho}>0.8) regions. Operated as a broadband swept-frequency (frequency-modulated continuous-wave) reflectometer, the diagnostic is expected to provide routine (shot-to-shot) time- ({<=}50 {mu}s) and spatially resolved ({approx}1 cm) density profiles. The previous hardware can be easilymore » reconfigured as a fixed-frequency reflectometer for density fluctuation measurements. The combination of measurements would be valuable for studying phenomena such as possible L- to H-mode transitions and edge-localized modes.« less

The topology of large-scale structure. I - Topology and the random phase hypothesis. [galactic formation models

NASA Technical Reports Server (NTRS)

Weinberg, David H.; Gott, J. Richard, III; Melott, Adrian L.

1987-01-01

Many models for the formation of galaxies and large-scale structure assume a spectrum of random phase (Gaussian), small-amplitude density fluctuations as initial conditions. In such scenarios, the topology of the galaxy distribution on large scales relates directly to the topology of the initial density fluctuations. Here a quantitative measure of topology - the genus of contours in a smoothed density distribution - is described and applied to numerical simulations of galaxy clustering, to a variety of three-dimensional toy models, and to a volume-limited sample of the CfA redshift survey. For random phase distributions the genus of density contours exhibits a universal dependence on threshold density. The clustering simulations show that a smoothing length of 2-3 times the mass correlation length is sufficient to recover the topology of the initial fluctuations from the evolved galaxy distribution. Cold dark matter and white noise models retain a random phase topology at shorter smoothing lengths, but massive neutrino models develop a cellular topology.

Density fluctuations in aqueous solution of ionic liquid with lower critical solution temperature: Mixture of tetrabutylphosphonium trifluoroacetate and water

NASA Astrophysics Data System (ADS)

Nitta, Ayako; Morita, Takeshi; Saita, Shohei; Kohno, Yuki; Ohno, Hiroyuki; Nishikawa, Keiko

2015-05-01

Aqueous solutions of tetrabutylphosphonium trifluoroacetate ([P4444]CF3COO) exhibit a LCST-type phase transition with the critical point near 0.025 in mole fraction of [P4444]CF3COO at T = 302 K. The phase behavior of [P4444]CF3COO-water mixtures was investigated by evaluating their density fluctuations, which provide quantitative descriptions of the mixing states of the solutions. The concentration dependence of the density fluctuations was investigated at 293 and 301 K for the mixtures without distinguishing the components and for the individual components ([P4444]CF3COO and water). A drastic change in the mixing state was observed for the solution when the critical point was approached.

Effects of density gradients and fluctuations at the plasma edge on ECEI measurements at ASDEX Upgrade

NASA Astrophysics Data System (ADS)

Vanovac, B.; Wolfrum, E.; Denk, S. S.; Mink, F.; Laggner, F. M.; Birkenmeier, G.; Willensdorfer, M.; Viezzer, E.; Hoelzl, M.; Freethy, S. J.; Dunne, M. G.; Lessig, A.; Luhmann, N. C., Jr.; the ASDEX Upgrade Team; the EUROfusion MST1 Team

2018-04-01

Electron cyclotron emission imaging (ECEI) provides measurements of electron temperature (T e ) and its fluctuations (δT e ). However, when measuring at the plasma edge, in the steep gradient region, radiation transport effects must be taken into account. It is shown that due to these effects, the scrape-off layer region is not accessible to the ECEI measurements in steady state conditions and that the signal is dominated by the shine-through emission. Transient effects, such as filaments, can change the radiation transport locally, but cannot be distinguished from the shine-through. Local density measurements are essential for the correct interpretation of the electron cyclotron emission, since the density fluctuations influence the temperature measurements at the plasma edge. As an example, a low frequency 8 kHz mode, which causes 10%-15% fluctuations in the signal level of the ECEI, is analysed. The same mode has been measured with the lithium beam emission spectroscopy density diagnostic, and is very well correlated in time with high frequency magnetic fluctuations. With radiation transport modelling of the electron cyclotron radiation in the ECEI geometry, it is shown that the density contributes significantly to the radiation temperature (T rad) and the experimental observations have shown the amplitude modulation in both density and temperature measurements. The poloidal velocity of the low frequency mode measured by the ECEI is 3 km s-1. The calculated velocity of the high frequency mode measured with the magnetic pick-up coils is about 25 km s-1. Velocities are compared with the E × B background flow velocity and possible explanations for the origin of the low frequency mode are discussed.

Thermophoresis of dissolved molecules and polymers: Consideration of the temperature-induced macroscopic pressure gradient

NASA Astrophysics Data System (ADS)

Semenov, Semen; Schimpf, Martin

2004-01-01

The movement of molecules and homopolymer chains dissolved in a nonelectrolyte solvent in response to a temperature gradient is considered a consequence of temperature-induced pressure gradients in the solvent layer surrounding the solute molecules. Local pressure gradients are produced by nonuniform London van der Waals interactions, established by gradients in the concentration (density) of solvent molecules. The density gradient is produced by variations in solvent thermal expansion within the nonuniform temperature field. The resulting expression for the velocity of the solute contains the Hamaker constants for solute-solvent and solute-solute interactions, the radius of the solute molecule, and the viscosity and cubic coefficient of thermal expansion of the solvent. In this paper we consider an additional force that arises from directional asymmetry in the interaction between solvent molecules. In a closed cell, the resulting macroscopic pressure gradient gives rise to a volume force that affects the motion of dissolved solutes. An expression for this macroscopic pressure gradient is derived and the resulting force is incorporated into the expression for the solute velocity. The expression is used to calculate thermodiffusion coefficients for polystyrene in several organic solvents. When these values are compared to those measured in the laboratory, the consistency is better than that found in previous reports, which did not consider the macroscopic pressure gradient that arises in a closed thermodiffusion cell. The model also allows for the movement of solute in either direction, depending on the relative values of the solvent and solute Hamaker constants.

Rayleigh Scattering Diagnostic for Measurement of Temperature, Velocity, and Density Fluctuation Spectra

NASA Technical Reports Server (NTRS)

Mielke, Amy F.; Elam, Kristie A.; Sung, Chih-Jen; Panda, Jayanta

2006-01-01

A molecular Rayleigh scattering technique is developed to measure dynamic gas temperature, velocity, and density in unseeded turbulent flows at sampling rates up to 10 kHz. A high power CW laser beam is focused at a point in a heated air jet plume and Rayleigh scattered light is collected and spectrally resolved. The spectrum of the light, which contains information about the temperature, velocity, and density of the flow, is analyzed using a Fabry-Perot interferometer. The circular interference fringe pattern is divided into four concentric regions and sampled at 1 and 10 kHz using photon counting electronics. Monitoring the relative change in intensity within each region allows for measurement of gas temperature and velocity. Independently monitoring the total scattered light intensity provides a measure of gas density. Power spectral density calculations of temperature, velocity, and density fluctuations, as well as mean and fluctuating quantities are demonstrated for various radial locations in the jet flow at a fixed axial distance from the jet exit plane. Results are compared with constant current anemometry and pitot probe measurements at the same locations.

Large Fluctuations for Spatial Diffusion of Cold Atoms

NASA Astrophysics Data System (ADS)

Aghion, Erez; Kessler, David A.; Barkai, Eli

2017-06-01

We use a new approach to study the large fluctuations of a heavy-tailed system, where the standard large-deviations principle does not apply. Large-deviations theory deals with tails of probability distributions and the rare events of random processes, for example, spreading packets of particles. Mathematically, it concerns the exponential falloff of the density of thin-tailed systems. Here we investigate the spatial density Pt(x ) of laser-cooled atoms, where at intermediate length scales the shape is fat tailed. We focus on the rare events beyond this range, which dominate important statistical properties of the system. Through a novel friction mechanism induced by the laser fields, the density is explored with the recently proposed non-normalized infinite-covariant density approach. The small and large fluctuations give rise to a bifractal nature of the spreading packet. We derive general relations which extend our theory to a class of systems with multifractal moments.

Dispersed three-pulse infrared photon echoes of nitrous oxide in water and octanol.

PubMed

Shattuck, J T; Schneck, J R; Chieffo, L R; Erramilli, S; Ziegler, L D

2013-12-12

Dispersed IR three-pulse photon echoes due to the antisymmetric (ν3) stretch mode of N2O dissolved in H2O and 1-octanol at room temperature are reported and analyzed. The experimentally determined transition frequency-frequency correlation function (FFCF) in these two solvents is explained in terms of inertial solvent contributions, hydrogen bond network fluctuations, and, for octanol, the motions of the alkyl chains. The H2O hydrogen bond fluctuations result in 1.5 ps FFCF decay, in agreement with relaxation rates determined from photon echo based measurements of other aqueous solutions including salt solutions. In octanol, hydrogen bond fluctuations decay on a slower time scale of 3.3 ps and alkyl chain motions result in an inhomogeneous broadening contribution to the ν3 absorption spectrum that decays on a 35 ps time scale. Rotational reorientation of N2O is nearly 3 times faster in octanol as compared to water. Although the vibrational ν3 N2O absorption line shapes in water and octanol are similar, the line widths result from different coherence loss mechanisms. A hot band contribution in the N2O in octanol solution is found to have a significant effect on the echo spectrum due to its correspondingly stronger transition moment than that of the fundamental transition. The dephasing dynamics of the N2O ν3 stretch mode is of interest as a probe in ultrafast studies of complex or nanoconfined systems with both hydrophobic and hydrophilic regions such as phospholipids, nucleic acids, and proteins. These results demonstrate the value of the N2O molecule to act as a reporter of equilibrium fluctuations in such complex systems particularly due to its solubility characteristics and long vibrational lifetime.

Mechanisms of solvent resistance mediated by interplay of cellular factors in Pseudomonas putida.

PubMed

Ramos, Juan-Luis; Sol Cuenca, Maria; Molina-Santiago, Carlos; Segura, Ana; Duque, Estrella; Gómez-García, María R; Udaondo, Zulema; Roca, Amalia

2015-07-01

A number of microorganisms have the ability to thrive in the presence of a range of toxic solvents. Tolerance to these chemicals is a multifactorial process, meaning that bacterial cells use a set of physiological and gene expression changes to overcome the damage imparted by these chemicals. This review focuses mainly on issues related to tolerance to aromatic hydrocarbons and butanol in Pseudomonas, although other microorganisms are also discussed. Pseudomonas putida strains contain a circular chromosome of approximately 6 Mbp which encodes about 5300 genes. A combination of physiological and biochemical assays, a genome-wide collection of mutants and several omics approaches have provided useful information to help identify functions involved in solvent tolerance in P. putida. The solvent response involves fine-tuning of lipid fluidity to adjust membrane functions including impermeabilization, activation of a general stress-response system, increased energy generation and induction of specific efflux pumps that extrude solvents to the medium. These responses are modulated at the transcriptional level by local and global regulators as well as by a number of sRNAs whose levels fluctuate with the presence of solvents in the environment. Taken as a whole these regulatory inputs orchestrate the complex network of metabolic responses observed after solvent addition. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

High-amplitude fluctuations and alternative dynamical states of midges in Lake Myvatn.

PubMed

Ives, Anthony R; Einarsson, Arni; Jansen, Vincent A A; Gardarsson, Arnthor

2008-03-06

Complex dynamics are often shown by simple ecological models and have been clearly demonstrated in laboratory and natural systems. Yet many classes of theoretically possible dynamics are still poorly documented in nature. Here we study long-term time-series data of a midge, Tanytarsus gracilentus (Diptera: Chironomidae), in Lake Myvatn, Iceland. The midge undergoes density fluctuations of almost six orders of magnitude. Rather than regular cycles, however, these fluctuations have irregular periods of 4-7 years, indicating complex dynamics. We fit three consumer-resource models capable of qualitatively distinct dynamics to the data. Of these, the best-fitting model shows alternative dynamical states in the absence of environmental variability; depending on the initial midge densities, the model shows either fluctuations around a fixed point or high-amplitude cycles. This explains the observed complex population dynamics: high-amplitude but irregular fluctuations occur because stochastic variability causes the dynamics to switch between domains of attraction to the alternative states. In the model, the amplitude of fluctuations depends strongly on minute resource subsidies into the midge habitat. These resource subsidies may be sensitive to human-caused changes in the hydrology of the lake, with human impacts such as dredging leading to higher-amplitude fluctuations. Tanytarsus gracilentus is a key component of the Myvatn ecosystem, representing two-thirds of the secondary productivity of the lake and providing vital food resources to fish and to breeding bird populations. Therefore the high-amplitude, irregular fluctuations in midge densities generated by alternative dynamical states dominate much of the ecology of the lake.

Sound Sources Identified in High-Speed Jets by Correlating Flow Density Fluctuations With Far-Field Noise

NASA Technical Reports Server (NTRS)

Panda, Jayanta; Seasholtz, Richard G.

2003-01-01

Noise sources in high-speed jets were identified by directly correlating flow density fluctuation (cause) to far-field sound pressure fluctuation (effect). The experimental study was performed in a nozzle facility at the NASA Glenn Research Center in support of NASA s initiative to reduce the noise emitted by commercial airplanes. Previous efforts to use this correlation method have failed because the tools for measuring jet turbulence were intrusive. In the present experiment, a molecular Rayleigh-scattering technique was used that depended on laser light scattering by gas molecules in air. The technique allowed accurate measurement of air density fluctuations from different points in the plume. The study was conducted in shock-free, unheated jets of Mach numbers 0.95, 1.4, and 1.8. The turbulent motion, as evident from density fluctuation spectra was remarkably similar in all three jets, whereas the noise sources were significantly different. The correlation study was conducted by keeping a microphone at a fixed location (at the peak noise emission angle of 30 to the jet axis and 50 nozzle diameters away) while moving the laser probe volume from point to point in the flow. The following figure shows maps of the nondimensional coherence value measured at different Strouhal frequencies ([frequency diameter]/jet speed) in the supersonic Mach 1.8 and subsonic Mach 0.95 jets. The higher the coherence, the stronger the source was.

Langmuir turbulence driven by beams in solar wind plasmas with long wavelength density fluctuations

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

Krafft, C., E-mail: catherine.krafft@u-psud.fr; Universite´ Paris Sud, 91405 Orsay Cedex; Volokitin, A., E-mail: a.volokitin@mail.ru

2016-03-25

The self-consistent evolution of Langmuir turbulence generated by electron beams in solar wind plasmas with density inhomogeneities is calculated by numerical simulations based on a 1D Hamiltonian model. It is shown, owing to numerical simulations performed with parameters relevant to type III solar bursts’ conditions at 1 AU, that the presence of long-wavelength random density fluctuations of sufficiently large average level crucially modifies the well-known process of beam interaction with Langmuir waves in homogeneous plasmas.

Periodic fluctuations in correlation-based connectivity density time series: Application to wind speed-monitoring network in Switzerland

NASA Astrophysics Data System (ADS)

Laib, Mohamed; Telesca, Luciano; Kanevski, Mikhail

2018-02-01

In this paper, we study the periodic fluctuations of connectivity density time series of a wind speed-monitoring network in Switzerland. By using the correlogram-based robust periodogram annual periodic oscillations were found in the correlation-based network. The intensity of such annual periodic oscillations is larger for lower correlation thresholds and smaller for higher. The annual periodicity in the connectivity density seems reasonably consistent with the seasonal meteo-climatic cycle.

Interplay of Anderson localization and quench dynamics

NASA Astrophysics Data System (ADS)

Rahmani, Armin; Vishveshwara, Smitha

2018-06-01

In the context of an isolated three-dimensional noninteracting fermionic lattice system, we study the effects of a sudden quantum quench between a disorder-free situation and one in which disorder results in a mobility edge and associated Anderson localization. Salient post-quench features hinge upon the overlap between momentum states and post-quench eigenstates and whether these latter states are extended or localized. We find that the post-quench momentum distribution directly reflects these overlaps. For the local density, we show that disorder generically prevents the equilibration of quantum expectation values to a steady state and that the persistent fluctuations have a nonmonotonic dependence on the strength of disorder. We identify two distinct types of fluctuations, namely, temporal fluctuations describing the time-dependent fluctuations of the local density around its time average and sample-to-sample fluctuations characterizing the variations of these time averages from one realization of disorder to another. We demonstrate that both of these fluctuations vanish for extremely extended as well as extremely localized states, peaking at some intermediate value.

Intramolecular vibrational redistribution of CH 2I 2 dissolved in supercritical Xe

NASA Astrophysics Data System (ADS)

Sekiguchi, K.; Shimojima, A.; Kajimoto, O.

2003-03-01

Intramolecular vibrational energy redistribution (IVR) of CH 2I 2 in supercritical Xe has been studied. The first overtone of the C-H stretching mode was excited with a near infrared laser pulse and the transient UV absorption near 390 nm was monitored. Signals showed a rise and decay profile, which gave the IVR and VET (intermolecular vibrational energy transfer) rates, respectively. Solvent density dependence of each rate was obtained by tuning the pressure at a constant temperature. The IVR rate in supercritical Xe increased with increasing solvent density and asymptotically reached a limiting value. This result suggests that the IVR process of CH 2I 2 in condensed phase is a solvent-assisted process.

Detection limit for rate fluctuations in inhomogeneous Poisson processes

NASA Astrophysics Data System (ADS)

Shintani, Toshiaki; Shinomoto, Shigeru

2012-04-01

Estimations of an underlying rate from data points are inevitably disturbed by the irregular occurrence of events. Proper estimation methods are designed to avoid overfitting by discounting the irregular occurrence of data, and to determine a constant rate from irregular data derived from a constant probability distribution. However, it can occur that rapid or small fluctuations in the underlying density are undetectable when the data are sparse. For an estimation method, the maximum degree of undetectable rate fluctuations is uniquely determined as a phase transition, when considering an infinitely long series of events drawn from a fluctuating density. In this study, we analytically examine an optimized histogram and a Bayesian rate estimator with respect to their detectability of rate fluctuation, and determine whether their detectable-undetectable phase transition points are given by an identical formula defining a degree of fluctuation in an underlying rate. In addition, we numerically examine the variational Bayes hidden Markov model in its detectability of rate fluctuation, and determine whether the numerically obtained transition point is comparable to those of the other two methods. Such consistency among these three principled methods suggests the presence of a theoretical limit for detecting rate fluctuations.

Detection limit for rate fluctuations in inhomogeneous Poisson processes.

PubMed

Shintani, Toshiaki; Shinomoto, Shigeru

2012-04-01

Estimations of an underlying rate from data points are inevitably disturbed by the irregular occurrence of events. Proper estimation methods are designed to avoid overfitting by discounting the irregular occurrence of data, and to determine a constant rate from irregular data derived from a constant probability distribution. However, it can occur that rapid or small fluctuations in the underlying density are undetectable when the data are sparse. For an estimation method, the maximum degree of undetectable rate fluctuations is uniquely determined as a phase transition, when considering an infinitely long series of events drawn from a fluctuating density. In this study, we analytically examine an optimized histogram and a Bayesian rate estimator with respect to their detectability of rate fluctuation, and determine whether their detectable-undetectable phase transition points are given by an identical formula defining a degree of fluctuation in an underlying rate. In addition, we numerically examine the variational Bayes hidden Markov model in its detectability of rate fluctuation, and determine whether the numerically obtained transition point is comparable to those of the other two methods. Such consistency among these three principled methods suggests the presence of a theoretical limit for detecting rate fluctuations.

Study of ion-gyroscale fluctuations in low-density L-mode plasmas heated by NBI on KSTAR

NASA Astrophysics Data System (ADS)

Lee, W.; Ko, S. H.; Leem, J.; Yun, G. S.; Park, H. K.; Wang, W. X.; Budny, R. V.; Kim, K. W.; Luhmann, N. C., Jr.; The KSTAR Team

2018-04-01

Broadband density fluctuations with peak frequency ranging from 150 to 400 kHz were measured using a multichannel microwave imaging reflectometer in core region of the low-density L-mode plasmas heated by neutral beam injection on KSTAR. These fluctuations have been studied by comparing the dominant mode scales estimated from the measurement with those predicted from linear gyrokinetic simulation. The measured poloidal wavenumbers are qualitatively comparable to those of the ‘fastest growing modes’ from simulations, whereas they are larger than those of the ‘transport-dominant modes’ by about a factor of three. The agreement on wavenumbers between the measurement and linear simulation (for the fastest growing modes) is probably due to sufficiently weak E × B flow shear compared to the maximum linear growth rate. Meanwhile, the transport-dominant modes seem to be related to the fluctuations in lower frequencies (˜80-150 kHz) observed in some of the measurement.

Observation of trapped-electron-mode microturbulence in reversed field pinch plasmas

NASA Astrophysics Data System (ADS)

Duff, J. R.; Williams, Z. R.; Brower, D. L.; Chapman, B. E.; Ding, W. X.; Pueschel, M. J.; Sarff, J. S.; Terry, P. W.

2018-01-01

Density fluctuations in the large-density-gradient region of improved confinement Madison Symmetric Torus reversed field pinch (RFP) plasmas exhibit multiple features that are characteristic of the trapped-electron mode (TEM). Core transport in conventional RFP plasmas is governed by magnetic stochasticity stemming from multiple long-wavelength tearing modes. Using inductive current profile control, these tearing modes are reduced, and global confinement is increased to that expected for comparable tokamak plasmas. Under these conditions, new short-wavelength fluctuations distinct from global tearing modes appear in the spectrum at a frequency of f ˜ 50 kHz, which have normalized perpendicular wavenumbers k⊥ρs≲ 0.2 and propagate in the electron diamagnetic drift direction. They exhibit a critical-gradient threshold, and the fluctuation amplitude increases with the local electron density gradient. These characteristics are consistent with predictions from gyrokinetic analysis using the Gene code, including increased TEM turbulence and transport from the interaction of remnant tearing magnetic fluctuations and zonal flow.

Modeling turbulent/chemistry interactions using assumed pdf methods

NASA Technical Reports Server (NTRS)

Gaffney, R. L, Jr.; White, J. A.; Girimaji, S. S.; Drummond, J. P.

1992-01-01

Two assumed probability density functions (pdfs) are employed for computing the effect of temperature fluctuations on chemical reaction. The pdfs assumed for this purpose are the Gaussian and the beta densities of the first kind. The pdfs are first used in a parametric study to determine the influence of temperature fluctuations on the mean reaction-rate coefficients. Results indicate that temperature fluctuations significantly affect the magnitude of the mean reaction-rate coefficients of some reactions depending on the mean temperature and the intensity of the fluctuations. The pdfs are then tested on a high-speed turbulent reacting mixing layer. Results clearly show a decrease in the ignition delay time due to increases in the magnitude of most of the mean reaction rate coefficients.

Role of water and steric constraints in the kinetics of cavity–ligand unbinding

PubMed Central

Tiwary, Pratyush; Mondal, Jagannath; Morrone, Joseph A.; Berne, B. J.

2015-01-01

A key factor influencing a drug’s efficacy is its residence time in the binding pocket of the host protein. Using atomistic computer simulation to predict this residence time and the associated dissociation process is a desirable but extremely difficult task due to the long timescales involved. This gets further complicated by the presence of biophysical factors such as steric and solvation effects. In this work, we perform molecular dynamics (MD) simulations of the unbinding of a popular prototypical hydrophobic cavity–ligand system using a metadynamics-based approach that allows direct assessment of kinetic pathways and parameters. When constrained to move in an axial manner, the unbinding time is found to be on the order of 4,000 s. In accordance with previous studies, we find that the cavity must pass through a region of sharp wetting transition manifested by sudden and high fluctuations in solvent density. When we remove the steric constraints on ligand, the unbinding happens predominantly by an alternate pathway, where the unbinding becomes 20 times faster, and the sharp wetting transition instead becomes continuous. We validate the unbinding timescales from metadynamics through a Poisson analysis, and by comparison through detailed balance to binding timescale estimates from unbiased MD. This work demonstrates that enhanced sampling can be used to perform explicit solvent MD studies at timescales previously unattainable, to our knowledge, obtaining direct and reliable pictures of the underlying physiochemical factors including free energies and rate constants. PMID:26371312

Role of water and steric constraints in the kinetics of cavity-ligand unbinding.

PubMed

Tiwary, Pratyush; Mondal, Jagannath; Morrone, Joseph A; Berne, B J

2015-09-29

A key factor influencing a drug's efficacy is its residence time in the binding pocket of the host protein. Using atomistic computer simulation to predict this residence time and the associated dissociation process is a desirable but extremely difficult task due to the long timescales involved. This gets further complicated by the presence of biophysical factors such as steric and solvation effects. In this work, we perform molecular dynamics (MD) simulations of the unbinding of a popular prototypical hydrophobic cavity-ligand system using a metadynamics-based approach that allows direct assessment of kinetic pathways and parameters. When constrained to move in an axial manner, the unbinding time is found to be on the order of 4,000 s. In accordance with previous studies, we find that the cavity must pass through a region of sharp wetting transition manifested by sudden and high fluctuations in solvent density. When we remove the steric constraints on ligand, the unbinding happens predominantly by an alternate pathway, where the unbinding becomes 20 times faster, and the sharp wetting transition instead becomes continuous. We validate the unbinding timescales from metadynamics through a Poisson analysis, and by comparison through detailed balance to binding timescale estimates from unbiased MD. This work demonstrates that enhanced sampling can be used to perform explicit solvent MD studies at timescales previously unattainable, to our knowledge, obtaining direct and reliable pictures of the underlying physiochemical factors including free energies and rate constants.

Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions.

PubMed

Marenich, Aleksandr V; Cramer, Christopher J; Truhlar, Donald G

2009-05-07

We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the "D" stands for "density" to denote that the full solute electron density is used without defining partial atomic charges. "Continuum" denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where "universal" denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which a few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calculation are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality constants called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aqueous ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and dimethyl sulfoxide, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaqueous organic solvents and water), and 143 transfer free energies for 93 neutral solutes between water and 15 organic solvents. The elements present in the solutes are H, C, N, O, F, Si, P, S, Cl, and Br. The SMD model employs a single set of parameters (intrinsic atomic Coulomb radii and atomic surface tension coefficients) optimized over six electronic structure methods: M05-2X/MIDI!6D, M05-2X/6-31G, M05-2X/6-31+G, M05-2X/cc-pVTZ, B3LYP/6-31G, and HF/6-31G. Although the SMD model has been parametrized using the IEF-PCM protocol for bulk electrostatics, it may also be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calculations in which the solute is represented by its electron density in real space. This includes, for example, the conductor-like screening algorithm. With the 6-31G basis set, the SMD model achieves mean unsigned errors of 0.6-1.0 kcal/mol in the solvation free energies of tested neutrals and mean unsigned errors of 4 kcal/mol on average for ions with either Gaussian03 or GAMESS.

The effect of electron cyclotron heating on density fluctuations at ion and electron scales in ITER baseline scenario discharges on the DIII-D tokamak

NASA Astrophysics Data System (ADS)

Marinoni, A.; Pinsker, R. I.; Porkolab, M.; Rost, J. C.; Davis, E. M.; Burrell, K. H.; Candy, J.; Staebler, G. M.; Grierson, B. A.; McKee, G. R.; Rhodes, T. L.; The DIII-D Team

2017-12-01

Experiments simulating the ITER baseline scenario on the DIII-D tokamak show that torque-free pure electron heating, when coupled to plasmas subject to a net co-current beam torque, affects density fluctuations at electron scales on a sub-confinement time scale, whereas fluctuations at ion scales change only after profiles have evolved to a new stationary state. Modifications to the density fluctuations measured by the phase contrast imaging diagnostic (PCI) are assessed by analyzing the time evolution following the switch-off of electron cyclotron heating (ECH), thus going from mixed beam/ECH to pure neutral beam heating at fixed βN . Within 20 ms after turning off ECH, the intensity of fluctuations is observed to increase at frequencies higher than 200 kHz in contrast, fluctuations at lower frequency are seen to decrease in intensity on a longer time scale, after other equilibrium quantities have evolved. Non-linear gyro-kinetic modeling at ion and electron scales scales suggest that, while the low frequency response of the diagnostic is consistent with the dominant ITG modes being weakened by the slow-time increase in flow shear, the high frequency response is due to prompt changes to the electron temperature profile that enhance electron modes and generate a larger heat flux and an inward particle pinch. These results suggest that electron heated regimes in ITER will feature multi-scale fluctuations that might affect fusion performance via modifications to profiles.

Lithiated imines: solvent-dependent aggregate structures and mechanisms of alkylation.

PubMed

Zuend, Stephan J; Ramirez, Antonio; Lobkovsky, Emil; Collum, David B

2006-05-03

We describe efforts to understand the structure and reactivity of lithiated cyclohexanone N-cyclohexylimine. The lithioimine affords complex solvent-dependent distributions of monomers, dimers, and trimers in a number of ethereal solvents. Careful selection of solvent provides exclusively monosolvated dimers. Rate studies on the C-alkylations reveal chronic mixtures of monomer- and dimer-based pathways. We explore the factors influencing reactants and alkylation transition structures and the marked differences between lithioimines and isostructural lithium dialkylamides with the aid of density functional theory calculations.

Viking S-band Doppler RMS phase fluctuations used to calibrate the mean 1976 equatorial corona

NASA Technical Reports Server (NTRS)

Berman, A. L.; Wackley, J. A.

1977-01-01

Viking S-band Doppler RMS phase fluctuations (noise) and comparisons of Viking Doppler noise to Viking differenced S-X range measurements are used to construct a mean equatorial electron density model for 1976. Using Pioneer Doppler noise results (at high heliographic latitudes, also from 1976), an equivalent nonequatorial electron density model is approximated.

Effect of sorbitol and glycerol on the stability of trypsin and difference between their stabilization effects in the various solvents.

PubMed

Pazhang, Mohammad; Mehrnejad, Faramarz; Pazhang, Yaghub; Falahati, Hanieh; Chaparzadeh, Nader

2016-01-01

The effect of glycerol and sorbitol on the stability of porcine pancreas trypsin was investigated in this work. Molecular dynamics simulation and thermostability results showed that trypsin has two flexible regions, and polyols (sorbitol and glycerol) stabilize the enzyme by decreasing the flexibility of these regions. Radial distribution function results exhibited that sorbitol and glycerol were excluded from the first water layer of the enzyme, therefore decrease the flexibility of the regions by preferential exclusion. Also, results showed that the stabilization effect of sorbitol is more than glycerol. This observation could be because of the larger decrease in the fluctuations of trypsin in the presence of sorbitol. We also examined the role of solvent's hydrophobicity in enzyme stabilization by sorbitol and glycerol. To do so, the thermostability of trypsin was evaluated in the presence of solvents with different hydrophobicity (methanol, ethanol, isopropanol and n-propanol) in addition to the polyols. Our results depicted that glycerol is a better stabilizer than sorbitol in the presence of hydrophobic solvents (n-propanol), whereas sorbitol is a better stabilizer than glycerol in the presence of hydrophilic solvents (methanol). © 2015 International Union of Biochemistry and Molecular Biology, Inc.

Dephasing dynamics in confined myoglobin

NASA Astrophysics Data System (ADS)

Goj, Anne; Loring, Roger F.

2007-11-01

Confinement of a solution can slow solvent dynamics and in turn influence the reactivity and structure of the solute. Encapsulating a protein in an aqueous pore affects its binding properties, stability to degradation, interconversion between conformational states, and energy relaxation. We perform molecular dynamics simulations of H64V-CO mutant myoglobin solvated by varying amounts of liquid water, and in turn enclosed by a matrix of immobilized solvent, to mimic differing degrees of confinement of H64V-CO in a glass. We calculate the three-pulse vibrational echo signal of the CO ligand from the autocorrelation function of fluctuations in the CO vibrational frequency. When the first solvation layer alone is free to relax, the correlation function displays only fast relaxation reminiscent of the case of a protein in a fixed, immobilized solvent matrix. However the vibrational echo signal in this case decays significantly more rapidly than for a static solvent. With two solvation layers mobile, the correlation function displays long time relaxation characteristic of the unconfined protein and the echo signal decays rapidly. The echo signal of the protein with two mobile solvation layers is nearly identical to that of the unconfined protein, despite the substantially constrained solvent dynamics in the confined case.

Spin-density fluctuations and the fluctuation-dissipation theorem in 3 d ferromagnetic metals

DOE PAGES

Wysocki, Alex L.; Valmispild, V. N.; Kutepov, A.; ...

2017-11-15

Spatial and time scales of spin-density fluctuations (SDFs) were analyzed in 3d ferromagnets using ab initio linear-response calculations of complete wave-vector and energy dependence of the dynamic spin susceptibility tensor. We demonstrate that SDFs are spread continuously over the entire Brillouin zone and while the majority of them reside within the 3d bandwidth, a significant amount comes from much higher energies. A validity of the adiabatic approximation in spin dynamics is discussed. The SDF spectrum is shown to have two main constituents: a minor low-energy spin-wave contribution and a much larger high-energy component from more localized excitations. Furthermore, using themore » fluctuation-dissipation theorem, the on-site spin correlator and the related effective fluctuating moment were properly evaluated and their universal dependence on the 3d band population is further discussed.« less

Origin of Stability in Particle Sedimentation

NASA Technical Reports Server (NTRS)

Segre, Philip N.

2003-01-01

Particle Image Velocimetry (PIV) is used to study the slow settling motions of spheres in suspensions ranging from dilute to highly concentrated, 0.0001 less than phi less than 0.50. During sedimentation, particle velocity fluctuations are found to be organized into regions of characteristic size xi approximately 11 a phi (exp -1/3). A simple model, based upon buoyant mass fluctuations DELTAm given by random density fluctuations in a region of size xi, accurately predicts the magnitudes of the velocity fluctuations DELTAV. We also find a new universal relation for particle diffusion during sedimentation. It can be written in a Stokes-Einstein form as Dapproximately(DELTAmxi)/(6pietaxi), where the effective temperature DELTAmgxi is the gravitational potential energy of density fluctuations. In addition related experiments examining inertial effects and transient states, that are aimed at uncovering the origin of the new lengthscale xi, will also be given.

Spin-density fluctuations and the fluctuation-dissipation theorem in 3 d ferromagnetic metals

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

Wysocki, Alex L.; Valmispild, V. N.; Kutepov, A.

Spatial and time scales of spin-density fluctuations (SDFs) were analyzed in 3d ferromagnets using ab initio linear-response calculations of complete wave-vector and energy dependence of the dynamic spin susceptibility tensor. We demonstrate that SDFs are spread continuously over the entire Brillouin zone and while the majority of them reside within the 3d bandwidth, a significant amount comes from much higher energies. A validity of the adiabatic approximation in spin dynamics is discussed. The SDF spectrum is shown to have two main constituents: a minor low-energy spin-wave contribution and a much larger high-energy component from more localized excitations. Furthermore, using themore » fluctuation-dissipation theorem, the on-site spin correlator and the related effective fluctuating moment were properly evaluated and their universal dependence on the 3d band population is further discussed.« less

Langmuir Probe Distortions and Probe Compensation in an Inductively Coupled Plasma

NASA Technical Reports Server (NTRS)

Ji, J. S.; Cappelli, M. A.; Kim, J. S.; Rao, M. V. V. S.; Sharma, S. P.

1999-01-01

In many RF discharges, Langmuir probe measurements are usually made against a background of sinusoidal (and not so sinusoidal) fluctuations in the plasma parameters such as the plasma potential (Vp), the electron number density (ne), and the electron temperature (Te). The compensation of sinusoidal fluctuations in Vp has been extensively studied and is relatively well understood. Less attention has been paid to the possible distortions introduced by small fluctuations in plasma density and/or plasma temperature, which may arise in the sheath and pre-sheath regions of RF discharges. Here, we present the results of a model simulation of probe characteristics subject to fluctuations in both Vp and ne. The modeling of probe distortion due to possible fluctuations in Te is less straightforward. A comparison is presented of calculations with experimental measurements using a compensated and uncompensated Langmuir probe in an inductively coupled GEC reference cell plasma, operating on Ar and Ar/CF4 mixtures. The plasma parameters determined from the compensated probe characteristics are compared to previous measurements of others made in similar discharges, and to our own measurements of the average electron density derived from electrical impedance measurements.

Enhanced hyperuniformity from random reorganization.

PubMed

Hexner, Daniel; Chaikin, Paul M; Levine, Dov

2017-04-25

Diffusion relaxes density fluctuations toward a uniform random state whose variance in regions of volume [Formula: see text] scales as [Formula: see text] Systems whose fluctuations decay faster, [Formula: see text] with [Formula: see text], are called hyperuniform. The larger [Formula: see text], the more uniform, with systems like crystals achieving the maximum value: [Formula: see text] Although finite temperature equilibrium dynamics will not yield hyperuniform states, driven, nonequilibrium dynamics may. Such is the case, for example, in a simple model where overlapping particles are each given a small random displacement. Above a critical particle density [Formula: see text], the system evolves forever, never finding a configuration where no particles overlap. Below [Formula: see text], however, it eventually finds such a state, and stops evolving. This "absorbing state" is hyperuniform up to a length scale [Formula: see text], which diverges at [Formula: see text] An important question is whether hyperuniformity survives noise and thermal fluctuations. We find that hyperuniformity of the absorbing state is not only robust against noise, diffusion, or activity, but that such perturbations reduce fluctuations toward their limiting behavior, [Formula: see text], a uniformity similar to random close packing and early universe fluctuations, but with arbitrary controllable density.

Ultraviolet luminosity density of the universe during the epoch of reionization

PubMed Central

Mitchell-Wynne, Ketron; Cooray, Asantha; Gong, Yan; Ashby, Matthew; Dolch, Timothy; Ferguson, Henry; Finkelstein, Steven; Grogin, Norman; Kocevski, Dale; Koekemoer, Anton; Primack, Joel; Smidt, Joseph

2015-01-01

The spatial fluctuations of the extragalactic background light trace the total emission from all stars and galaxies in the Universe. A multiwavelength study can be used to measure the integrated emission from first galaxies during reionization when the Universe was about 500 million years old. Here we report arcmin-scale spatial fluctuations in one of the deepest sky surveys with the Hubble Space Telescope in five wavebands between 0.6 and 1.6 μm. We model-fit the angular power spectra of intensity fluctuation measurements to find the ultraviolet luminosity density of galaxies at redshifts greater than 8 to be . This level of integrated light emission allows for a significant surface density of fainter primeval galaxies that are below the point-source detection level in current surveys. PMID:26348033

Ultraviolet luminosity density of the universe during the epoch of reionization

NASA Astrophysics Data System (ADS)

Mitchell-Wynne, Ketron; Cooray, Asantha; Gong, Yan; Ashby, Matthew; Dolch, Timothy; Ferguson, Henry; Finkelstein, Steven; Grogin, Norman; Kocevski, Dale; Koekemoer, Anton; Primack, Joel; Smidt, Joseph

2015-09-01

The spatial fluctuations of the extragalactic background light trace the total emission from all stars and galaxies in the Universe. A multiwavelength study can be used to measure the integrated emission from first galaxies during reionization when the Universe was about 500 million years old. Here we report arcmin-scale spatial fluctuations in one of the deepest sky surveys with the Hubble Space Telescope in five wavebands between 0.6 and 1.6 μm. We model-fit the angular power spectra of intensity fluctuation measurements to find the ultraviolet luminosity density of galaxies at redshifts greater than 8 to be . This level of integrated light emission allows for a significant surface density of fainter primeval galaxies that are below the point-source detection level in current surveys.

Drift of Phase Fluctuations in the ABC Model

NASA Astrophysics Data System (ADS)

Bertini, Lorenzo; Buttà, Paolo

2013-07-01

In a recent work, Bodineau and Derrida analyzed the phase fluctuations in the ABC model. In particular, they computed the asymptotic variance and, on the basis of numerical simulations, they conjectured the presence of a drift, which they guessed to be an antisymmetric function of the three densities. By assuming the validity of the fluctuating hydrodynamic approximation, we prove the presence of such a drift, providing an analytical expression for it. This expression is then shown to be an antisymmetric function of the three densities. The antisymmetry of the drift can also be inferred from a symmetry property of the underlying microscopic dynamics.

High-sensitivity density fluctuation detector

NASA Technical Reports Server (NTRS)

Azzazy, M.; Modarress, D.; Hoeft, T.

1987-01-01

A high-sensitivity differential interferometer has been developed to detect small density fluctuations over an optical path length of the order of the boundary layer thickness near transition. Two experimental configurations have been used to evaluate the performance of the interferometer: an open shear-layer configuration and a wind-tunnel turbulent spot configuration. In each experiment small temperature fluctuations were introduced as the signal source. Simultaneous cold-wire measurements have been compared with the interferometer data. The comparison shows that the interferometer is sensitive to very weak phase variations of the order of 0.001 of the laser wavelength.

Joint constraints on galaxy bias and σ{sub 8} through the N-pdf of the galaxy number density

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

Arnalte-Mur, Pablo; Martínez, Vicent J.; Vielva, Patricio

We present a full description of the N-probability density function of the galaxy number density fluctuations. This N-pdf is given in terms, on the one hand, of the cold dark matter correlations and, on the other hand, of the galaxy bias parameter. The method relies on the assumption commonly adopted that the dark matter density fluctuations follow a local non-linear transformation of the initial energy density perturbations. The N-pdf of the galaxy number density fluctuations allows for an optimal estimation of the bias parameter (e.g., via maximum-likelihood estimation, or Bayesian inference if there exists any a priori information on themore » bias parameter), and of those parameters defining the dark matter correlations, in particular its amplitude (σ{sub 8}). It also provides the proper framework to perform model selection between two competitive hypotheses. The parameters estimation capabilities of the N-pdf are proved by SDSS-like simulations (both, ideal log-normal simulations and mocks obtained from Las Damas simulations), showing that our estimator is unbiased. We apply our formalism to the 7th release of the SDSS main sample (for a volume-limited subset with absolute magnitudes M{sub r} ≤ −20). We obtain b-circumflex  = 1.193 ± 0.074 and σ-bar{sub 8} = 0.862 ± 0.080, for galaxy number density fluctuations in cells of the size of 30h{sup −1}Mpc. Different model selection criteria show that galaxy biasing is clearly favoured.« less

Correlated isocurvature fluctuation in quintessence and suppressed cosmic microwave background anisotropies at low multipoles.

PubMed

Moroi, Takeo; Takahashi, Tomo

2004-03-05

We consider cosmic microwave background (CMB) anisotropy in models with quintessence, taking into account isocurvature fluctuation. It is shown that, if the primordial fluctuation of the quintessence has a correlation with the adiabatic density fluctuations, the CMB angular power spectrum C(l) at low multipoles can be suppressed without affecting C(l) at high multipoles. A possible scenario for generating a correlated mixture of the quintessence and adiabatic fluctuations is also discussed.

Spontaneous density fluctuations in granular flow and traffic

NASA Astrophysics Data System (ADS)

Herrmann, Hans J.

It is known that spontaneous density waves appear in granular material flowing through pipes or hoppers. A similar phenomenon is known from traffic jams on highways. Using numerical simulations we show that several types of waves exist and find that the density fluctuations follow a power law spectrum. We also investigate one-dimensional traffic models. If positions and velocities are continuous variables the model shows self-organized criticality driven by the slowest car. Lattice gas and lattice Boltzmann models reproduce the experimentally observed effects. Density waves are spontaneously generated when the viscosity has a non-linear dependence on density or shear rate as it is the case in traffic or granular flow.

Nitropyrroles, Diels-Alder reactions assisted by microwave irradiation and solvent effect. An experimental and theoretical study

NASA Astrophysics Data System (ADS)

Mancini, Pedro M. E.; Kneeteman, María N.; Cainelli, Mauro; Ormachea, Carla M.; Domingo, Luis R.

2017-11-01

The behaviors of N-tosylnitropyrroles acting as electrophilic dienophiles in polar Diels-Alder reactions joint to different dienes of increeased nucleophilicity are analyzed. The reactions were developed under microwave irradiation using toluene or protic ionic liquids (PILs) as solvents and in free solvent conditions. In all the cases explored we observed good yields in short reaction times. For these reactions, the free solvent condition and the use of protic ionic liquids as solvents offer similar results. However, the free solvent conditions favor environmental sustainability. The role of PILs in these polar Diels-Alder reactions has been theoretically studied within the Molecular Electron Density Theory.

Thermoplastic composite matrices with improved solvent resistance

NASA Technical Reports Server (NTRS)

Hergenrother, P. M.; Jensen, B. J.; Havens, S. J.

1984-01-01

In order to improve solvent resistance of aromatic thermoplastic polymers, ethynyl-terminated aromatic sulfone polymers (ETS), sulfone/ester polymers (SEPE) containing pendent ethynyl groups, and phenoxy resin containing pendent ethynyl groups are synthesized. Cured polysulfones and phenoxy resins containing ethynyl groups on the ends or pendent on the molecules exhibited systematic behavior in solvent resistance, film flexibility, and toughness as a function of crosslink density. The film and composite properties of a cured solvent-resistant ETS were better than those of a commercially available solvent sensitive polysulfone. The study was part of a NASA program to better understand the trade-offs between solvent resistance, processability and mechanical properties which may be useful in designing composite structures for aerospace vehicles.

Droplet-Based Production of Liposomes

NASA Technical Reports Server (NTRS)

Ackley, Donald E.; Forster, Anita

2009-01-01

A process for making monodisperse liposomes having lipid bilayer membranes involves fewer, simpler process steps than do related prior methods. First, a microfluidic, cross junction droplet generator is used to produce vesicles comprising aqueous solution droplets contained in single layer lipid membranes. The vesicles are collected in a lipid-solvent mix that is at most partially soluble in water and is less dense than is water. A layer of water is dispensed on top of the solvent. By virtue of the difference in densities, the water sinks to the bottom and the solvent floats to the top. The vesicles, which have almost the same density as that of water, become exchanged into the water instead of floating to the top. As there are excess lipids in the solvent solution, in order for the vesicles to remain in the water, the addition of a second lipid layer to each vesicle is energetically favored. The resulting lipid bilayers present the hydrophilic ends of the lipid molecules to both the inner and outer membrane surfaces. If lipids of a second kind are dissolved in the solvent in sufficient excess before use, then asymmetric liposomes may be formed.

Extraction of basil leaves (ocimum canum) oleoresin with ethyl acetate solvent by using soxhletation method

NASA Astrophysics Data System (ADS)

Tambun, R.; Purba, R. R. H.; Ginting, H. K.

2017-09-01

The goal of this research is to produce oleoresin from basil leaves (Ocimum canum) by using soxhletation method and ethyl acetate as solvent. Basil commonly used in culinary as fresh vegetables. Basil contains essential oils and oleoresin that are used as flavouring agent in food, in cosmetic and ingredient in traditional medicine. The extraction method commonly used to obtain oleoresin is maceration. The problem of this method is many solvents necessary and need time to extract the raw material. To resolve the problem and to produce more oleoresin, we use soxhletation method with a combination of extraction time and ratio from the material with a solvent. The analysis consists of yield, density, refractive index, and essential oil content. The best treatment of basil leaves oleoresin extraction is at ratio of material and solvent 1:6 (w / v) for 6 hours extraction time. In this condition, the yield of basil oleoresin is 20.152%, 0.9688 g/cm3 of density, 1.502 of refractive index, 15.77% of essential oil content, and the colour of oleoresin product is dark-green.

Ion isotropy and fluctuations in the solar wind

NASA Technical Reports Server (NTRS)

Kellogg, Paul J.; Lin, Naiguo

1997-01-01

The effects of measured fluctuations, with only general considerations as to their source, are considered. Data from interplanetary scintillations and fluctuations in plasma density provided data on electric fields, while fluctuations in magnetic fields are measured directly. Data from the unified radio and plasma experiment (URAP) on Ulysses is used to fill in higher frequency ranges, to assess the variations in the fluctuations with time and space, and to help to identify wave modes. It is shown that electric field fluctuations are of the right order of magnitude to maintain ion isotropy.

Binary collision approximations for the memory function for density fluctuations in equilibrium atomic liquids

NASA Astrophysics Data System (ADS)

Noah, Joyce E.

Time correlation functions of density fluctuations of liquids at equilibrium can be used to relate the microscopic dynamics of a liquid to its macroscopic transport properties. Time correlation functions are especially useful since they can be generated in a variety of ways, from scattering experiments to computer simulation to analytic theory. The kinetic theory of fluctuations in equilibrium liquids is an analytic theory for calculating correlation functions using memory functions. In this work, we use a diagrammatic formulation of the kinetic theory to develop a series of binary collision approximations for the collisional part of the memory function. We define binary collisions as collisions between two distinct density fluctuations whose identities are fixed during the duration of a collsion. R approximations are for the short time part of the memory function, and build upon the work of Ranganathan and Andersen. These approximations have purely repulsive interactions between the fluctuations. The second type of approximation, RA approximations, is for the longer time part of the memory function, where the density fluctuations now interact via repulsive and attractive forces. Although RA approximations are a natural extension of R approximations, they permit two density fluctuations to become trapped in the wells of the interaction potential, leading to long-lived oscillatory behavior, which is unphysical. Therefore we consider S approximations which describe binary particles which experience the random effect of the surroundings while interacting via repulsive or repulsive and attractive interactions. For each of these approximations for the memory function we numerically solve the kinetic equation to generate correlation functions. These results are compared to molecular dynamics results for the correlation functions. Comparing the successes and failures of the different approximations, we conclude that R approximations give more accurate intermediate and long time results while RA and S approximations do particularly well at predicting the short time behavior. Lastly, we also develop a series of non-graphically derived approximations and use an optimization procedure to determine the underlying memory function from the simulation data. These approaches provide valuable information about the memory function that will be used in the development of future kinetic theories.

Compressed air-assisted solvent extraction (CASX) for metal removal.

PubMed

Li, Chi-Wang; Chen, Yi-Ming; Hsiao, Shin-Tien

2008-03-01

A novel process, compressed air-assisted solvent extraction (CASX), was developed to generate micro-sized solvent-coated air bubbles (MSAB) for metal extraction. Through pressurization of solvent with compressed air followed by releasing air-oversaturated solvent into metal-containing wastewater, MSAB were generated instantaneously. The enormous surface area of MSAB makes extraction process extremely fast and achieves very high aqueous/solvent weight ratio (A/S ratio). CASX process completely removed Cr(VI) from acidic electroplating wastewater under A/S ratio of 115 and extraction time of less than 10s. When synthetic wastewater containing Cd(II) of 50mgl(-1) was treated, A/S ratios of higher than 714 and 1190 could be achieved using solvent with extractant/diluent weight ratio of 1:1 and 5:1, respectively. Also, MSAB have very different physical properties, such as size and density, compared to the emulsified solvent droplets, making separation and recovery of solvent from treated effluent very easy.

Face-Dependent Solvent Adsorption: A Comparative Study on the Interfaces of HMX Crystal with Three Solvents.

PubMed

Liu, Yingzhe; Lai, Weipeng; Ma, Yiding; Yu, Tao; Kang, Ying; Ge, Zhongxue

2017-07-27

To understand the crystal-solvent interfacial interactions on the molecular scale, the interfaces between three solvents, that is, acetone, γ-butyrolactone, and cyclohexanone, and three growth faces of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) crystal have been investigated with the aid of theoretical chemistry. The results show that the structural features of crystal faces play a critical role in the energetic, structural, and dynamic properties at the interfaces. For each solvent, the same change trend of some properties among the three faces of HMX crystal is observed, including adsorption affinity, local mass density, and solvent diffusion. For example, the rate of solvent diffusion at the three faces ranks as (011) > (110) > (020) regardless of solvent species. This can be attributed to the similar adsorption sites for solvent incorporation at the same face, which are concentrated at the cavities formed by surficial HMX molecules.

The local phase transitions of the solvent in the neighborhood of a solvophobic polymer at high pressures

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

Budkov, Yu. A., E-mail: urabudkov@rambler.ru; National Research University Higher School of Economics, Moscow; Department of Chemistry, Lomonosov Moscow State University, Moscow

2014-11-28

We investigate local phase transitions of the solvent in the neighborhood of a solvophobic polymer chain which is induced by a change of the polymer-solvent repulsion and the solvent pressure in the bulk solution. We describe the polymer in solution by the Edwards model, where the conditional partition function of the polymer chain at a fixed radius of gyration is described by a mean-field theory. The contributions of the polymer-solvent and the solvent-solvent interactions to the total free energy are described within the mean-field approximation. We obtain the total free energy of the solution as a function of the radiusmore » of gyration and the average solvent number density within the gyration volume. The resulting system of coupled equations is solved varying the polymer-solvent repulsion strength at high solvent pressure in the bulk. We show that the coil-globule (globule-coil) transition occurs accompanied by a local solvent evaporation (condensation) within the gyration volume.« less

Water equivalence of NIPAM based polymer gel dosimeters with enhanced sensitivity for x-ray CT

NASA Astrophysics Data System (ADS)

Gorjiara, Tina; Hill, Robin; Bosi, Stephen; Kuncic, Zdenka; Baldock, Clive

2013-10-01

Two new formulations of N-isopropylacrylamide (NIPAM) based three dimensional (3D) gel dosimeters have recently been developed with improved sensitivity to x-ray CT readout, one without any co-solvent and the other one with isopropanol co-solvent. The water equivalence of the NIPAM gel dosimeters was investigated using different methods to calculate their radiological properties including: density, electron density, number of electrons per grams, effective atomic number, photon interaction probabilities, mass attenuation and energy absorption coefficients, electron collisional, radiative and total mass stopping powers and electron mass scattering power. Monte Carlo modelling was also used to compare the dose response of these gel dosimeters with water for kilovoltage and megavoltage x-ray beams and for megavoltage electron beams. We found that the density and electron density of the co-solvent free gel dosimeter are more water equivalent with less than a 2.6% difference compared to a 5.7% difference for the isopropanol gel dosimeter. Both the co-solvent free and isopropanol solvent gel dosimeters have lower effective atomic numbers than water, differing by 2.2% and 6.5%, respectively. As a result, their photoelectric absorption interaction probabilities are up to 6% and 19% different from water, respectively. Compton scattering and pair production interaction probabilities of NIPAM gel with isopropanol differ by up to 10% from water while for the co-solvent free gel, the differences are 3%. Mass attenuation and energy absorption coefficients of the co-solvent free gel dosimeter and the isopropanol gel dosimeter are up to 7% and 19% lower than water, respectively. Collisional and total mass stopping powers of both gel dosimeters differ by less than 2% from those of water. The dose response of the co-solvent free gel dosimeter is water equivalent (with <1% discrepancy) for dosimetry of x-rays with energies <100 keV while the discrepancy increases (up to 5%) for the isopropanol gel dosimeter over the same energy range. For x-ray beams over the energy range 180 keV-18 MV, both gel dosimeters have less than 2% discrepancy with water. For megavoltage electron beams, the dose differences with water reach 7% and 14% for the co-solvent free gel dosimeter and the isopropanol gel dosimeter, respectively. Our results demonstrate that for x-ray beam dosimetry with photon energies higher than 100 keV and megavoltage electron beams, correction factors are needed for both NIPAM gels to be used as water equivalent dosimeters.

Anion-π aromatic neutral tweezers complexes: are they stable in polar solvents?

PubMed

Sánchez-Lozano, Marta; Otero, Nicolás; Hermida-Ramón, Jose M; Estévez, Carlos M; Mandado, Marcos

2011-03-17

The impact of the solvent environment on the stabilization of the complexes formed by fluorine (T-F) and cyanide (T-CN) substituted tweezers with halide anions has been investigated theoretically. The study was carried out using computational methodologies based on density functional theory (DFT) and symmetry adapted perturbation theory (SAPT). Interaction energies were obtained at the M05-2X/6-31+G* level. The obtained results show a large stability of the complexes in solvents with large dielectric constant and prove the suitability of these molecular tweezers as potential hosts for anion recognition in solution. A detailed analysis of the effects of the solvent on the electron withdrawing ability of the substituents and its influence on the complex stability has been performed. In particular, the interaction energy in solution was split up into intermonomer and solvent-complex terms. In turn, the intermonomer interaction energy was partitioned into electrostatic, exchange, and polarization terms. Polar resonance structures in T-CN complexes are favored by polar solvents, giving rise to a stabilization of the intermonomer interaction, the opposite is found for T-F complexes. The solvent-complex energy increases with the polarity of the solvent in T-CN complexes, nonetheless the energy reaches a maximum and then decreases slowly in T-F complexes. An electron density analysis was also performed before and after complexation, providing an explanation to the trends followed by the interaction energies and their different components in solution.

Low-density microcellular foam and method of making same

DOEpatents

Rinde, James A.

1977-01-01

Low-density microcellular foam having a cell size of not greater than 2 .mu.m and method of making by dissolving cellulose acetate in an acetone-based solvent, gelling the solution in a water bath maintained at 0.degree.-10.degree. C for a selected period of time to allow impurities to diffuse out, freezing the gel, and then freeze-drying wherein water and solvents sublime and the gel structure solidifies into low-density microcellular foam. The foam has a density of 0.065 to 0.6.times.10.sup.3 kg/m.sup.3 and cell size of about 0.3 to 2 .mu.m. The small cell size foam is particularly applicable for encapsulation of laser targets.

Method of making a cellulose acetate low density microcellular foam

DOEpatents

Rinde, James A.

1978-01-01

Low-density microcellular foam having a cell size of not greater than 2 .mu.m and method of making by dissolving cellulose acetate in an acetone-based solvent, gelling the solution in a water bath maintained at 0-10.degree. C for a selected period of time to allow impurities to diffuse out, freezing the gel, and then freeze-drying wherein water and solvents sublime and the gel structure solidifies into low-density microcellular foam. The foam has a density of 0.065 to 0.6.times.10.sup.3 kg/m.sup.3 and cell size of about 0.3 to 2 .mu.m. The small cell size foam is particularly adaptable for encapsulation of laser targets.

Differential geometry-based solvation and electrolyte transport models for biomolecular modeling: a review

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

Wei, Guowei; Baker, Nathan A.

2016-11-11

This chapter reviews the differential geometry-based solvation and electrolyte transport for biomolecular solvation that have been developed over the past decade. A key component of these methods is the differential geometry of surfaces theory, as applied to the solvent-solute boundary. In these approaches, the solvent-solute boundary is determined by a variational principle that determines the major physical observables of interest, for example, biomolecular surface area, enclosed volume, electrostatic potential, ion density, electron density, etc. Recently, differential geometry theory has been used to define the surfaces that separate the microscopic (solute) domains for biomolecules from the macroscopic (solvent) domains. In thesemore » approaches, the microscopic domains are modeled with atomistic or quantum mechanical descriptions, while continuum mechanics models (including fluid mechanics, elastic mechanics, and continuum electrostatics) are applied to the macroscopic domains. This multiphysics description is integrated through an energy functional formalism and the resulting Euler-Lagrange equation is employed to derive a variety of governing partial differential equations for different solvation and transport processes; e.g., the Laplace-Beltrami equation for the solvent-solute interface, Poisson or Poisson-Boltzmann equations for electrostatic potentials, the Nernst-Planck equation for ion densities, and the Kohn-Sham equation for solute electron density. Extensive validation of these models has been carried out over hundreds of molecules, including proteins and ion channels, and the experimental data have been compared in terms of solvation energies, voltage-current curves, and density distributions. We also propose a new quantum model for electrolyte transport.« less

Accurate theoretical prediction of vibrational frequencies in an inhomogeneous dynamic environment: A case study of a glutamate molecule in water solution and in a protein-bound form

PubMed Central

Speranskiy, Kirill; Kurnikova, Maria

2012-01-01

We propose a hierarchical approach to model vibrational frequencies of a ligand in a strongly fluctuating inhomogeneous environment such as a liquid solution or when bound to a macromolecule, e.g., a protein. Vibrational frequencies typically measured experimentally are ensemble averaged quantities which result (in part) from the influence of the strongly fluctuating solvent. Solvent fluctuations can be sampled effectively by a classical molecular simulation, which in our model serves as the first, low level of the hierarchy. At the second high level of the hierarchy a small subset of system coordinates is used to construct a patch of the potential surface (ab initio) relevant to the vibration in question. This subset of coordinates is under the influence of an instantaneous external force exerted by the environment. The force is calculated at the lower level of the hierarchy. The proposed methodology is applied to model vibrational frequencies of a glutamate in water and when bound to the Glutamate receptor protein and its mutant. Our results are in close agreement with the experimental values and frequency shifts measured by the Jayaraman group by the Fourier transform infrared spectroscopy [Q. Cheng et al., Biochem. 41, 1602 (2002)]. Our methodology proved useful in successfully reproducing vibrational frequencies of a ligand in such a soft, flexible, and strongly inhomogeneous protein as the Glutamate receptor. PMID:15260697

Polder maps: Improving OMIT maps by excluding bulk solvent

DOE PAGES

Liebschner, Dorothee; Afonine, Pavel V.; Moriarty, Nigel W.; ...

2017-02-01

The crystallographic maps that are routinely used during the structure-solution workflow are almost always model-biased because model information is used for their calculation. As these maps are also used to validate the atomic models that result from model building and refinement, this constitutes an immediate problem: anything added to the model will manifest itself in the map and thus hinder the validation. OMIT maps are a common tool to verify the presence of atoms in the model. The simplest way to compute an OMIT map is to exclude the atoms in question from the structure, update the corresponding structure factorsmore » and compute a residual map. It is then expected that if these atoms are present in the crystal structure, the electron density for the omitted atoms will be seen as positive features in this map. This, however, is complicated by the flat bulk-solvent model which is almost universally used in modern crystallographic refinement programs. This model postulates constant electron density at any voxel of the unit-cell volume that is not occupied by the atomic model. Consequently, if the density arising from the omitted atoms is weak then the bulk-solvent model may obscure it further. A possible solution to this problem is to prevent bulk solvent from entering the selected OMIT regions, which may improve the interpretative power of residual maps. This approach is called a polder (OMIT) map. Polder OMIT maps can be particularly useful for displaying weak densities of ligands, solvent molecules, side chains, alternative conformations and residues both in terminal regions and in loops. As a result, the tools described in this manuscript have been implemented and are available in PHENIX.« less

Thermal Density Functional Theory: Time-Dependent Linear Response and Approximate Functionals from the Fluctuation-Dissipation Theorem

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

Pribram-Jones, Aurora; Grabowski, Paul E.; Burke, Kieron

We present that the van Leeuwen proof of linear-response time-dependent density functional theory (TDDFT) is generalized to thermal ensembles. This allows generalization to finite temperatures of the Gross-Kohn relation, the exchange-correlation kernel of TDDFT, and fluctuation dissipation theorem for DFT. Finally, this produces a natural method for generating new thermal exchange-correlation approximations.

Thermal Density Functional Theory: Time-Dependent Linear Response and Approximate Functionals from the Fluctuation-Dissipation Theorem

DOE PAGES

Pribram-Jones, Aurora; Grabowski, Paul E.; Burke, Kieron

2016-06-08

We present that the van Leeuwen proof of linear-response time-dependent density functional theory (TDDFT) is generalized to thermal ensembles. This allows generalization to finite temperatures of the Gross-Kohn relation, the exchange-correlation kernel of TDDFT, and fluctuation dissipation theorem for DFT. Finally, this produces a natural method for generating new thermal exchange-correlation approximations.

Helical variation of density profiles and fluctuations in the tokamak pedestal with applied 3D fields and implications for confinement

DOE PAGES

Wilcox, R. S.; Rhodes, T. L.; Shafer, M. W.; ...

2018-04-19

Smore » mall 3D perturbations to the magnetic field in DIII-D ( δ B / B ~ 2 × 10 - 4 ) result in large modulations of density fluctuation amplitudes in the pedestal, which are shown using Doppler backscattering measurements to vary by a factor of 2. Helical perturbations of equilibrium density within flux surfaces have previously been observed in the pedestal of DIII-D plasmas when 3D fields are applied and were correlated with density fluctuation asymmetries in the pedestal. These intra-surface density and pressure variations are shown through two fluid MHD modeling studies using the M3D-C1 code to be due to the misalignment of the density and temperature equilibrium iso-surfaces in the pedestal region. This modeling demonstrates that the phase shift between the two iso-surfaces corresponds to the diamagnetic direction of the two species, with the mass density surfaces shifted in the ion diamagnetic direction relative to the temperature and magnetic flux iso-surfaces. Finally, the resulting pedestal density, potential, and turbulence asymmetries within flux surfaces near the separatrix may be at least partially responsible for several poorly understood phenomena that occur with the application of 3D fields in tokamaks, including density pump out and the increase in power required to transition from L- to H-mode.« less

Helical variation of density profiles and fluctuations in the tokamak pedestal with applied 3D fields and implications for confinement

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

Wilcox, R. S.; Rhodes, T. L.; Shafer, M. W.

Smore » mall 3D perturbations to the magnetic field in DIII-D ( δ B / B ~ 2 × 10 - 4 ) result in large modulations of density fluctuation amplitudes in the pedestal, which are shown using Doppler backscattering measurements to vary by a factor of 2. Helical perturbations of equilibrium density within flux surfaces have previously been observed in the pedestal of DIII-D plasmas when 3D fields are applied and were correlated with density fluctuation asymmetries in the pedestal. These intra-surface density and pressure variations are shown through two fluid MHD modeling studies using the M3D-C1 code to be due to the misalignment of the density and temperature equilibrium iso-surfaces in the pedestal region. This modeling demonstrates that the phase shift between the two iso-surfaces corresponds to the diamagnetic direction of the two species, with the mass density surfaces shifted in the ion diamagnetic direction relative to the temperature and magnetic flux iso-surfaces. Finally, the resulting pedestal density, potential, and turbulence asymmetries within flux surfaces near the separatrix may be at least partially responsible for several poorly understood phenomena that occur with the application of 3D fields in tokamaks, including density pump out and the increase in power required to transition from L- to H-mode.« less

Helical variation of density profiles and fluctuations in the tokamak pedestal with applied 3D fields and implications for confinement

NASA Astrophysics Data System (ADS)

Wilcox, R. S.; Rhodes, T. L.; Shafer, M. W.; Sugiyama, L. E.; Ferraro, N. M.; Lyons, B. C.; McKee, G. R.; Paz-Soldan, C.; Wingen, A.; Zeng, L.

2018-05-01

Small 3D perturbations to the magnetic field in DIII-D ( δB /B ˜2 ×10-4 ) result in large modulations of density fluctuation amplitudes in the pedestal, which are shown using Doppler backscattering measurements to vary by a factor of 2. Helical perturbations of equilibrium density within flux surfaces have previously been observed in the pedestal of DIII-D plasmas when 3D fields are applied and were correlated with density fluctuation asymmetries in the pedestal. These intra-surface density and pressure variations are shown through two fluid MHD modeling studies using the M3D-C1 code to be due to the misalignment of the density and temperature equilibrium iso-surfaces in the pedestal region. This modeling demonstrates that the phase shift between the two iso-surfaces corresponds to the diamagnetic direction of the two species, with the mass density surfaces shifted in the ion diamagnetic direction relative to the temperature and magnetic flux iso-surfaces. The resulting pedestal density, potential, and turbulence asymmetries within flux surfaces near the separatrix may be at least partially responsible for several poorly understood phenomena that occur with the application of 3D fields in tokamaks, including density pump out and the increase in power required to transition from L- to H-mode.

Current Fluctuations in Stochastic Lattice Gases

NASA Astrophysics Data System (ADS)

Bertini, L.; de Sole, A.; Gabrielli, D.; Jona-Lasinio, G.; Landim, C.

2005-01-01

We study current fluctuations in lattice gases in the macroscopic limit extending the dynamic approach for density fluctuations developed in previous articles. More precisely, we establish a large deviation theory for the space-time fluctuations of the empirical current which include the previous results. We then estimate the probability of a fluctuation of the average current over a large time interval. It turns out that recent results by Bodineau and Derrida [Phys. Rev. Lett.922004180601] in certain cases underestimate this probability due to the occurrence of dynamical phase transitions.

Evolution of Structure in the Intergalactic Medium and the Nature of the LY-Alpha Forest

NASA Technical Reports Server (NTRS)

Bi, Hongguang; Davidsen, Arthur F.

1997-01-01

We have performed a detailed statistical study of the evolution of structure in a photoionized intergalactic medium (IGM) using analytical simulations to extend the calculation into the mildly nonlinear density regime found to prevail at z = 3. Our work is based on a simple fundamental conjecture: that the probability distribution function of the density of baryonic diffuse matter in the universe is described by a lognormal (LN) random field. The LN distribution has several attractive features and follows plausibly from the assumption of initial linear Gaussian density and velocity fluctuations at arbitrarily early times. Starting with a suitably normalized power spectrum of primordial fluctuations in a universe dominated by cold dark matter (CDM), we compute the behavior of the baryonic matter, which moves slowly toward minima in the dark matter potential on scales larger than the Jeans length. We have computed two models that succeed in matching observations. One is a nonstandard CDM model with OMEGA = 1, h = 0.5, and GAMMA = 0.3, and the other is a low-density flat model with a cosmological constant (LCDM), with OMEGA = 0.4, OMEGA(sub LAMBDA) = 0.6, and h = 0.65. In both models, the variance of the density distribution function grows with time, reaching unity at about z = 4, where the simulation yields spectra that closely resemble the Ly-alpha forest absorption seen in the spectra of high-z quasars. The calculations also successfully predict the observed properties of the Ly-alpha forest clouds and their evolution from z = 4 down to at least z = 2, assuming a constant intensity for the metagalactic UV background over this redshift range. However, in our model the forest is not due to discrete clouds, but rather to fluctuations in a continuous intergalactic medium. At z = 3; typical clouds with measured neutral hydrogen column densities N(sub H I) = 10(exp 13.3), 10(exp 13.5), and 10(exp 11.5) /sq cm correspond to fluctuations with mean total densities approximately 10, 1, and 0.1 times the universal mean baryon density. Perhaps surprisingly, fluctuations whose amplitudes are less than or equal to the mean density still appear as "clouds" because in our model more than 70% of the volume of the IGM at z = 3 is filled with gas at densities below the mean value.

A simple phenomenological model for grain clustering in turbulence

NASA Astrophysics Data System (ADS)

Hopkins, Philip F.

2016-01-01

We propose a simple model for density fluctuations of aerodynamic grains, embedded in a turbulent, gravitating gas disc. The model combines a calculation for the behaviour of a group of grains encountering a single turbulent eddy, with a hierarchical approximation of the eddy statistics. This makes analytic predictions for a range of quantities including: distributions of grain densities, power spectra and correlation functions of fluctuations, and maximum grain densities reached. We predict how these scale as a function of grain drag time ts, spatial scale, grain-to-gas mass ratio tilde{ρ }, strength of turbulence α, and detailed disc properties. We test these against numerical simulations with various turbulence-driving mechanisms. The simulations agree well with the predictions, spanning ts Ω ˜ 10-4-10, tilde{ρ }˜ 0{-}3, α ˜ 10-10-10-2. Results from `turbulent concentration' simulations and laboratory experiments are also predicted as a special case. Vortices on a wide range of scales disperse and concentrate grains hierarchically. For small grains this is most efficient in eddies with turnover time comparable to the stopping time, but fluctuations are also damped by local gas-grain drift. For large grains, shear and gravity lead to a much broader range of eddy scales driving fluctuations, with most power on the largest scales. The grain density distribution has a log-Poisson shape, with fluctuations for large grains up to factors ≳1000. We provide simple analytic expressions for the predictions, and discuss implications for planetesimal formation, grain growth, and the structure of turbulence.

Feasibility of measuring temperature and density fluctuations in air using laser-induced O2 fluorescence

NASA Technical Reports Server (NTRS)

Massey, G. A.; Lemon, C. J.

1984-01-01

A tunable line-narrowed ArF laser can selectively excite several rotation al lines of the Schumann-Runge band system of O2 in air. The resulting ultraviolet fluorescence can be monitored at 90 deg to the laser beam axis, permitting space and time resolved observation of density and temperature fluctuations in turbulence. Experiments and calculations show that + or - 1 K, + or - 1 percent density, 1 cu mm spatial, and 1 microsecond temporal resolution can be achieved simultaneously under some conditions.

Low-frequency fluctuation spectra and associated particle transport in the NASA Lewis bumpy-torus plasma

NASA Technical Reports Server (NTRS)

Singh, C. M.; Krawczonek, W. M.; Roth, J. R.; Hong, J. Y.; Kim, Y. C.; Powers, E. J.

1978-01-01

The strong radial electric field associated with the Penning discharge and the strong toroidal magnetic field give rise to a diversity of E/B phenomena, such as rotating waves and spokes, which in turn manifest themselves as space-time fluctuations of the plasma density and potential. Work is done to further understand the nature and origin of the fluctuations and their connection with fluctuation-induced transport. The approach is to monitor the density and potential fluctuations; to digitize the data; and to generate, with the aid of a computer, various spectral properties by means of the fast fourier transform. Of particular interest is the computer-generated transport spectrum that indicates in a quantitative way which fluctuation spectral components contribute to transport and which do not. All experimental measurements of the spectral characteristics of the plasma are given in absolute units rather than as relative values. Preliminary measurements of the transport spectrum of the ion population are given, and it is shown that the fluctuation-induced transport is in order-of-magnitude agreement with that inferred from the steady state current flowing to the electrodes that generate the plasma.

Active Brownian particles with velocity-alignment and active fluctuations

NASA Astrophysics Data System (ADS)

Großmann, R.; Schimansky-Geier, L.; Romanczuk, P.

2012-07-01

We consider a model of active Brownian particles (ABPs) with velocity alignment in two spatial dimensions with passive and active fluctuations. Here, active fluctuations refers to purely non-equilibrium stochastic forces correlated with the heading of an individual active particle. In the simplest case studied here, they are assumed to be independent stochastic forces parallel (speed noise) and perpendicular (angular noise) to the velocity of the particle. On the other hand, passive fluctuations are defined by a noise vector independent of the direction of motion of a particle, and may account, for example, for thermal fluctuations. We derive a macroscopic description of the ABP gas with velocity-alignment interaction. Here, we start from the individual-based description in terms of stochastic differential equations (Langevin equations) and derive equations of motion for the coarse-grained kinetic variables (density, velocity and temperature) via a moment expansion of the corresponding probability density function. We focus here on the different impact of active and passive fluctuations on onset of collective motion and show how active fluctuations in the active Brownian dynamics can change the phase-transition behaviour of the system. In particular, we show that active angular fluctuations lead to an earlier breakdown of collective motion and to the emergence of a new bistable regime in the mean-field case.

The effect of Electron Cyclotron Heating on density fluctuations at ion and electron scales in ITER Baseline Scenario discharges on the DIII-D tokamak

DOE PAGES

Marinoni, Alessandro; Pinsker, Robert I.; Porkolab, Miklos; ...

2017-08-01

Experiments simulating the ITER Baseline Scenario on the DIII-D tokamak show that torque-free pure electron heating, when coupled to plasmas subject to a net co-current beam torque, affects density fluctuations at electron scales on a sub-confinement time scale, whereas fluctuations at ion scales change only after profiles have evolved to a new stationary state. Modifications to the density fluctuations measured by the Phase Contrast Imaging diagnostic (PCI) are assessed by analyzing the time evolution following the switch-off of Electron Cyclotron Heating (ECH), thus going from mixed beam/ECH to pure neutral beam heating at fixed β N . Within 20 msmore » after turning off ECH, the intensity of fluctuations is observed to increase at frequencies higher than 200 kHz; in contrast, fluctuations at lower frequency are seen to decrease in intensity on a longer time scale, after other equilibrium quantities have evolved. Non-linear gyro-kinetic modeling at ion and electron scales scales suggest that, while the low frequency response of the diagnostic is consistent with the dominant ITG modes being weakened by the slow-time increase in flow shear, the high frequency response is due to prompt changes to the electron temperature profile that enhance electron modes and generate a larger heat flux and an inward particle pinch. Furthermore, these results suggest that electron heated regimes in ITER will feature multi-scale fluctuations that might affect fusion performance via modifications to profiles.« less

Gas discharge visualization evaluation of ultramolecular doses of homeopathic medicines under blinded, controlled conditions.

PubMed

Bell, Iris R; Lewis, Daniel A; Brooks, Audrey J; Lewis, Sabrina E; Schwartz, Gary E

2003-02-01

To determine the feasibility of using a computerized biophysical method, gas discharge visualization (GDV), to differentiate ultramolecular doses of homeopathic remedies from solvent controls and from each other. Blinded, randomized assessment of four split samples each of 30c potencies of three homeopathic remedies from different kingdoms, for example, Natrum muriaticum (mineral), Pulsatilla (plant), and Lachesis (animal), dissolved in a 20% alcohol-water solvent versus two different control solutions (that is, solvent with untreated lactose/sucrose pellets and unsuccussed solvent alone). GDV measurements, involving application of a brief electrical impulse at four different voltage levels, were performed over 10 successive images on each of 10 drops from each bottle (total 400 images per test solution per voltage). The dependent variables were the quantified image characteristics of the liquid drops (form coefficient, area, and brightness) from the resultant burst of electron-ion emission and optical radiation in the visual and ultraviolet ranges. The procedure generated measurable images at the two highest voltage levels. At 17 kV, the remedies exhibited overall lower image parameter values compared with solvents (significant for Pulsatilla and Lachesis), as well as differences from solvents in fluctuations over repeated images (exposures to the same voltage). At 24 kV, other patterns emerged, with individual remedies showing higher or lower image parameters compared with other remedies and the solvent controls. GDV technology may provide an electromagnetic probe into the properties of homeopathic remedies as distinguished from solvent controls. However, the present findings also highlight the need for additional research to evaluate factors that may affect reproducibility of results.

Measurements of density, temperature, and their fluctuations in turbulent supersonic flow using UV laser spectroscopy

NASA Technical Reports Server (NTRS)

Fletcher, Douglas G.; Mckenzie, R. L.

1992-01-01

Nonintrusive measurements of density, temperature, and their turbulent fluctuation levels were obtained in the boundary layer of an unseeded, Mach 2 wind tunnel flow. The spectroscopic technique that was used to make the measurements is based on the combination of laser-induced oxygen fluorescence and Raman scattering by oxygen and nitrogen from the same laser pulse. Results from this demonstration experiment are compared with previous measurements obtained in the same facility using conventional probes and an earlier spectroscopic technique. Densities and temperatures measured with the current technique agree with the previous surveys to within 3 percent and 2 percent, respectively. The fluctuation amplitudes for both variables agree with the measurements obtained using the earlier spectroscopic technique and show evidence of an unsteady, weak shock wave that perturbs the boundary layer.

Detection of the power spectrum of cosmic microwave background lensing by the Atacama Cosmology Telescope.

PubMed

Das, Sudeep; Sherwin, Blake D; Aguirre, Paula; Appel, John W; Bond, J Richard; Carvalho, C Sofia; Devlin, Mark J; Dunkley, Joanna; Dünner, Rolando; Essinger-Hileman, Thomas; Fowler, Joseph W; Hajian, Amir; Halpern, Mark; Hasselfield, Matthew; Hincks, Adam D; Hlozek, Renée; Huffenberger, Kevin M; Hughes, John P; Irwin, Kent D; Klein, Jeff; Kosowsky, Arthur; Lupton, Robert H; Marriage, Tobias A; Marsden, Danica; Menanteau, Felipe; Moodley, Kavilan; Niemack, Michael D; Nolta, Michael R; Page, Lyman A; Parker, Lucas; Reese, Erik D; Schmitt, Benjamin L; Sehgal, Neelima; Sievers, Jon; Spergel, David N; Staggs, Suzanne T; Swetz, Daniel S; Switzer, Eric R; Thornton, Robert; Visnjic, Katerina; Wollack, Ed

2011-07-08

We report the first detection of the gravitational lensing of the cosmic microwave background through a measurement of the four-point correlation function in the temperature maps made by the Atacama Cosmology Telescope. We verify our detection by calculating the levels of potential contaminants and performing a number of null tests. The resulting convergence power spectrum at 2° angular scales measures the amplitude of matter density fluctuations on comoving length scales of around 100 Mpc at redshifts around 0.5 to 3. The measured amplitude of the signal agrees with Lambda cold dark matter cosmology predictions. Since the amplitude of the convergence power spectrum scales as the square of the amplitude of the density fluctuations, the 4σ detection of the lensing signal measures the amplitude of density fluctuations to 12%.

Methods for recovering a solvent from a fluid volume and methods of removing at least one compound from a nonpolar solvent

DOEpatents

Ginosar, Daniel M.; Wendt, Daniel S.; Petkovic, Lucia M.

2014-06-10

A method of removing a nonpolar solvent from a fluid volume that includes at least one nonpolar compound, such as a fat, an oil or a triglyceride, is provided. The method comprises contacting a fluid volume with an expanding gas to expand the nonpolar solvent and form a gas-expanded solvent. The gas-expanded solvent may have a substantially reduced density in comparison to the at least one nonpolar compound and/or a substantially reduced capacity to solubilize the nonpolar compound, causing the nonpolar compounds to separate from the gas-expanded nonpolar solvent into a separate liquid phase. The liquid phase including the at least one nonpolar compound may be separated from the gas-expanded solvent using conventional techniques. After separation of the liquid phase, at least one of the temperature and pressure may be reduced to separate the nonpolar solvent from the expanding gas such that the nonpolar solvent may be recovered and reused.

Adsorption of flexible polymer chains on a surface: Effects of different solvent conditions

NASA Astrophysics Data System (ADS)

Martins, P. H. L.; Plascak, J. A.; Bachmann, M.

2018-05-01

Polymer chains undergoing a continuous adsorption-desorption transition are studied through extensive computer simulations. A three-dimensional self-avoiding walk lattice model of a polymer chain grafted onto a surface has been treated for different solvent conditions. We have used an advanced contact-density chain-growth algorithm, in which the density of contacts can be directly obtained. From this quantity, the order parameter and its fourth-order Binder cumulant are computed, as well as the corresponding critical exponents and the adsorption-desorption transition temperature. As the number of configurations with a given number of surface contacts and monomer-monomer contacts is independent of the temperature and solvent conditions, it can be easily applied to get results for different solvent parameter values without the need of any extra simulations. In analogy to continuous magnetic phase transitions, finite-size-scaling methods have been employed. Quite good results for the critical properties and phase diagram of very long single polymer chains have been obtained by properly taking into account the effects of corrections to scaling. The study covers all solvent effects, going from the limit of super-self-avoiding walks, characterized by effective monomer-monomer repulsion, to poor solvent conditions that enable the formation of compact polymer structures.

Essential roles of protein-solvent many-body correlation in solvent-entropy effect on protein folding and denaturation: comparison between hard-sphere solvent and water.

PubMed

Oshima, Hiraku; Kinoshita, Masahiro

2015-04-14

In earlier works, we showed that the entropic effect originating from the translational displacement of water molecules plays the pivotal role in protein folding and denaturation. The two different solvent models, hard-sphere solvent and model water, were employed in theoretical methods wherein the entropic effect was treated as an essential factor. However, there were similarities and differences in the results obtained from the two solvent models. In the present work, to unveil the physical origins of the similarities and differences, we simultaneously consider structural transition, cold denaturation, and pressure denaturation for the same protein by employing the two solvent models and considering three different thermodynamic states for each solvent model. The solvent-entropy change upon protein folding/unfolding is decomposed into the protein-solvent pair (PA) and many-body (MB) correlation components using the integral equation theories. Each component is further decomposed into the excluded-volume (EV) and solvent-accessible surface (SAS) terms by applying the morphometric approach. The four physically insightful constituents, (PA, EV), (PA, SAS), (MB, EV), and (MB, SAS), are thus obtained. Moreover, (MB, SAS) is discussed by dividing it into two factors. This all-inclusive investigation leads to the following results: (1) the protein-water many-body correlation always plays critical roles in a variety of folding/unfolding processes; (2) the hard-sphere solvent model fails when it does not correctly reproduce the protein-water many-body correlation; (3) the hard-sphere solvent model becomes problematic when the dependence of the many-body correlation on the solvent number density and temperature is essential: it is not quite suited to studies on cold and pressure denaturating of a protein; (4) when the temperature and solvent number density are limited to the ambient values, the hard-sphere solvent model is usually successful; and (5) even at the ambient values, however, the many-body correlation plays significant roles in the β-sheet formation and argument of relative stabilities of very similar structures of a protein. These results are argued in detail with respect to the four physically insightful constituents and the two factors mentioned above. The relevance to the absence or presence of hydrogen-bonding properties in the solvent is also discussed in detail.

Essential roles of protein-solvent many-body correlation in solvent-entropy effect on protein folding and denaturation: Comparison between hard-sphere solvent and water

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

Oshima, Hiraku; Kinoshita, Masahiro, E-mail: kinoshit@iae.kyoto-u.ac.jp

In earlier works, we showed that the entropic effect originating from the translational displacement of water molecules plays the pivotal role in protein folding and denaturation. The two different solvent models, hard-sphere solvent and model water, were employed in theoretical methods wherein the entropic effect was treated as an essential factor. However, there were similarities and differences in the results obtained from the two solvent models. In the present work, to unveil the physical origins of the similarities and differences, we simultaneously consider structural transition, cold denaturation, and pressure denaturation for the same protein by employing the two solvent modelsmore » and considering three different thermodynamic states for each solvent model. The solvent-entropy change upon protein folding/unfolding is decomposed into the protein-solvent pair (PA) and many-body (MB) correlation components using the integral equation theories. Each component is further decomposed into the excluded-volume (EV) and solvent-accessible surface (SAS) terms by applying the morphometric approach. The four physically insightful constituents, (PA, EV), (PA, SAS), (MB, EV), and (MB, SAS), are thus obtained. Moreover, (MB, SAS) is discussed by dividing it into two factors. This all-inclusive investigation leads to the following results: (1) the protein-water many-body correlation always plays critical roles in a variety of folding/unfolding processes; (2) the hard-sphere solvent model fails when it does not correctly reproduce the protein-water many-body correlation; (3) the hard-sphere solvent model becomes problematic when the dependence of the many-body correlation on the solvent number density and temperature is essential: it is not quite suited to studies on cold and pressure denaturating of a protein; (4) when the temperature and solvent number density are limited to the ambient values, the hard-sphere solvent model is usually successful; and (5) even at the ambient values, however, the many-body correlation plays significant roles in the β-sheet formation and argument of relative stabilities of very similar structures of a protein. These results are argued in detail with respect to the four physically insightful constituents and the two factors mentioned above. The relevance to the absence or presence of hydrogen-bonding properties in the solvent is also discussed in detail.« less

Cosmological consequences of grand unified theories on density fluctuations

NASA Astrophysics Data System (ADS)

Lindley, D.

1981-05-01

Recent investigations into the cosmological consequences of grand unified theories (GUTs) of elementary particles have shown that the observed matter-antimatter asymmetry of the Universe can be explained without recourse to the hypothesis of specific initial conditions. It is shown here that the origin of inhomogeneities in the matter distribution, which are thought to be responsible for the later formation of galaxies, cannot be explained by a simple addition of density fluctuations to the standard model. The appearance of these fluctuations, after the epoch when baryon number is fixed, is almost purely adiabatic, any departure from adiabaticity falling off in inverse proportion to the mass of the perturbation.

Measurements of surface-pressure fluctuations on the XB-70 airplane at local Mach numbers up to 2.45

NASA Technical Reports Server (NTRS)

Lewis, T. L.; Dods, J. B., Jr.; Hanly, R. D.

1973-01-01

Measurements of surface-pressure fluctuations were made at two locations on the XB-70 airplane for nine flight-test conditions encompassing a local Mach number range from 0.35 to 2.45. These measurements are presented in the form of estimated power spectral densities, coherence functions, and narrow-band-convection velocities. The estimated power spectral densities compared favorably with wind-tunnel data obtained by other experimenters. The coherence function and convection velocity data supported conclusions by other experimenters that low-frequency surface-pressure fluctuations consist of small-scale turbulence components with low convection velocity.

Structural dynamics inside a functionalized metal–organic framework probed by ultrafast 2D IR spectroscopy

DOE PAGES

Nishida, Jun; Tamimi, Amr; Fei, Honghan; ...

2014-12-15

One key property of metal-organic frameworks (MOFs) are their structural elasticity. IHere we show that 2D IR spectroscopy with pulse-shaping techniques can probe the ultrafast structural fluctuations of MOFs. 2D IR data, obtained from a vibrational probe attached to the linkers of UiO-66 MOF in low concentration, revealed that the structural fluctuations have time constants of 7 and 670 ps with no solvent. Filling the MOF pores with dimethylformamide (DMF) slows the structural fluctuations by reducing the ability of the MOF to undergo deformations, and the dynamics of the DMF molecules are also greatly restricted. Finally, methodology advances were requiredmore » to remove the severe light scattering caused by the macroscopic-sized MOF particles, eliminate interfering oscillatory components from the 2D IR data, and address Förster vibrational excitation transfer.« less

X-ray diffraction measurement of cosolvent accessible volume in rhombohedral insulin crystals

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

Soares, Alexei S.; Caspar, Donald L. D.

We report x-ray crystallographic measurement of the number of solvent electrons in the unit cell of a protein crystal equilibrated with aqueous solutions of different densities provides information about preferential hydration in the crystalline state. Room temperature and cryo-cooled rhombohedral insulin crystals were equilibrated with 1.2 M trehalose to study the effect of lowered water activity. The native and trehalose soaked crystals were isomorphous and had similar structures. Including all the low resolution data, the amplitudes of the structure factors were put on an absolute scale (in units of electrons per asymmetric unit) by constraining the integrated number of electronsmore » inside the envelope of the calculated protein density map to equal the number deduced from the atomic model. This procedure defines the value of F(0 0 0), the amplitude at the origin of the Fourier transform, which is equal to the total number of electrons in the asymmetric unit (i.e. protein plus solvent). Comparison of the F(0 0 0) values for three isomorphous pairs of room temperature insulin crystals, three with trehalose and three without trehalose, indicates that 75 ± 12 electrons per asymmetric unit were added to the crystal solvent when soaked in 1.2 M trehalose. If all the water in the crystal were available as solvent for the trehalose, 304 electrons would have been added. Thus, the co-solvent accessible volume is one quarter of the total water in the crystal. Finally, determination of the total number of electrons in a protein crystal is an essential first step for mapping the average density distribution of the disordered solvent.« less

X-ray diffraction measurement of cosolvent accessible volume in rhombohedral insulin crystals

DOE PAGES

Soares, Alexei S.; Caspar, Donald L. D.

2017-08-31

We report x-ray crystallographic measurement of the number of solvent electrons in the unit cell of a protein crystal equilibrated with aqueous solutions of different densities provides information about preferential hydration in the crystalline state. Room temperature and cryo-cooled rhombohedral insulin crystals were equilibrated with 1.2 M trehalose to study the effect of lowered water activity. The native and trehalose soaked crystals were isomorphous and had similar structures. Including all the low resolution data, the amplitudes of the structure factors were put on an absolute scale (in units of electrons per asymmetric unit) by constraining the integrated number of electronsmore » inside the envelope of the calculated protein density map to equal the number deduced from the atomic model. This procedure defines the value of F(0 0 0), the amplitude at the origin of the Fourier transform, which is equal to the total number of electrons in the asymmetric unit (i.e. protein plus solvent). Comparison of the F(0 0 0) values for three isomorphous pairs of room temperature insulin crystals, three with trehalose and three without trehalose, indicates that 75 ± 12 electrons per asymmetric unit were added to the crystal solvent when soaked in 1.2 M trehalose. If all the water in the crystal were available as solvent for the trehalose, 304 electrons would have been added. Thus, the co-solvent accessible volume is one quarter of the total water in the crystal. Finally, determination of the total number of electrons in a protein crystal is an essential first step for mapping the average density distribution of the disordered solvent.« less

Separating effective high density polyethylene segments from olefin block copolymers using high temperature liquid chromatography with a preloaded discrete adsorption promoting solvent barrier.

PubMed

Chatterjee, Tirtha; Rickard, Mark A; Pearce, Eric; Pangburn, Todd O; Li, Yongfu; Lyons, John W; Cong, Rongjuan; deGroot, A Willem; Meunier, David M

2016-09-23

Recent advances in catalyst technology have enabled the synthesis of olefin block copolymers (OBC). One type is a "hard-soft" OBC with a high density polyethylene (HDPE) block and a relatively low density polyethylene (VLDPE) block targeted as thermoplastic elastomers. Presently, one of the major challenges is to fractionate HDPE segments from the other components in an experimental OBC sample (block copolymers and VLDPE segments). Interactive high temperature liquid chromatography (HTLC) is ineffective for OBC separation as the HDPE segments and block copolymer chains experience nearly identical enthalpic interactions with the stationary phase and co-elute. In this work we have overcome this challenge by using liquid chromatography under the limiting conditions of desorption (LC LCD). A solvent plug (discrete barrier) is introduced in front of the sample which specifically promotes the adsorption of HDPE segments on the stationary phase (porous graphitic carbon). Under selected thermodynamic conditions, VLDPE segments and block copolymer chains crossed the barrier while HDPE segments followed the pore-included barrier solvent and thus enabled separation. The barrier solvent composition was optimized and the chemical composition of fractionated polymer chains was investigated as a function of barrier solvent strength using an online Fourier-transform infrared (FTIR) detector. Our study revealed that both the HDPE segments as well as asymmetric block copolymer chains (HDPE block length≫VLDPE block length) are retained in the separation and the barrier strength can be tailored to retain a particular composition. At the optimum barrier solvent composition, this method can be applied to separate effective HDPE segments from the other components, which has been demonstrated using an experimental OBC sample. Copyright © 2016 Elsevier B.V. All rights reserved.

Low density microcellular foams

DOEpatents

Aubert, James H.; Clough, Roger L.; Curro, John G.; Quintana, Carlos A.; Russick, Edward M.; Shaw, Montgomery T.

1987-01-01

Low density, microporous polymer foams are provided by a process which comprises forming a solution of polymer and a suitable solvent followed by rapid cooling of the solution to form a phase-separated system and freeze the phase-separated system. The phase-separated system comprises a polymer phase and a solvent phase, each of which is substantially continuous within the other. The morphology of the polymer phase prior to and subsequent to freezing determine the morphology of the resultant foam. Both isotropic and anisotropic foams can be produced. If isotropic foams are produced, the polymer and solvent are tailored such that the solution spontaneously phase-separates prior to the point at which any component freezes. The morphology of the resultant polymer phase determines the morphology of the resultant foam and the morphology of the polymer phase is retained by cooling the system at a rate sufficient to freeze one or both components of the system before a change in morphology can occur. Anisotropic foams are produced by forming a solution of polymer and solvent that will not phase separate prior to freezing of one or both components of the solution. In such a process, the solvent typically freezes before phase separation occurs. The morphology of the resultant frozen two-phase system determines the morphology of the resultant foam. The process involves subjecting the solution to essentially one-dimensional cooling. Means for subjecting such a solvent to one-dimensional cooling are also provided. Foams having a density of less than 0.1 g/cc and a uniform cell size of less than 10 .mu.m and a volume such that the foams have a length greater than 1 cm are provided.

Direct 1H NMR evidence of spin-rotation coupling as a source of para → ortho-H2 conversion in diamagnetic solvents

NASA Astrophysics Data System (ADS)

Terenzi, Camilla; Bouguet-Bonnet, Sabine; Canet, Daniel

2017-04-01

At ambient temperature, conversion from 100% enriched para-hydrogen (p-H2; singlet state) to ortho-hydrogen (o-H2; triplet state) leads necessarily to the thermodynamic equilibrium proportions: 75% of o-H2 and 25% of p-H2. When p-H2 is dissolved in a diamagnetic organic solvent, conversion is very slow and can be considered as arising from nuclear spin relaxation phenomena. A first relaxation mechanism, specific to the singlet state and involving a combination of auto-correlation and cross correlation spectral densities, can be retained: randomly fluctuating magnetic fields due to inter-molecular dipolar interactions. We demonstrate here that (i) this dipolar mechanism is not sufficient for accounting for the p a r a →o r t h o conversion rate, (ii) spin-rotation interaction, an intra-molecular mechanism, behaves similarly to random-field interaction and, thus, may be involved in the singlet relaxation rate. Also, as the p a r a →o r t h o conversion is monitored by proton nuclear magnetic resonance (NMR) of dissolved o-H2 (p-H2 is NMR-silent), one has to account for H2 exchange between the liquid phase and the gas phase within the NMR tube, as well as for dissolution effects. Experimental evidence of the above statements is brought here in the case of two organic solvents: acetone-d6 and carbon disulfide. The observed temperature dependence of the p a r a →o r t h o conversion rate shows that spin-rotation can be the dominant contribution to the p-H2 relaxation rate in the absence of tangible dipolar interactions. Our findings shed new light on the "mysterious" mechanism of the p a r a →o r t h o conversion which has been searched for several decades.

Fundamental Flaws In The Derivation Of Stevens' Law For Taste Within Norwich's Entropy Theory of Perception

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

Nizami, Lance

2010-03-01

Norwich's Entropy Theory of Perception (1975-present) is a general theory of perception, based on Shannon's Information Theory. Among many bold claims, the Entropy Theory presents a truly astounding result: that Stevens' Law with an Index of 1, an empirical power relation of direct proportionality between perceived taste intensity and stimulus concentration, arises from theory alone. Norwich's theorizing starts with several extraordinary hypotheses. First, 'multiple, parallel receptor-neuron units' without collaterals 'carry essentially the same message to the brain', i.e. the rate-level curves are identical. Second, sensation is proportional to firing rate. Third, firing rate is proportional to the taste receptor's 'resolvablemore » uncertainty'. Fourth, the 'resolvable uncertainty' is obtained from Shannon's Information Theory. Finally, 'resolvable uncertainty' also depends upon the microscopic thermodynamic density fluctuation of the tasted solute. Norwich proves that density fluctuation is density variance, which is proportional to solute concentration, all based on the theory of fluctuations in fluid composition from Tolman's classic physics text, 'The Principles of Statistical Mechanics'. Altogether, according to Norwich, perceived taste intensity is theoretically proportional to solute concentration. Such a universal rule for taste, one that is independent of solute identity, personal physiological differences, and psychophysical task, is truly remarkable and is well-deserving of scrutiny. Norwich's crucial step was the derivation of density variance. That step was meticulously reconstructed here. It transpires that the appropriate fluctuation is Tolman's mean-square fractional density fluctuation, not density variance as used by Norwich. Tolman's algebra yields a 'Stevens Index' of -1 rather than 1. As 'Stevens Index' empirically always exceeds zero, the Index of -1 suggests that it is risky to infer psychophysical laws of sensory response from information theory and stimulus physics while ignoring empirical biological transformations, such as sensory transduction. Indeed, it raises doubts as to whether the Entropy Theory actually describes psychophysical laws at all.« less

Numerical investigation of frequency spectrum in the Hasegawa-Wakatani model

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

Kim, Juhyung; Terry, P. W.

2013-10-15

The wavenumber-frequency spectrum of the two-dimensional Hasegawa-Wakatani model is investigated in the hydrodynamic, intermediate, and adiabatic regimes. A nonlinear frequency and a line width related to energy transfer properties provide a measure of the average frequency and spectral broadening, respectively. In the adiabatic regime, narrow spectra, typical of wave turbulence, are observed with a nonlinear frequency shift in the electron drift direction. In the hydrodynamic regime, broad spectra with almost zero nonlinear frequencies are observed. Nonlinear frequency shifts are shown to be related to nonlinear energy transfer by vorticity advection through the high frequency region of the spectrum. In themore » intermediate regime, the nonlinear frequency shift for density fluctuations is observed to be weaker than that of electrostatic potential fluctuations. The weaker frequency shift of the density fluctuations is due to nonlinear density advection, which favors energy transfer in the low frequency range. Both the nonlinear frequency and the spectral width increase with poloidal wavenumber k{sub y}. In addition, in the adiabatic regime where the nonlinear interactions manifest themselves in the nonlinear frequency shift, the cross-phase between the density and potential fluctuations is observed to match a linear relation, but only if the linear response of the linearly stable eigenmode branch is included. Implications of these numerical observations are discussed.« less

Relationship between frequency power spectra and intermittent, large-amplitude bursts in the Alcator C-Mod scrape-off layer

NASA Astrophysics Data System (ADS)

Theodorsen, A.; Garcia, O. E.; Kube, R.; LaBombard, B.; Terry, J. L.

2017-11-01

Fluctuations in the boundary region of the Alcator C-Mod tokamak have been analyzed using gas puff imaging data from a set of Ohmically heated plasma density scan experiments. It is found that the relative fluctuation amplitudes are modest and close to normally distributed at the separatrix but become increasingly larger and skewed towards the main chamber wall. The frequency power spectra are nevertheless similar for all radial positions and line-averaged densities. Predictions of a stochastic model, describing the plasma fluctuations as a super-position of uncorrelated pulses, are shown to be in excellent agreement with the measurements. This implies that the pulse duration is the same, while the degree of pulse overlap decreases radially outwards in the scrape-off layer. The universal frequency power spectral density is thus determined by the shape and duration of the large-amplitude bursts associated with blob-like structures. The model also describes the rate of threshold level crossings, for which the exponential tails underline the intermittency of the fluctuations in the far scarpe-off layer.

Energy dynamics in a simulation of LAPD turbulence

NASA Astrophysics Data System (ADS)

Friedman, B.; Carter, T. A.; Umansky, M. V.; Schaffner, D.; Dudson, B.

2012-10-01

Energy dynamics calculations in a 3D fluid simulation of drift wave turbulence in the linear Large Plasma Device [W. Gekelman et al., Rev. Sci. Instrum. 62, 2875 (1991)] illuminate processes that drive and dissipate the turbulence. These calculations reveal that a nonlinear instability dominates the injection of energy into the turbulence by overtaking the linear drift wave instability that dominates when fluctuations about the equilibrium are small. The nonlinear instability drives flute-like (k∥=0) density fluctuations using free energy from the background density gradient. Through nonlinear axial wavenumber transfer to k∥≠0 fluctuations, the nonlinear instability accesses the adiabatic response, which provides the requisite energy transfer channel from density to potential fluctuations as well as the phase shift that causes instability. The turbulence characteristics in the simulations agree remarkably well with experiment. When the nonlinear instability is artificially removed from the system through suppressing k∥=0 modes, the turbulence develops a coherent frequency spectrum which is inconsistent with experimental data. This indicates the importance of the nonlinear instability in producing experimentally consistent turbulence.

FINAL REPORT: Room Temperature Hydrogen Storage in Nano-Confined Liquids

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

VAJO, JOHN

2014-06-12

DOE continues to seek solid-state hydrogen storage materials with hydrogen densities of ≥6 wt% and ≥50 g/L that can deliver hydrogen and be recharged at room temperature and moderate pressures enabling widespread use in transportation applications. Meanwhile, development including vehicle engineering and delivery infrastructure continues for compressed-gas hydrogen storage systems. Although compressed gas storage avoids the materials-based issues associated with solid-state storage, achieving acceptable volumetric densities has been a persistent challenge. This project examined the possibility of developing storage materials that would be compatible with compressed gas storage technology based on enhanced hydrogen solubility in nano-confined liquid solvents. These materialsmore » would store hydrogen in molecular form eliminating many limitations of current solid-state materials while increasing the volumetric capacity of compressed hydrogen storage vessels. Experimental methods were developed to study hydrogen solubility in nano-confined liquids. These methods included 1) fabrication of composites comprised of volatile liquid solvents for hydrogen confined within the nano-sized pore volume of nanoporous scaffolds and 2) measuring the hydrogen uptake capacity of these composites without altering the composite composition. The hydrogen storage capacities of these nano-confined solvent/scaffold composites were compared with bulk solvents and with empty scaffolds. The solvents and scaffolds were varied to optimize the enhancement in hydrogen solubility that accompanies confinement of the solvent. In addition, computational simulations were performed to study the molecular-scale structure of liquid solvent when confined within an atomically realistic nano-sized pore of a model scaffold. Confined solvent was compared with similar simulations of bulk solvent. The results from the simulations were used to formulate a mechanism for the enhanced solubility and to guide the experiments. Overall, the combined experimental measurements and simulations indicate that hydrogen storage based on enhanced solubility in nano-confined liquids is unlikely to meet the storage densities required for practical use. Only low gravimetric capacities of < 0.5 wt% were achieved. More importantly, solvent filled scaffolds had lower volumetric capacities than corresponding empty scaffolds. Nevertheless, several of the composites measured did show significant (>~ 5x) enhanced hydrogen solubility relative to bulk solvent solubility, when the hydrogen capacity was attributed only to dissolution in the confined solvent. However, when the hydrogen capacity was compared to an empty scaffold that is known to store hydrogen by surface adsorption on the scaffold walls, including the solvent always reduced the hydrogen capacity. For the best composites, this reduction relative to an empty scaffold was ~30%; for the worst it was ~90%. The highest capacities were obtained with the largest solvent molecules and with scaffolds containing 3- dimensionally confined pore geometries. The simulations suggested that the capacity of the composites originated from hydrogen adsorption on the scaffold pore walls at sites not occupied by solvent molecules. Although liquid solvent filled the pores, not all of the adsorption sites on the pore walls were occupied due to restricted motion of the solvent molecules within the confined pore space.« less

Molecular simulation of CO chemisorption on Co(0001) in presence of supercritical fluid solvent: A potential of mean force study

NASA Astrophysics Data System (ADS)

Asiaee, Alireza; Benjamin, Kenneth M.

2016-08-01

For several decades, heterogeneous catalytic processes have been improved through utilizing supercritical fluids (SCFs) as solvents. While numerous experimental studies have been established across a range of chemistries, such as oxidation, pyrolysis, amination, and Fischer-Tropsch synthesis, still there is little fundamental, molecular-level information regarding the role of the SCF on elementary heterogeneous catalytic steps. In this study, the influence of hexane solvent on the adsorption of carbon monoxide on Co(0001), as the first step in the reaction mechanism of many processes involving syngas conversion, is probed. Simulations are performed at various bulk hexane densities, ranging from ideal gas conditions (no SCF hexane) to various near- and super-critical hexane densities. For this purpose, both density functional theory and molecular dynamics simulations are employed to determine the adsorption energy and free energy change during CO chemisorption. Potential of mean force calculations, utilizing umbrella sampling and the weighted histogram analysis method, provide the first commentary on SCF solvent effects on the energetic aspects of the chemisorption process. Simulation results indicate an enhanced stability of CO adsorption on the catalyst surface in the presence of supercritical hexane within the reduced pressure range of 1.0-1.5 at a constant temperature of 523 K. Furthermore, it is shown that the maximum stability of CO in the adsorbed state as a function of supercritical hexane density at 523 K nearly coincides with the maximum isothermal compressibility of bulk hexane at this temperature.

An evaporation-assisted dispersive liquid-liquid microextraction technique as a simple tool for high performance liquid chromatography tandem-mass spectrometry determination of insecticides in wine.

PubMed

Timofeeva, Irina; Kanashina, Daria; Moskvin, Leonid; Bulatov, Andrey

2017-08-25

A sample pre-treatment technique based on evaporation-assisted dispersive liquid-liquid microextraction (EVA-DLLME), followed by HPLC-MS/MS has been developed for the determination of organophosphate insecticides (malathion, diazinon, phosalone) in wine samples. The procedure includes the addition of mixture of organic solvents (with density higher than water), consisting of the extraction (low density) and volatile (high density) solvents, to aqueous sample followed by heating of the mixture obtained, what promotes the volatile solvent evaporation and moving extraction solvent droplets from down to top of the aqueous sample and, as a consequence, microextraction of target analytes. To initiate the evaporation process an initiator is required. It was established that hexanol (extraction solvent) and dichloromethane (volatile solvent) mixture (1:1, v/v) provides effective microextraction of the insecticides from wine samples with recovery from 92 to 103%. The conditions of insecticides' microextraction such as selection of extraction solvent, ratio of hexanol/dichloromethane and hexanol/sample, type and concentration of initiator, and effect of ethanol as one of the main components of wine have been studied. Under optimal experimental conditions the linear detection ranges were found to be 10 -7 -10 -3 gL -1 for malathion, 10 -9 -10 -4 gL -1 for diazinon, and 10 -6 -10 -2 gL -1 for phosalone. The LODs, calculated from a blank test, based on 3σ, found to be 3×10 -8 gL -1 for malathion, 3×10 -10 gL -1 for diazinon and 3×10 -7 gL -1 for phosalone. The advantages of EVA-DLLME are the rapidity, simplicity, high sample throughput and low cost. As an outcome, the analytical results agreed fairly well with the results obtained by a reference GC-MS method. Copyright © 2017 Elsevier B.V. All rights reserved.

Solidification of floating organic droplet in dispersive liquid-liquid microextraction as a green analytical tool.

PubMed

Mansour, Fotouh R; Danielson, Neil D

2017-08-01

Dispersive liquid-liquid microextraction (DLLME) is a special type of microextraction in which a mixture of two solvents (an extracting solvent and a disperser) is injected into the sample. The extraction solvent is then dispersed as fine droplets in the cloudy sample through manual or mechanical agitation. Hence, the sample is centrifuged to break the formed emulsion and the extracting solvent is manually separated. The organic solvents commonly used in DLLME are halogenated hydrocarbons that are highly toxic. These solvents are heavier than water, so they sink to the bottom of the centrifugation tube which makes the separation step difficult. By using solvents of low density, the organic extractant floats on the sample surface. If the selected solvent such as undecanol has a freezing point in the range 10-25°C, the floating droplet can be solidified using a simple ice-bath, and then transferred out of the sample matrix; this step is known as solidification of floating organic droplet (SFOD). Coupling DLLME to SFOD combines the advantages of both approaches together. The DLLME-SFOD process is controlled by the same variables of conventional liquid-liquid extraction. The organic solvents used as extractants in DLLME-SFOD must be immiscible with water, of lower density, low volatility, high partition coefficient and low melting and freezing points. The extraction efficiency of DLLME-SFOD is affected by types and volumes of organic extractant and disperser, salt addition, pH, temperature, stirring rate and extraction time. This review discusses the principle, optimization variables, advantages and disadvantages and some selected applications of DLLME-SFOD in water, food and biomedical analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

Control of ion gyroscale fluctuations via electrostatic biasing and sheared E×B flow in the C-2 field reversed configuration

NASA Astrophysics Data System (ADS)

Schmitz, L.; Ruskov, E.; Deng, B. H.; Binderbauer, M.; Tajima, T.; Gota, H.; Tuszewski, M.

2016-03-01

Control of radial particle and thermal transport is instrumental for achieving and sustaining well-confined high-β plasma in a Field-Reversed Configuration (FRC). Radial profiles of low frequency ion gyro-scale density fluctuations (0.5≤kρs≤40), consistent with drift- or drift-interchange modes, have been measured in the scrape-off layer (SOL) and core of the C-2 Field-Reversed Configuration (FRC), together with the toroidal E×B velocity. It is shown here that axial electrostatic SOL biasing controls and reduces gyro-scale density fluctuations, resulting in very low FRC core fluctuation levels. When the radial E×B flow shearing rate decreases below the turbulence decorrelation rate, fluctuation levels increase substantially, concomitantly with onset of the n=2 instability and rapid loss of diamagnetism. Low turbulence levels, improved energy/particle confinement and substantially increased FRC life times are achieved when E×B shear near the separatrix is maintained via axial SOL biasing using an annular washer gun.

Increase in the Random Dopant Induced Threshold Fluctuations and Lowering in Sub 100 nm MOSFETs Due to Quantum Effects: A 3-D Density-Gradient Simulation Study

NASA Technical Reports Server (NTRS)

Asenov, Asen; Slavcheva, G.; Brown, A. R.; Davies, J. H.; Saini, S.

2000-01-01

In this paper we present a detailed simulation study of the influence of quantum mechanical effects in the inversion layer on random dopant induced threshold voltage fluctuations and lowering in sub 100 nm MOSFETs. The simulations have been performed using a 3-D implementation of the density gradient (DG) formalism incorporated in our established 3-D atomistic simulation approach. This results in a self-consistent 3-D quantum mechanical picture, which implies not only the vertical inversion layer quantisation but also the lateral confinement effects related to current filamentation in the 'valleys' of the random potential fluctuations. We have shown that the net result of including quantum mechanical effects, while considering statistical dopant fluctuations, is an increase in both threshold voltage fluctuations and lowering. At the same time, the random dopant induced threshold voltage lowering partially compensates for the quantum mechanical threshold voltage shift in aggressively scaled MOSFETs with ultrathin gate oxides.

[Determination of solubility parameters of high density polyethylene by inverse gas chromatography].

PubMed

Wang, Qiang; Chen, Yali; Liu, Ruiting; Shi, Yuge; Zhang, Zhengfang; Tang, Jun

2011-11-01

Inverse gas chromatographic (IGC) technology was used to determine the solubility parameters of high density polyethylene (HDPE) at the absolute temperatures from 303.15 to 343.15 K. Six solvents were applied as test probes including hexane (n-C6), heptane (n-C7), octane (n-C8), nonane (n-C9), chloroform (CHCl3) and ethyl acetate (EtAc). Some thermodynamic parameters were obtained by IGC data analysis such as the specific retention volumes of the solvents (V(0)(g)), the molar enthalpy of sorption (delta H(S)(1)), the partial molar enthalpy of mixing at infinite dilution (delta H(1)(infinity)), the molar enthalpy of vaporization (delta H(v)), the activity coefficients at infinite dilution (omega (1)(infinity)), and Flow-Huggins interaction parameters (X(1,2)(infinity)) between HDPE and probe solvents. The results showed that the above six probes are poor solvents for HDPE. The solubility parameter of HDPE at room temperature (298.15 K) was also derived as 19.00 (J/cm3)(0.5).

Shock wave oscillation driven by turbulent boundary layer fluctuations

NASA Technical Reports Server (NTRS)

Plotkin, K. J.

1972-01-01

Pressure fluctuations due to the interaction of a shock wave with a turbulent boundary layer were investigated. A simple model is proposed in which the shock wave is convected from its mean position by velocity fluctuations in the turbulent boundary layer. Displacement of the shock is assumed limited by a linear restoring mechanism. Predictions of peak root mean square pressure fluctuation and spectral density are in excellent agreement with available experimental data.

Numerical methods for the stochastic Landau-Lifshitz Navier-Stokes equations.

PubMed

Bell, John B; Garcia, Alejandro L; Williams, Sarah A

2007-07-01

The Landau-Lifshitz Navier-Stokes (LLNS) equations incorporate thermal fluctuations into macroscopic hydrodynamics by using stochastic fluxes. This paper examines explicit Eulerian discretizations of the full LLNS equations. Several computational fluid dynamics approaches are considered (including MacCormack's two-step Lax-Wendroff scheme and the piecewise parabolic method) and are found to give good results for the variance of momentum fluctuations. However, neither of these schemes accurately reproduces the fluctuations in energy or density. We introduce a conservative centered scheme with a third-order Runge-Kutta temporal integrator that does accurately produce fluctuations in density, energy, and momentum. A variety of numerical tests, including the random walk of a standing shock wave, are considered and results from the stochastic LLNS solver are compared with theory, when available, and with molecular simulations using a direct simulation Monte Carlo algorithm.

SNW 2000 Proceedings. Oxide Thickness Variation Induced Threshold Voltage Fluctuations in Decanano MOSFETs: a 3D Density Gradient Simulation Study

NASA Technical Reports Server (NTRS)

Asenov, Asen; Kaya, S.; Davies, J. H.; Saini, S.

2000-01-01

We use the density gradient (DG) simulation approach to study, in 3D, the effect of local oxide thickness fluctuations on the threshold voltage of decanano MOSFETs in a statistical manner. A description of the reconstruction procedure for the random 2D surfaces representing the 'atomistic' Si-SiO2 interface variations is presented. The procedure is based on power spectrum synthesis in the Fourier domain and can include either Gaussian or exponential spectra. The simulations show that threshold voltage variations induced by oxide thickness fluctuation become significant when the gate length of the devices become comparable to the correlation length of the fluctuations. The extent of quantum corrections in the simulations with respect to the classical case and the dependence of threshold variations on the oxide thickness are examined.

Effect of reduction in the density of states on fluctuation conductivity in Bi 2Sr 2CaCu 2O 8+ x single crystals

NASA Astrophysics Data System (ADS)

Chowdhury, P.; Bhatia, S. N.

1999-06-01

The in-plane ( ρab) and out-of-plane ( ρc) resistivities of BSCCO single crystals have been measured by six terminals technique. The ρab and ρc are well described by the fluctuation theory developed by Dorin et al. The main effect of these fluctuations is to cause a reduction in the quasi-particle density of states (DOS), leading to a negative contribution in the fluctuation conductivity Lawrence-Doniach (LD) and Maki-Thompson (MT) contributions. We have analyzed paraconductivity by adding this DOS contribution to LD and MT contributions. The analysis shows that approaches based on the conventional LD model alone cannot explain the paraconductivity along ab-plane and c-axis, even when the MT contribution is included.

Dynamic density functional theory with hydrodynamic interactions and fluctuations

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

Donev, Aleksandar, E-mail: donev@courant.nyu.edu; Vanden-Eijnden, Eric, E-mail: eve2@courant.nyu.edu

2014-06-21

We derive a closed equation for the empirical concentration of colloidal particles in the presence of both hydrodynamic and direct interactions. The ensemble average of our functional Langevin equation reproduces known deterministic Dynamic Density Functional Theory (DDFT) [M. Rex and H. Löwen, “Dynamical density functional theory with hydrodynamic interactions and colloids in unstable traps,” Phys. Rev. Lett. 101(14), 148302 (2008)], and, at the same time, it also describes the microscopic fluctuations around the mean behavior. We suggest separating the ideal (non-interacting) contribution from additional corrections due to pairwise interactions. We find that, for an incompressible fluid and in the absencemore » of direct interactions, the mean concentration follows Fick's law just as for uncorrelated walkers. At the same time, the nature of the stochastic terms in fluctuating DDFT is shown to be distinctly different for hydrodynamically-correlated and uncorrelated walkers. This leads to striking differences in the behavior of the fluctuations around Fick's law, even in the absence of pairwise interactions. We connect our own prior work [A. Donev, T. G. Fai, and E. Vanden-Eijnden, “A reversible mesoscopic model of diffusion in liquids: from giant fluctuations to Fick's law,” J. Stat. Mech.: Theory Exp. (2014) P04004] on fluctuating hydrodynamics of diffusion in liquids to the DDFT literature, and demonstrate that the fluid cannot easily be eliminated from consideration if one wants to describe the collective diffusion in colloidal suspensions.« less

Study of molecular interactions in binary mixtures of 2-chloro-4'methoxy benzoin with various solvents through ultrasonic speed measurements

NASA Astrophysics Data System (ADS)

Thanuja, B.; Kanakam, C.; Nithya, G.

2013-12-01

Density ( ρ) and ultrasonic velocity ( U), for binary mixtures of 2-chloro-4'-methoxy benzoin with ethanol, chloroform, acetonitrile, benzene and 1,4-dioxane of different compositions have been measured at 298 K and explanation of solute solvent interactions and effect of polarity of the solvent on type of interactions are presented in this paper. From the above data, adiabatic compressibility ( β), intermolecular free length ( L f ) and relative association ( R A ) have been calculated. Other useful parameters such as excess density, excess velocity, excess intermolecular freelength and excess adiabatic compressibility have also been calculated. These parameters have been used to study the nature and extent of intermolecular interactions between component molecules in present binary mixtures.

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

Sun, Liang; Akgun, Bulent; Narayanan, Suresh

Swollen polymer brushes are found in many systems where the brush is intended to mediate interactions with the surroundings. The surface height fluctuations of planar polystyrene brushes (0.04 – 0.63 chains/nm2) highly swollen in toluene vapor are so strongly slowed by the tethering of the chains that they are unobservable in the current experimental window of length and time. This is the case despite the fact that the segmental dynamics of the brush chains should be very fast due to the substantial plasticization by the solvent. With respect to thermally stimulated fluctuations, the surfaces of these swollen brushes are solid-likemore » on time scales and length scales pertinent to many practical applications.« less

Growth and dissolution of spherical density enhancements in SCDEW cosmologies

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

Bonometto, Silvio A.; Mainini, Roberto, E-mail: bonometto@oats.inaf.it, E-mail: roberto.mainini@mib.infn.it

2017-06-01

Strongly Coupled Dark Energy plus Warm dark matter (SCDEW) cosmologies are based on the finding of a conformally invariant (CI) attractor solution during the early radiative expansion, requiring then the stationary presence of ∼ 1 % of coupled-DM and DE, since inflationary reheating. In these models, coupled-DM fluctuations, even in the early radiative expansion, grow up to non-linearity, as shown in a previous associated paper. Such early non-linear stages are modelized here through the evolution of a top-hat density enhancement. As expected, its radius R increases up to a maximum and then starts to decrease. Virial balance is reached whenmore » the coupled-DM density contrast is just 25–26 and DM density enhancement is O(10 %) of total density. Moreover, we find that this is not an equilibrium configuration as, afterwards, coupling causes DM particle velocities to increase, so that the fluctuation gradually dissolves. We estimate the duration of the whole process, from horizon crossing to dissolution, and find z {sub horizon}/ z {sub erasing} ∼ 3 × 10{sup 4}. Therefore, only fluctuations entering the horizon at z ∼< 10{sup 9}–10{sup 10} are able to accrete WDM with mass ∼ 100 eV—as soon as it becomes non-relativistic—so avoiding full disruption. Accordingly, SCDEW cosmologies, whose WDM has mass ∼ 100 eV, can preserve primeval fluctuations down to stellar mass scale.« less

Evidence for r- and K-selection in a wild bird population: a reciprocal link between ecology and evolution.

PubMed

Sæther, Bernt-Erik; Visser, Marcel E; Grøtan, Vidar; Engen, Steinar

2016-04-27

Understanding the variation in selection pressure on key life-history traits is crucial in our rapidly changing world. Density is rarely considered as a selective agent. To study its importance, we partition phenotypic selection in fluctuating environments into components representing the population growth rate at low densities and the strength of density dependence, using a new stochastic modelling framework. We analysed the number of eggs laid per season in a small song-bird, the great tit, and found balancing selection favouring large clutch sizes at small population densities and smaller clutches in years with large populations. A significant interaction between clutch size and population size in the regression for the Malthusian fitness reveals that those females producing large clutch sizes at small population sizes also are those that show the strongest reduction in fitness when population size is increased. This provides empirical support for ongoing r- and K-selection in this population, favouring phenotypes with large growth rates r at small population sizes and phenotypes with high competitive skills when populations are close to the carrying capacity K This selection causes long-term fluctuations around a stable mean clutch size caused by variation in population size, implying that r- and K-selection is an important mechanism influencing phenotypic evolution in fluctuating environments. This provides a general link between ecological dynamics and evolutionary processes, operating through a joint influence of density dependence and environmental stochasticity on fluctuations in population size. © 2016 The Author(s).

Nonequilibrium forces following quenches in active and thermal matter.

PubMed

Rohwer, Christian M; Solon, Alexandre; Kardar, Mehran; Krüger, Matthias

2018-03-01

Nonequilibrium systems with conserved quantities like density or momentum are known to exhibit long-ranged correlations. This, in turn, leads to long-ranged fluctuation-induced (Casimir) forces, predicted to arise in a variety of nonequilibrium settings. Here, we study such forces, which arise transiently between parallel plates or compact inclusions in a gas of particles, following a change ("quench") in temperature or activity of the medium. Analytical calculations, as well as numerical simulations of passive or active Brownian particles, indicate two distinct forces: (i) The immediate effect of the quench is adsorption or desorption of particles of the medium to the immersed objects, which in turn initiates a front of relaxing (mean) density. This leads to time-dependent density-induced forces. (ii) A long-term effect of the quench is that density fluctuations are modified, manifested as transient (long-ranged) (pair-)correlations that relax diffusively to their (short-ranged) steady-state limit. As a result, transient fluctuation-induced forces emerge. We discuss the properties of fluctuation-induced and density-induced forces as regards universality, relaxation as a function of time, and scaling with distance between objects. Their distinct signatures allow us to distinguish the two types of forces in simulation data. Our simulations also show that a quench of the effective temperature of an active medium gives rise to qualitatively similar effects to a temperature quench in a passive medium. Based on this insight, we propose several scenarios for the experimental observation of the forces described here.

Nonequilibrium forces following quenches in active and thermal matter

NASA Astrophysics Data System (ADS)

Rohwer, Christian M.; Solon, Alexandre; Kardar, Mehran; Krüger, Matthias

2018-03-01

Nonequilibrium systems with conserved quantities like density or momentum are known to exhibit long-ranged correlations. This, in turn, leads to long-ranged fluctuation-induced (Casimir) forces, predicted to arise in a variety of nonequilibrium settings. Here, we study such forces, which arise transiently between parallel plates or compact inclusions in a gas of particles, following a change ("quench") in temperature or activity of the medium. Analytical calculations, as well as numerical simulations of passive or active Brownian particles, indicate two distinct forces: (i) The immediate effect of the quench is adsorption or desorption of particles of the medium to the immersed objects, which in turn initiates a front of relaxing (mean) density. This leads to time-dependent density-induced forces. (ii) A long-term effect of the quench is that density fluctuations are modified, manifested as transient (long-ranged) (pair-)correlations that relax diffusively to their (short-ranged) steady-state limit. As a result, transient fluctuation-induced forces emerge. We discuss the properties of fluctuation-induced and density-induced forces as regards universality, relaxation as a function of time, and scaling with distance between objects. Their distinct signatures allow us to distinguish the two types of forces in simulation data. Our simulations also show that a quench of the effective temperature of an active medium gives rise to qualitatively similar effects to a temperature quench in a passive medium. Based on this insight, we propose several scenarios for the experimental observation of the forces described here.

Density of states and magnetotransport in Weyl semimetals with long-range disorder

NASA Astrophysics Data System (ADS)

Pesin, D. A.; Mishchenko, E. G.; Levchenko, A.

2015-11-01

We study the density of states and magnetotransport properties of disordered Weyl semimetals, focusing on the case of a strong long-range disorder. To calculate the disorder-averaged density of states close to nodal points, we treat exactly the long-range random potential fluctuations produced by charged impurities, while the short-range component of disorder potential is included systematically and controllably with the help of a diagram technique. We find that, for energies close to the degeneracy point, long-range potential fluctuations lead to a finite density of states. In the context of transport, we discuss that a self-consistent theory of screening in magnetic field may conceivably lead to nonmonotonic low-field magnetoresistance.

High-density QCD phase transitions inside neutron stars: Glitches and gravitational waves

NASA Astrophysics Data System (ADS)

Srivastava, A. M.; Bagchi, P.; Das, A.; Layek, B.

2017-10-01

We discuss physics of exotic high baryon density QCD phases which are believed to exist in the core of a neutron star. This can provide a laboratory for exploring exotic physics such as axion emission, KK graviton production etc. Much of the physics of these high-density phases is model-dependent and not very well understood, especially the densities expected to occur inside neutron stars. We follow a different approach and use primarily universal aspects of the physics of different high-density phases and associated phase transitions. We study effects of density fluctuations during transitions with and without topological defect production and study the effect on pulsar timings due to changing moment of inertia of the star. We also discuss gravitational wave production due to rapidly changing quadrupole moment of the star due to these fluctuations.

Pressure effects on collective density fluctuations in water and protein solutions

PubMed Central

Russo, Daniela; Laloni, Alessio; Filabozzi, Alessandra; Heyden, Matthias

2017-01-01

Neutron Brillouin scattering and molecular dynamics simulations have been used to investigate protein hydration water density fluctuations as a function of pressure. Our results show significant differences between the pressure and density dependence of collective dynamics in bulk water and in concentrated protein solutions. Pressure-induced changes in the tetrahedral order of the water HB network have direct consequences for the high-frequency sound velocity and damping coefficients, which we find to be a sensitive probe for changes in the HB network structure as well as the wetting of biomolecular surfaces. PMID:29073065

Amplitude of primeval fluctuations from cosmological mass density reconstructions

NASA Technical Reports Server (NTRS)

Seljak, Uros; Bertschinger, Edmund

1994-01-01

We use the POTENT reconstruction of the mass density field in the nearby universe to estimate the amplitude of the density fluctuation power spectrum for various cosmological models. We find that sigma(sub 8) Omega(sub m sup 0.6) = 1.3(sub -0.3 sup +0.4), almost independently of the power spectrum. This value agrees well with the Cosmic Background Explorer (COBE) normalization for the standard cold dark matter model, while alternative models predict an excessive amplitude compared with COBE. Flat, low Omega(sub m) models and tilted models with spectral index n less than 0.8 are particularly discordant.

Chaotic density fluctuations in L-mode plasmas of the DIII-D tokamak

DOE PAGES

Maggs, J. E.; Rhodes, Terry L.; Morales, G. J.

2015-03-05

Analysis of the time series obtained with the Doppler backscattering system (DBS) in the DIII-D tokamak shows that intermediate wave number plasma density fluctuations in low confinement (L-mode) tokamak plasmas are chaotic. Here, the supporting evidence is based on the shape of the power spectrum; the location of the signal in the complexity-entropy plane (C-H plane); and the population of the corresponding Bandt-Pompe probability distributions.

Electron-cyclotron wave scattering by edge density fluctuations in ITER

NASA Astrophysics Data System (ADS)

Tsironis, Christos; Peeters, Arthur G.; Isliker, Heinz; Strintzi, Dafni; Chatziantonaki, Ioanna; Vlahos, Loukas

2009-11-01

The effect of edge turbulence on the electron-cyclotron wave propagation in ITER is investigated with emphasis on wave scattering, beam broadening, and its influence on localized heating and current drive. A wave used for electron-cyclotron current drive (ECCD) must cross the edge of the plasma, where density fluctuations can be large enough to bring on wave scattering. The scattering angle due to the density fluctuations is small, but the beam propagates over a distance of several meters up to the resonance layer and even small angle scattering leads to a deviation of several centimeters at the deposition location. Since the localization of ECCD is crucial for the control of neoclassical tearing modes, this issue is of great importance to the ITER design. The wave scattering process is described on the basis of a Fokker-Planck equation, where the diffusion coefficient is calculated analytically as well as computed numerically using a ray tracing code.

Ultraviolet luminosity density of the universe during the epoch of reionization.

PubMed

Mitchell-Wynne, Ketron; Cooray, Asantha; Gong, Yan; Ashby, Matthew; Dolch, Timothy; Ferguson, Henry; Finkelstein, Steven; Grogin, Norman; Kocevski, Dale; Koekemoer, Anton; Primack, Joel; Smidt, Joseph

2015-09-08

The spatial fluctuations of the extragalactic background light trace the total emission from all stars and galaxies in the Universe. A multiwavelength study can be used to measure the integrated emission from first galaxies during reionization when the Universe was about 500 million years old. Here we report arcmin-scale spatial fluctuations in one of the deepest sky surveys with the Hubble Space Telescope in five wavebands between 0.6 and 1.6 μm. We model-fit the angular power spectra of intensity fluctuation measurements to find the ultraviolet luminosity density of galaxies at redshifts greater than 8 to be log ρ(UV) = 27.4(+0.2)(-1.2) ergs(-1) Hz(-1) Mpc(-3) (1σ). This level of integrated light emission allows for a significant surface density of fainter primeval galaxies that are below the point-source detection level in current surveys.

Experimental evaluation of fluctuating density and radiated noise from a high temperature jet

NASA Technical Reports Server (NTRS)

Massier, P. F.; Parthasarathy, S. P.; Cuffel, R. F.

1973-01-01

An experimental investigation has been conducted to characterize the fluctuating density within a high-temperature (1100 K) subsonic jet and to characterize by the noise radiated to the surroundings. Cross correlations obtained by introducing time delay to the signals detected from spatially separated crossed laser beams set up as a Schlieren system were used to determine radial and axial distributions of the convection velocity of the moving noise sources (eddies). In addition, the autocorrelation of the fluctuating density was evaluated in the moving frame of reference of the eddies. Also, the autocorrelation of the radiated noise in the moving reference frame was evaluated from cross correlations by introducing time delay to the signals detected by spatially separated pairs of microphones. Radial distributions of the mean velocity were obtained from measurements of the stagnation temperature, and stagnation and static pressures with the use of probes.

Effects of Density Fluctuations on Weakly Nonlinear Alfven Waves: An IST Perspective

NASA Astrophysics Data System (ADS)

Hamilton, R.; Hadley, N.

2012-12-01

The effects of random density fluctuations on oblique, 1D, weakly nonlinear Alfven waves is examined through a numerical study of an analytical model developed by Ruderman [M.S. Ruderman, Phys. Plasmas, 9 (7), pp. 2940-2945, (2002).]. Consistent with Ruderman's application to the one-parameter dark soliton, the effects on both one-parameter bright and dark solitons, the two-parameter soliton as well as pairs of one-parameter solitons were similar to that of Ohmic dissipation found by Hamilton et al. [R. Hamilton, D. Peterson, and S. Libby, J. Geophys. Res 114, A03104,doi:10.1029/2008JA013582 (2009).] It was found in all cases where bright or two-parameter solitons are present initially, that the effects of density fluctuations results in the eventual damping of such compressive wave forms and the formation of a train of dark solitons, or magnetic depressions.

A phase contrast imaging-interferometer system for detection of multiscale electron density fluctuations on DIII-D

NASA Astrophysics Data System (ADS)

Davis, E. M.; Rost, J. C.; Porkolab, M.; Marinoni, A.; Van Zeeland, M. A.

2016-11-01

Heterodyne interferometry and phase contrast imaging (PCI) are robust, mature techniques for measuring low-k and high-k electron density fluctuations, respectively. This work describes the first-ever implementation of a combined PCI-interferometer. The combined system uses a single 10.6 μm probe beam, two interference schemes, and two detectors to measure electron density fluctuations at large spatiotemporal bandwidth (10 kHz

Angular fluctuations of a multi-component order describe the pseudogap regime of the cuprate superconductors

NASA Astrophysics Data System (ADS)

Sachdev, Subir

2014-03-01

The hole-doped cuprate high temperature superconductors enter the pseudogap regime as their superconducting critical temperature, Tc, falls with decreasing hole density. Experiments have probed this regime for over two decades, but we argue that decisive new information has emerged from recent X-ray scattering experiments. The experiments observe incommensurate charge density wave fluctuations whose strength rises gradually over a wide temperature range above Tc, but then decreases as the temperature is lowered below Tc. We propose a theory in which the superconducting and charge-density wave orders exhibit angular fluctuations in a 6-dimensional space. The theory provides a natural quantitative fit to the X-ray data, and is consistent with other observed characteristics of the pseudogap. Results will also be presented on the microscopic origins of these order parameters. Work in collaboration with Lauren Hayward, Roger Melko, David Hawthorn, and Jay Sau.

Modeling Electronic-Nuclear Interactions for Excitation Energy Transfer Processes in Light-Harvesting Complexes.

PubMed

Lee, Mi Kyung; Coker, David F

2016-08-18

An accurate approach for computing intermolecular and intrachromophore contributions to spectral densities to describe the electronic-nuclear interactions relevant for modeling excitation energy transfer processes in light harvesting systems is presented. The approach is based on molecular dynamics (MD) calculations of classical correlation functions of long-range contributions to excitation energy fluctuations and a separate harmonic analysis and single-point gradient quantum calculations for electron-intrachromophore vibrational couplings. A simple model is also presented that enables detailed analysis of the shortcomings of standard MD-based excitation energy fluctuation correlation function approaches. The method introduced here avoids these problems, and its reliability is demonstrated in accurate predictions for bacteriochlorophyll molecules in the Fenna-Matthews-Olson pigment-protein complex, where excellent agreement with experimental spectral densities is found. This efficient approach can provide instantaneous spectral densities for treating the influence of fluctuations in environmental dissipation on fast electronic relaxation.

Plasma fluctuations as Markovian noise.

PubMed

Li, B; Hazeltine, R D; Gentle, K W

2007-12-01

Noise theory is used to study the correlations of stationary Markovian fluctuations that are homogeneous and isotropic in space. The relaxation of the fluctuations is modeled by the diffusion equation. The spatial correlations of random fluctuations are modeled by the exponential decay. Based on these models, the temporal correlations of random fluctuations, such as the correlation function and the power spectrum, are calculated. We find that the diffusion process can give rise to the decay of the correlation function and a broad frequency spectrum of random fluctuations. We also find that the transport coefficients may be estimated by the correlation length and the correlation time. The theoretical results are compared with the observed plasma density fluctuations from the tokamak and helimak experiments.

Entropy Production in Field Theories without Time-Reversal Symmetry: Quantifying the Non-Equilibrium Character of Active Matter

NASA Astrophysics Data System (ADS)

Nardini, Cesare; Fodor, Étienne; Tjhung, Elsen; van Wijland, Frédéric; Tailleur, Julien; Cates, Michael E.

2017-04-01

Active-matter systems operate far from equilibrium because of the continuous energy injection at the scale of constituent particles. At larger scales, described by coarse-grained models, the global entropy production rate S quantifies the probability ratio of forward and reversed dynamics and hence the importance of irreversibility at such scales: It vanishes whenever the coarse-grained dynamics of the active system reduces to that of an effective equilibrium model. We evaluate S for a class of scalar stochastic field theories describing the coarse-grained density of self-propelled particles without alignment interactions, capturing such key phenomena as motility-induced phase separation. We show how the entropy production can be decomposed locally (in real space) or spectrally (in Fourier space), allowing detailed examination of the spatial structure and correlations that underly departures from equilibrium. For phase-separated systems, the local entropy production is concentrated mainly on interfaces, with a bulk contribution that tends to zero in the weak-noise limit. In homogeneous states, we find a generalized Harada-Sasa relation that directly expresses the entropy production in terms of the wave-vector-dependent deviation from the fluctuation-dissipation relation between response functions and correlators. We discuss extensions to the case where the particle density is coupled to a momentum-conserving solvent and to situations where the particle current, rather than the density, should be chosen as the dynamical field. We expect the new conceptual tools developed here to be broadly useful in the context of active matter, allowing one to distinguish when and where activity plays an essential role in the dynamics.

On the theory of electric double layer with explicit account of a polarizable co-solvent.

PubMed

Budkov, Yu A; Kolesnikov, A L; Kiselev, M G

2016-05-14

We present a continuation of our theoretical research into the influence of co-solvent polarizability on a differential capacitance of the electric double layer. We formulate a modified Poisson-Boltzmann theory, using the formalism of density functional approach on the level of local density approximation taking into account the electrostatic interactions of ions and co-solvent molecules as well as their excluded volume. We derive the modified Poisson-Boltzmann equation, considering the three-component symmetric lattice gas model as a reference system and minimizing the grand thermodynamic potential with respect to the electrostatic potential. We apply present modified Poisson-Boltzmann equation to the electric double layer theory, showing that accounting for the excluded volume of co-solvent molecules and ions slightly changes the main result of our previous simplified theory. Namely, in the case of small co-solvent polarizability with its increase under the enough small surface potentials of electrode, the differential capacitance undergoes the significant growth. Oppositely, when the surface potential exceeds some threshold value (which is slightly smaller than the saturation potential), the increase in the co-solvent polarizability results in a differential capacitance decrease. However, when the co-solvent polarizability exceeds some threshold value, its increase generates a considerable enhancement of the differential capacitance in a wide range of surface potentials. We demonstrate that two qualitatively different behaviors of the differential capacitance are related to the depletion and adsorption of co-solvent molecules at the charged electrode. We show that an additive of the strongly polarizable co-solvent to an electrolyte solution can shift significantly the saturation potential in two qualitatively different manners. Namely, a small additive of strongly polarizable co-solvent results in a shift of saturation potential to higher surface potentials. On the contrary, a sufficiently large additive of co-solvent shifts the saturation potential to lower surface potentials. We obtain that an increase in the co-solvent polarizability makes the electrostatic potential profile longer-ranged. However, increase in the co-solvent concentration in the bulk leads to non-monotonic behavior of the electrostatic potential profile. An increase in the co-solvent concentration in the bulk at its sufficiently small values makes the electrostatic potential profile longer-ranged. Oppositely, when the co-solvent concentration in the bulk exceeds some threshold value, its further increase leads to decrease in electrostatic potential at all distances from the electrode.

Large-scale anisotropy of the cosmic microwave background radiation

NASA Technical Reports Server (NTRS)

Silk, J.; Wilson, M. L.

1981-01-01

Inhomogeneities in the large-scale distribution of matter inevitably lead to the generation of large-scale anisotropy in the cosmic background radiation. The dipole, quadrupole, and higher order fluctuations expected in an Einstein-de Sitter cosmological model have been computed. The dipole and quadrupole anisotropies are comparable to the measured values, and impose important constraints on the allowable spectrum of large-scale matter density fluctuations. A significant dipole anisotropy is generated by the matter distribution on scales greater than approximately 100 Mpc. The large-scale anisotropy is insensitive to the ionization history of the universe since decoupling, and cannot easily be reconciled with a galaxy formation theory that is based on primordial adiabatic density fluctuations.

Colloidal gas-liquid condensation of polystyrene latex particles with intermediate kappa a values (5 to 160, a > kappa(-1)).

PubMed

Ishikawa, Masamichi; Kitano, Ryota

2010-02-16

Polystyrene latex particles showed gas-liquid condensation under the conditions of large particle radius (a > kappa(-1)) and intermediate kappa a, where kappa is the Debye-Hückel parameter and a is the particle radius. The particles were dissolved in deionized water containing ethanol from 0 to 77 vol %, settled to the bottom of the glass plate within 1 h, and then laterally moved toward the center of a cell over a 20 h period in reaching a state of equilibrium condensation. All of the suspensions that were 1 and 3 microm in diameter and 0.01-0.20 vol % in concentration realized similar gas-liquid condensation with clear gas-liquid boundaries. In 50 vol % ethanol solvent, additional ethanol was added to enhance the sedimentation force so as to restrict the particles in a monoparticle layer thickness. The coexistence of gas-liquid-solid (crystalline solid) was microscopically recognized from the periphery to the center of the condensates. A phase diagram of the gas-liquid condensation was created as a function of KCl concentration at a particle diameter of 3 microm, 0.10 vol % concentration, and 50:50 water/ethanol solvent at room temperature. The miscibility gap was observed in the concentration range from 1 to 250 microM. There was an upper limit of salt concentration where the phase separation disappeared, showing nearly critical behavior of macroscopic density fluctuation from 250 microM to 1 mM. These results add new experimental evidence to the existence of colloidal gas-liquid condensation and specify conditions of like-charge attraction between particles.

Single fiber lignin distributions based on the density gradient column method

Treesearch

Brian Boyer; Alan W. Rudie

2007-01-01

The density gradient column method was used to determine the effects of uniform and non-uniform pulping processes on variation in individual fiber lignin concentrations of the resulting pulps. A density gradient column uses solvents of different densities and a mixing process to produce a column of liquid with a smooth transition from higher density at the bottom to...

The Theory of Nearly Incompressible Magnetohydrodynamic Turbulence: Homogeneous Description

NASA Astrophysics Data System (ADS)

Zank, G. P.; Adhikari, L.; Hunana, P.; Shiota, D.; Bruno, R.; Telloni, D.; Avinash, K.

2017-09-01

The theory of nearly incompressible magnetohydrodynamics (NI MHD) was developed to understand the apparent incompressibility of the solar wind and other plasma environments, particularly the relationship of density fluctuations to incompressible manifestations of turbulence in the solar wind and interstellar medium. Of interest was the identification of distinct leading-order incompressible descriptions for plasma beta β ≫ 1 and β ∼ 1 or ≪ 1 environments. In the first case, the “dimensionality” of the MHD description is 3D whereas for the latter two, there is a collapse of dimensionality in that the leading-order incompressible MHD description is 2D in a plane orthogonal to the large-scale or mean magnetic field. Despite the success of NI MHD in describing fluctuations in a low-frequency plasma environment such as the solar wind, a basic turbulence description has not been developed. Here, we rewrite the NI MHD system in terms of Elsässer variables. We discuss the distinction that emerges between the three cases. However, we focus on the β ∼ 1 or ≪ 1 regimes since these are appropriate to the solar wind and solar corona. In both cases, the leading-order turbulence model describes 2D turbulence and the higher-order description corresponds to slab turbulence, which forms a minority component. The Elsäasser β ∼ 1 or ≪ 1 formulation exhibits the nonlinear couplings between 2D and slab components very clearly, and shows that slab fluctuations respond in a passive scalar sense to the turbulently evolving majority 2D component fluctuations. The coupling of 2D and slab fluctuations through the β ∼ 1 or ≪ 1 NI MHD description leads to a very natural emergence of the “Goldreich-Sridhar” critical balance scaling parameter, although now with a different interpretation. Specifically, the critical balance parameter shows that the energy flux in wave number space is a consequence of the intensity of Alfvén wave sweeping versus passive scalar convection by leading-order 2D Elsässer fluctuations, with critical balance being achieved when Alfvén wave sweeping balances passive scalar convection by leading-order 2D Elsässer fluctuations. Besides yielding predictions of 2D and slab spectra for Elsässer fluctuations, NI MHD shows that density fluctuations are advected by the majority or dominant incompressible velocity fluctuations. In the case of β ∼ 1 or ≪ 1, the density spectrum is Kolmogorov in the perpendicular wave number, thus providing a possible explanation for the observed extended Kolmogorov-like power law spectrum for electron density fluctuations in the interstellar medium.

A Colorful Solubility Exercise for Organic Chemistry

ERIC Educational Resources Information Center

Shugrue, Christopher R.; Mentzen, Hans H., II; Linton, Brian R.

2015-01-01

A discovery chemistry laboratory has been developed for the introductory organic chemistry student to investigate the concepts of polarity, miscibility, solubility, and density. The simple procedure takes advantage of the solubility of two colored dyes in a series of solvents or solvent mixtures, and the diffusion of colors can be easily…

Measurement of dielectric constant of organic solvents by indigenously developed dielectric probe

NASA Astrophysics Data System (ADS)

Keshari, Ajay Kumar; Rao, J. Prabhakar; Rao, C. V. S. Brahmmananda; Ramakrishnan, R.; Ramanarayanan, R. R.

2018-04-01

The extraction, separation and purification of actinides (uranium and plutonium) from various matrices are an important step in nuclear fuel cycle. One of the separation process adopted in an industrial scale is the liquid-liquid extraction or solvent extraction. Liquid-liquid extraction uses a specific ligand/extractant in conjunction with suitable diluent. Solvent extraction or liquid-liquid extraction, involves the partitioning of the solute between two immiscible phases. In most cases, one of the phases is aqueous, and the other one is an organic solvent. The solvent used in solvent extraction should be selective for the metal of interest, it should have optimum distribution ratio, and the loaded metal from the organic phase should be easily stripped under suitable experimental conditions. Some of the important physical properties which are important for the solvent are density, viscosity, phase separation time, interfacial surface tension and the polarity of the extractant.

Stabilization of electron-scale turbulence by electron density gradient in national spherical torus experiment

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

Ruiz Ruiz, J.; White, A. E.; Ren, Y.

2015-12-15

Theory and experiments have shown that electron temperature gradient (ETG) turbulence on the electron gyro-scale, k{sub ⊥}ρ{sub e} ≲ 1, can be responsible for anomalous electron thermal transport in NSTX. Electron scale (high-k) turbulence is diagnosed in NSTX with a high-k microwave scattering system [D. R. Smith et al., Rev. Sci. Instrum. 79, 123501 (2008)]. Here we report on stabilization effects of the electron density gradient on electron-scale density fluctuations in a set of neutral beam injection heated H-mode plasmas. We found that the absence of high-k density fluctuations from measurements is correlated with large equilibrium density gradient, which ismore » shown to be consistent with linear stabilization of ETG modes due to the density gradient using the analytical ETG linear threshold in F. Jenko et al. [Phys. Plasmas 8, 4096 (2001)] and linear gyrokinetic simulations with GS2 [M. Kotschenreuther et al., Comput. Phys. Commun. 88, 128 (1995)]. We also found that the observed power of electron-scale turbulence (when it exists) is anti-correlated with the equilibrium density gradient, suggesting density gradient as a nonlinear stabilizing mechanism. Higher density gradients give rise to lower values of the plasma frame frequency, calculated based on the Doppler shift of the measured density fluctuations. Linear gyrokinetic simulations show that higher values of the electron density gradient reduce the value of the real frequency, in agreement with experimental observation. Nonlinear electron-scale gyrokinetic simulations show that high electron density gradient reduces electron heat flux and stiffness, and increases the ETG nonlinear threshold, consistent with experimental observations.« less

Density functional theory and conductivity studies of boron-based anion receptors

DOE PAGES

Leung, Kevin; Chaudhari, Mangesh I.; Rempe, Susan B.; ...

2015-07-10

Anion receptors that bind strongly to fluoride anions in organic solvents can help dissolve the lithium fluoride discharge products of primary carbon monofluoride (CFx) batteries, thereby preventing the clogging of cathode surfaces and improving ion conductivity. The receptors are also potentially beneficial to rechargeable lithium ion and lithium air batteries. We apply Density Functional Theory (DFT) to show that an oxalate-based pentafluorophenyl-boron anion receptor binds as strongly, or more strongly, to fluoride anions than many phenyl-boron anion receptors proposed in the literature. Experimental data shows marked improvement in electrolyte conductivity when this oxalate anion receptor is present. The receptor ismore » sufficiently electrophilic that organic solvent molecules compete with F – for boron-site binding, and specific solvent effects must be considered when predicting its F – affinity. To further illustrate the last point, we also perform computational studies on a geometrically constrained boron ester that exhibits much stronger gas-phase affinity for both F – and organic solvent molecules. After accounting for specific solvent effects, however, its net F – affinity is about the same as the simple oxalate-based anion receptor. Lastly, we propose that LiF dissolution in cyclic carbonate organic solvents, in the absence of anion receptors, is due mostly to the formation of ionic aggregates, not isolated F – ions.« less

Solvent dynamics and electron transfer reactions

NASA Astrophysics Data System (ADS)

Rasaiah, Jayendran C.; Zhu, Jianjun

1994-02-01

Recent experimental and theoretical studies of the influence of solvent dynamics on electron transfer (ET) reactions are discussed. It is seen that the survival probabilities of the reactants and products can be obtained as the solution to an integral equation using experimental or simulation data on the solvation dynamics. The theory developed for ET between thermally equilibrated reactants in solution, in which the ligand vibrations were treated classically, is extended to include quantum effects on the inner-shell ligand vibration and electron transfer from a nonequilibrium initial state prepared, for example, by laser excitation. This leads to a slight modification of the integral equation which is easily solved on a personal computer to provide results that can be directly compared with experiment. Analytic approximations to the solutions of the integral equation, ranging from a single exponential to multiexponential time dependence of the survival probabilities are discussed. The rate constant for the single exponential decay of the reactants interpolates between the thermal equilibrium rate constant kie (that is independent of solvent dynamics) and a diffusion controlled rate constant kid (determined by solvent dynamics) and also between the wide (A=0) and narrow (A=1) window limits dominated by inner-sphere ligand vibration and outer-sphere solvent reorganization respectively. The explicit dependence of the integral equation solutions on solvation dynamics S(t), the free energy of reaction ΔG0, the total reorganization energy λ and its partitioning between ligand vibration λq and solvent polarization fluctuations λ0, and the nature of the initial state should be useful in the analysis and design of ET experiments in different solvents.

Precursor of superfluidity in a strongly interacting Fermi gas with negative effective range

NASA Astrophysics Data System (ADS)

Tajima, Hiroyuki

2018-04-01

We investigate theoretically the effects of pairing fluctuations in an ultracold Fermi gas near a Feshbach resonance with a negative effective range. By employing a many-body T -matrix theory with a coupled fermion-boson model, we show that the single-particle density of states exhibits the so-called pseudogap phenomenon, which is a precursor of superfluidity induced by strong pairing fluctuations. We clarify the region where strong pairing fluctuations play a crucial role in single-particle properties, from the broad-resonance region to the narrow-resonance limit at the divergent two-body scattering length. We also extrapolate the effects of pairing fluctuations to the positive-effective-range region from our results near the narrow Feshbach resonance. Results shown in this paper are relevant to the connection between ultracold Fermi gases and low-density neutron matter from the viewpoint of finite-effective-range corrections.

Spectroscopic interpretation and velocimetry analysis of fluctuations in a cylindrical plasma recorded by a fast camera

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

Oldenbuerger, S.; Brandt, C.; Brochard, F.

2010-06-15

Fast visible imaging is used on a cylindrical magnetized argon plasma produced by thermionic discharge in the Mirabelle device. To link the information collected with the camera to a physical quantity, fast camera movies of plasma structures are compared to Langmuir probe measurements. High correlation is found between light fluctuations and plasma density fluctuations. Contributions from neutral argon and ionized argon to the overall light intensity are separated by using interference filters and a light intensifier. Light emitting transitions are shown to involve a metastable neutral argon state that can be excited by thermal plasma electrons, thus explaining the goodmore » correlation between light and density fluctuations. The propagation velocity of plasma structures is calculated by adapting velocimetry methods to the fast camera movies. The resulting estimates of instantaneous propagation velocity are in agreement with former experiments. The computation of mean velocities is discussed.« less

Local time dependence of turbulent magnetic fields in Saturn's magnetodisc

NASA Astrophysics Data System (ADS)

Kaminker, V.; Delamere, P. A.; Ng, C. S.; Dennis, T.; Otto, A.; Ma, X.

2017-04-01

Net plasma transport in magnetodiscs around giant planets is outward. Observations of plasma temperature have shown that the expanding plasma is heating nonadiabatically during this process. Turbulence has been suggested as a source of heating. However, the mechanism and distribution of magnetic fluctuations in giant magnetospheres are poorly understood. In this study we attempt to quantify the radial and local time dependence of fluctuating magnetic field signatures that are suggestive of turbulence, quantifying the fluctuations in terms of a plasma heating rate density. In addition, the inferred heating rate density is correlated with magnetic field configurations that include azimuthal bend forward/back and magnitude of the equatorial normal component of magnetic field relative to the dipole. We find a significant local time dependence in magnetic fluctuations that is consistent with flux transport triggered in the subsolar and dusk sectors due to magnetodisc reconnection.

Continuous description of fluctuating eccentricities

NASA Astrophysics Data System (ADS)

Blaizot, Jean-Paul; Broniowski, Wojciech; Ollitrault, Jean-Yves

2014-11-01

We consider the initial energy density in the transverse plane of a high energy nucleus-nucleus collision as a random field ρ (x), whose probability distribution P [ ρ ], the only ingredient of the present description, encodes all possible sources of fluctuations. We argue that it is a local Gaussian, with a short-range 2-point function, and that the fluctuations relevant for the calculation of the eccentricities that drive the anisotropic flow have small relative amplitudes. In fact, this 2-point function, together with the average density, contains all the information needed to calculate the eccentricities and their variances, and we derive general model independent expressions for these quantities. The short wavelength fluctuations are shown to play no role in these calculations, except for a renormalization of the short range part of the 2-point function. As an illustration, we compare to a commonly used model of independent sources, and recover the known results of this model.

Spectroscopic interpretation and velocimetry analysis of fluctuations in a cylindrical plasma recorded by a fast camera

NASA Astrophysics Data System (ADS)

Oldenbürger, S.; Brandt, C.; Brochard, F.; Lemoine, N.; Bonhomme, G.

2010-06-01

Fast visible imaging is used on a cylindrical magnetized argon plasma produced by thermionic discharge in the Mirabelle device. To link the information collected with the camera to a physical quantity, fast camera movies of plasma structures are compared to Langmuir probe measurements. High correlation is found between light fluctuations and plasma density fluctuations. Contributions from neutral argon and ionized argon to the overall light intensity are separated by using interference filters and a light intensifier. Light emitting transitions are shown to involve a metastable neutral argon state that can be excited by thermal plasma electrons, thus explaining the good correlation between light and density fluctuations. The propagation velocity of plasma structures is calculated by adapting velocimetry methods to the fast camera movies. The resulting estimates of instantaneous propagation velocity are in agreement with former experiments. The computation of mean velocities is discussed.

Far-forward collective scattering measurements by FIR polarimeter-interferometer on J-TEXT tokamak

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

Shi, P.; Chen, J., E-mail: jiech@hust.edu.cn; Gao, L.

The multi-channel three-wave polarimeter-interferometer system on J-TEXT tokamak has been exploited to measure far-forward collective scattering from electron density fluctuations. The diagnostic utilizes far infrared lasers operated at 432 μm with 17-channel vertical chords (3 cm chord spacing), covering the entire cross section of plasma. Scattering laser power is measured using a high-sensitivity Schottky planar diode mixer which can also detect polarimetric and interferometric phase simultaneously. The system provides a line-integrated measurement of density fluctuations with maximum measurable wave number: k{sub ⊥max} ≤ 2 cm{sup −1} and time response up to 350 kHz. Feasibility of the diagnostic has been tested,more » showing higher sensitivity to detect fluctuation than interferometric measurement. Capability of providing spatial-resolved information of fluctuation has also been demonstrated in preliminary experimental applications.« less

Biodiesel production from ethanolysis of palm oil using deep eutectic solvent (DES) as co-solvent

NASA Astrophysics Data System (ADS)

Manurung, R.; Winarta, A.; Taslim; Indra, L.

2017-06-01

Biodiesel produced from ethanolysis is more renewable and have better properties (higher oxidation stability, lower cloud and pour point) compared to methanolysis, but it has a disadvantage such as complicated purification. To improve ethanolysis process, deep eutectic solvent (DES) can be prepared from choline chloride and glycerol and used as co-solvent in ethanolysis. The deep eutectic solvent is formed from a quaternary ammonium salt (choline chloride) and a hydrogen bond donor (Glycerol), it is a non-toxic, biodegradable solvent compared to a conventional volatile organic solvent such as hexane. The deep eutectic solvent is prepared by mixing choline chloride and glycerol with molar ratio 1:2 at temperature 80 °C, stirring speed 300 rpm for 1 hour. The DES is characterized by its density and viscosity. The ethanolysis is performed at a reaction temperature of 70 °C, ethanol to oil molar ratio of 9:1, potassium hydroxide as catalyst concentration of 1.2 wt. DES as co-solvent with concentration 0.5 to 3 wt. stirring speed 400 rpm, and a reaction time 1 hour. The obtained biodiesel is then characterized by its density, viscosity, and ester content. The oil - ethanol phase condition is observed in the reaction tube. The oil - ethanol phase with DES tends to form meniscus compared to without DES, showed that oil and ethanol become more slightly miscible, which favors the reaction. Using DES as co-solvent in ethanolysis showed increasing in yield and easier purification. The esters properties meet the international standards ASTM D6751, with the highest yield achieved 83,67 with 99,77 conversion at DES concentration 2 . Increasing DES concentration above 2 in ethanolysis decrease the conversion and yield, because of the excessive glycerol in the systems makes the reaction equilibrium moves to the reactant side.

Low Density Resin Impregnated Ceramic Article Having an Average Density of 0.15 to 0.40 G/CC

NASA Technical Reports Server (NTRS)

Tran, Huy K. (Inventor); Henline, William D. (Inventor); Hsu, Ming-ta S. (Inventor); Rasky, Daniel J. (Inventor); Riccitiello, Salvatore R. (Inventor)

1996-01-01

A low-density resin impregnated ceramic article advantageously employed as a structural ceramic ablator comprising a fired preform of ceramic fibers. The fibers of the ceramic preform are coated with an organic resin film. The organic resin can be a thermoplastic resin or a cured thermosetting resin. In one embodiment, the resin is uniformly distributed within the ceramic article. In a second embodiment, the resin is distributed so as to provide a density gradient along at least one direction of the ceramic article. The resin impregnated ceramic article is prepared by providing a fired preform of ceramic fibers; immersing the preform of ceramic fibers in a solution of a solvent and an organic resin infiltrant; and removing the solvent to form a resin film on the ceramic fibers.

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions

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

Marenich, Aleksandr; Cramer, Christopher J; Truhlar, Donald G

2009-04-30

We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the “D” stands for “density” to denote that the full solute electron density is used without defining partial atomic charges. “Continuum” denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where “universal” denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which amore » few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calculation are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality constants called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aqueous ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and dimethyl sulfoxide, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaqueous organic solvents and water), and 143 transfer free energies for 93 neutral solutes between water and 15 organic solvents. The elements present in the solutes are H, C, N, O, F, Si, P, S, Cl, and Br. The SMD model employs a single set of parameters (intrinsic atomic Coulomb radii and atomic surface tension coefficients) optimized over six electronic structure methods: M05-2X/MIDI!6D, M05-2X/6-31G*, M05-2X/6-31+G**, M05-2X/cc-pVTZ, B3LYP/6-31G*, and HF/6-31G*. Although the SMD model has been parametrized using the IEF-PCM protocol for bulk electrostatics, it may also be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calculations in which the solute is represented by its electron density in real space. This includes, for example, the conductor-like screening algorithm. With the 6-31G* basis set, the SMD model achieves mean unsigned errors of 0.6-1.0 kcal/mol in the solvation free energies of tested neutrals and mean unsigned errors of 4 kcal/mol on average for ions with either Gaussian03 or GAMESS.« less

Spectral Behavior of Weakly Compressible Aero-Optical Distortions

NASA Astrophysics Data System (ADS)

Mathews, Edwin; Wang, Kan; Wang, Meng; Jumper, Eric

2016-11-01

In classical theories of optical distortions by atmospheric turbulence, an appropriate and key assumption is that index-of-refraction variations are dominated by fluctuations in temperature and the effects of turbulent pressure fluctuations are negligible. This assumption is, however, not generally valid for aero-optical distortions caused by turbulent flow over an optical aperture, where both temperature and pressures fluctuations may contribute significantly to the index-of-refraction fluctuations. A general expression for weak fluctuations in refractive index is derived using the ideal gas law and Gladstone-Dale relation and applied to describe the spectral behavior of aero-optical distortions. Large-eddy simulations of weakly compressible, temporally evolving shear layers are then used to verify the theoretical results. Computational results support theoretical findings and confirm that if the log slope of the 1-D density spectrum in the inertial range is -mρ , the optical phase distortion spectral slope is given by - (mρ + 1) . The value of mρ is then shown to be dependent on the ratio of shear-layer free-stream densities and bounded by the spectral slopes of temperature and pressure fluctuations. Supported by HEL-JTO through AFOSR Grant FA9550-13-1-0001 and Blue Waters Graduate Fellowship Program.

Jumping the gap: the formation conditions and mass function of `pebble-pile' planetesimals

NASA Astrophysics Data System (ADS)

Hopkins, Philip F.

2016-03-01

In a turbulent proto-planetary disc, dust grains undergo large-density fluctuations and under the right circumstances, grain overdensities can collapse under self-gravity (forming a `pebble-pile' planetesimal). Using a simple model for fluctuations predicted in simulations, we estimate the rate of formation and mass function of self-gravitating planetesimal-mass bodies formed by this mechanism. This depends sensitively on the grain size, disc surface density, and turbulent Mach numbers. However, when it occurs, the resulting planetesimal mass function is broad and quasi-universal, with a slope dN/dM ∝ M-(1-2), spanning size/mass range ˜10-104 km (˜10-9-5 M⊕). Collapse to planetesimal through super-Earth masses is possible. The key condition is that grain density fluctuations reach large amplitudes on large scales, where gravitational instability proceeds most easily (collapse of small grains is suppressed by turbulence). This leads to a new criterion for `pebble-pile' formation: τs ≳ 0.05 ln (Q1/2/Zd)/ln (1 + 10 α1/4) ˜ 0.3 ψ(Q, Z, α) where τs = ts Ω is the dimensionless particle stopping time. In a minimum-mass solar nebula, this requires grains larger than a = (50, 1, 0.1) cm at r=(1, 30, 100) au}. This may easily occur beyond the ice line, but at small radii would depend on the existence of large boulders. Because density fluctuations depend strongly on τs (inversely proportional to disc surface density), lower density discs are more unstable. Conditions for pebble-pile formation also become more favourable around lower mass, cooler stars.

Low density microcellular foams

DOEpatents

Aubert, J.H.; Clough, R.L.; Curro, J.G.; Quintana, C.A.; Russick, E.M.; Shaw, M.T.

1985-10-02

Low density, microporous polymer foams are provided by a process which comprises forming a solution of polymer and a suitable solvent followed by rapid cooling of the solution to form a phase-separated system and freeze the phase-separated system. The phase-separated system comprises a polymer phase and a solvent phase, each of which is substantially continuous within the other. The morphology of the polymer phase prior to and subsequent to freezing determine the morphology of the resultant foam. Both isotropic and anisotropic foams can be produced. If isotropic foams are produced, the polymer and solvent are tailored such that the solution spontaneously phase-separates prior to the point at which any component freezes. The morphology of the resultant polymer phase determines the morphology of the reusltant foam and the morphology of the polymer phase is retained by cooling the system at a rate sufficient to freeze one or both components of the system before a change in morphology can occur. Anisotropic foams are produced by forming a solution of polymer and solvent that will not phase separate prior to freezing of one or both components of the solution. In such a process, the solvent typically freezes before phase separation occurs. The morphology of the resultant frozen two-phase system determines the morphology of the resultant foam. The process involves subjecting the solution to essentially one-dimensional cooling. Foams having a density of less than 0.1 g/cc and a uniform cell size of less than 10 ..mu..m and a volume such that the foams have a length greater than 1 cm are provided.

Pulsational mode fluctuations and their basic conservation laws

NASA Astrophysics Data System (ADS)

Borah, B.; Karmakar, P. K.

2015-01-01

We propose a theoretical hydrodynamic model for investigating the basic features of nonlinear pulsational mode stability in a partially charged dust molecular cloud within the framework of the Jeans homogenization assumption. The inhomogeneous cloud is modeled as a quasi-neutral multifluid consisting of the warm electrons, warm ions, and identical inertial cold dust grains with partial ionization in a neutral gaseous background. The grain-charge is assumed not to vary in the fluctuation evolution time scale. The active inertial roles of the thermal species are included. We apply a standard multiple scaling technique centered on the gravito-electrostatic equilibrium to understand the fluctuations on the astrophysical scales of space and time. This is found that electrostatic and self-gravitational eigenmodes co-exist as diverse solitary spectral patterns governed by a pair of Korteweg-de Vries (KdV) equations. In addition, all the relevant classical conserved quantities associated with the KdV system under translational invariance are methodologically derived and numerically analyzed. A full numerical shape-analysis of the fluctuations, scale lengths and perturbed densities with multi-parameter variation of judicious plasma conditions is carried out. A correlation of the perturbed densities and gravito-electrostatic spectral patterns is also graphically indicated. It is demonstrated that the solitary mass, momentum and energy densities also evolve like solitary spectral patterns which remain conserved throughout the spatiotemporal scales of the fluctuation dynamics. Astrophysical and space environments significant to our results are briefly highlighted.

Dark matter and cosmology

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

Schramm, D.N.

1992-03-01

The cosmological dark matter problem is reviewed. The Big Bang Nucleosynthesis constraints on the baryon density are compared with the densities implied by visible matter, dark halos, dynamics of clusters, gravitational lenses, large-scale velocity flows, and the {Omega} = 1 flatness/inflation argument. It is shown that (1) the majority of baryons are dark; and (2) non-baryonic dark matter is probably required on large scales. It is also noted that halo dark matter could be either baryonic or non-baryonic. Descrimination between ``cold`` and ``hot`` non-baryonic candidates is shown to depend on the assumed ``seeds`` that stimulate structure formation. Gaussian density fluctuations,more » such as those induced by quantum fluctuations, favor cold dark matter, whereas topological defects such as strings, textures or domain walls may work equally or better with hot dark matter. A possible connection between cold dark matter, globular cluster ages and the Hubble constant is mentioned. Recent large-scale structure measurements, coupled with microwave anisotropy limits, are shown to raise some questions for the previously favored density fluctuation picture. Accelerator and underground limits on dark matter candidates are also reviewed.« less

Dark matter and cosmology

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

Schramm, D.N.

1992-03-01

The cosmological dark matter problem is reviewed. The Big Bang Nucleosynthesis constraints on the baryon density are compared with the densities implied by visible matter, dark halos, dynamics of clusters, gravitational lenses, large-scale velocity flows, and the {Omega} = 1 flatness/inflation argument. It is shown that (1) the majority of baryons are dark; and (2) non-baryonic dark matter is probably required on large scales. It is also noted that halo dark matter could be either baryonic or non-baryonic. Descrimination between cold'' and hot'' non-baryonic candidates is shown to depend on the assumed seeds'' that stimulate structure formation. Gaussian density fluctuations,more » such as those induced by quantum fluctuations, favor cold dark matter, whereas topological defects such as strings, textures or domain walls may work equally or better with hot dark matter. A possible connection between cold dark matter, globular cluster ages and the Hubble constant is mentioned. Recent large-scale structure measurements, coupled with microwave anisotropy limits, are shown to raise some questions for the previously favored density fluctuation picture. Accelerator and underground limits on dark matter candidates are also reviewed.« less

Dark matter and cosmology

NASA Astrophysics Data System (ADS)

Schramm, David N.

1992-07-01

The cosmological dark matter problem is reviewed. The Big Bang Nucleosynthesis constraints on the baryon density are compared with the densities implied by visible matter, dark halos, dynamics of clusters, gravitational lenses, large-scale velocity flows, and the Ω = 1 flatness/inflation argument. It is shown that (1) the majority of baryons are dark; and (2) non-baryonic dark matter is probably required on large scales. It is also noted that halo dark matter could be either baryonic or non-baryonic. Descrimination between ``cold'' and ``hot'' non-baryonic candidates is shown to depend on the assumed ``seeds'' that stimulate structure formation. Gaussian density fluctuations, such as those induced by quantum fluctuations, favor cold dark matter, whereas topological defects such as strings, textures or domain walls may work equally or better with hot dark matter. A possible connection between cold dark matter, globular cluster ages and the Hubble constant is mentioned. Recent large-scale structure measurements, coupled with microwave anisotropy limits, are shown to raise some questions for the previously favored density fluctuation picture. Accelerator and underground limits on dark matter candidates are also reviewed.

Dark matter and cosmology

NASA Astrophysics Data System (ADS)

Schramm, D. N.

1992-03-01

The cosmological dark matter problem is reviewed. The Big Bang nucleosynthesis constraints on the baryon density are compared with the densities implied by visible matter, dark halos, dynamics of clusters, gravitational lenses, large-scale velocity flows, and the omega = 1 flatness/inflation argument. It is shown that (1) the majority of baryons are dark; and (2) non-baryonic dark matter is probably required on large scales. It is also noted that halo dark matter could be either baryonic or non-baryonic. Descrimination between 'cold' and 'hot' non-baryonic candidates is shown to depend on the assumed 'seeds' that stimulate structure formation. Gaussian density fluctuations, such as those induced by quantum fluctuations, favor cold dark matter, whereas topological defects such as strings, textures or domain walls may work equally or better with hot dark matter. A possible connection between cold dark matter, globular cluster ages, and the Hubble constant is mentioned. Recent large-scale structure measurements, coupled with microwave anisotropy limits, are shown to raise some questions for the previously favored density fluctuation picture. Accelerator and underground limits on dark matter candidates are also reviewed.

The effect of density fluctuations on electron cyclotron beam broadening and implications for ITER

NASA Astrophysics Data System (ADS)

Snicker, A.; Poli, E.; Maj, O.; Guidi, L.; Köhn, A.; Weber, H.; Conway, G.; Henderson, M.; Saibene, G.

2018-01-01

We present state-of-the-art computations of propagation and absorption of electron cyclotron waves, retaining the effects of scattering due to electron density fluctuations. In ITER, injected microwaves are foreseen to suppress neoclassical tearing modes (NTMs) by driving current at the q=2 and q=3/2 resonant surfaces. Scattering of the beam can spoil the good localization of the absorption and thus impair NTM control capabilities. A novel tool, the WKBeam code, has been employed here in order to investigate this issue. The code is a Monte Carlo solver for the wave kinetic equation and retains diffraction, full axisymmetric tokamak geometry, determination of the absorption profile and an integral form of the scattering operator which describes the effects of turbulent density fluctuations within the limits of the Born scattering approximation. The approach has been benchmarked against the paraxial WKB code TORBEAM and the full-wave code IPF-FDMC. In particular, the Born approximation is found to be valid for ITER parameters. In this paper, we show that the radiative transport of EC beams due to wave scattering in ITER is diffusive unlike in present experiments, thus causing up to a factor of 2-4 broadening in the absorption profile. However, the broadening depends strongly on the turbulence model assumed for the density fluctuations, which still has large uncertainties.

SOLVENT HOLD TANK SAMPLE RESULTS FOR MCU-11-1452, MCU-11-1453, MCU-11-1454, MCU-11-1455, MCU-11-1456 AND MCU-11-1457

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

Peters, T.; Fondeur, F.; Fink, S.

Solvent Hold Tank (SHT) samples are sent to Savannah River National Laboratory (SRNL) to examine solvent composition changes over time. On December 5, 2011, Operations personnel delivered six samples from the SHT (MCU-11-1452 through -1457) for analysis. These samples are intended to verify that the solvent is within the specified composition range. The results from the analyses are presented in this document. Samples were received in p-nut vials containing {approx}10 mL each. Once taken into the Shielded Cells, the samples were combined. Samples were removed for analysis by density, semi-volatile organic analysis (SVOA), high performance liquid chromatography (HPLC), and Fourier-Transformmore » Infra-Red spectroscopy (FTIR). Details for the work are contained in a controlled laboratory notebook. Each of the six p-nut vials contained a single phase, with no apparent solids contamination or cloudiness. Table 1 contains the results of the analyses for the combined samples. A duplicate density measurement of the organic phase gave a result of 0.844 g/mL (1.2% residual standard deviation - RSD). Using the density as a starting point, we know that the Isopar{reg_sign} L should be slightly higher than nominal and the other components should be slightly lower than nominal. The results as a whole are internally consistent. All measurements indicate Isopar{reg_sign} L higher than nominal, and Modifier lower than nominal. The extractant result is higher than expected - given the other results, the extractant concentration should be under nominal values. Using the measured density as well as the Isopar{reg_sign} L and Modifier concentrations from the FTIR results, we calculate an extractant concentration of 6888 mg/L. This value is outside the analytical uncertainty of the reported HPLC value. Given the other results, this most likely indicates that the HPLC extractant result was biased high. When compared to the MCU density target of 0.845 g/mL, there is no need to add an Isopar{reg_sign} L trim. However, it is advisable to add sufficient trioctylamine (TOA) to return the solvent composition to within specifications as that component has declined to about 64% the concentration since the last analysis. The TOA measurement was performed twice, so the result is not an analytical aberration. TOA has not been added to the system since the previous quarterly sample in October 2011. As with the previous solvent sample results, these analyses indicate that the solvent does not require Isopar{reg_sign} L trimming at this time. However, addition of TOA is warranted. These findings indicate that the new protocols for solvent monitoring and control are yielding favorable results. Nevertheless, the deviation in the TOA concentration since the last analysis indicates continued periodic (i.e., quarterly) monitoring is recommended.« less

Using Grand Canonical Monte Carlo Simulations to Understand the Role of Interfacial Fluctuations on Solvation at the Water-Vapor Interface.

PubMed

Rane, Kaustubh; van der Vegt, Nico F A

2016-09-15

The present work investigates the effect of interfacial fluctuations (predominantly capillary wave-like fluctuations) on the solvation free energy (Δμ) of a monatomic solute at the water-vapor interface. We introduce a grand-canonical-ensemble-based simulation approach that quantifies the contribution of interfacial fluctuations to Δμ. This approach is used to understand how the above contribution depends on the strength of dispersive and electrostatic solute-water interactions at the temperature of 400 K. At this temperature, we observe that interfacial fluctuations do play a role in the variation of Δμ with the strength of the electrostatic solute-water interaction. We also use grand canonical simulations to further investigate how interfacial fluctuations affect the propensity of the solute toward the water-vapor interface. To this end, we track a quantity called the interface potential (surface excess free energy) with the number of water molecules. With increasing number of water molecules, the liquid-vapor interface moves across a solute, which is kept at a fixed position in the simulation. Hence, the dependence of the interface potential on the number of waters models the process of moving the solute through the water-vapor interface. We analyze the change of the interface potential with the number of water molecules to explain that solute-induced changes in the interfacial fluctuations, like the pinning of capillary-wave-like undulations, do not play any role in the propensity of solutes toward water-vapor interfaces. The above analysis also shows that the dampening of interfacial fluctuations accompanies the adsorption of any solute at the liquid-vapor interface, irrespective of the chemical nature of the solute and solvent. However, such a correlation does not imply that dampening of fluctuations causes adsorption.

The statistics of peaks of Gaussian random fields. [cosmological density fluctuations

NASA Technical Reports Server (NTRS)

Bardeen, J. M.; Bond, J. R.; Kaiser, N.; Szalay, A. S.

1986-01-01

A set of new mathematical results on the theory of Gaussian random fields is presented, and the application of such calculations in cosmology to treat questions of structure formation from small-amplitude initial density fluctuations is addressed. The point process equation is discussed, giving the general formula for the average number density of peaks. The problem of the proper conditional probability constraints appropriate to maxima are examined using a one-dimensional illustration. The average density of maxima of a general three-dimensional Gaussian field is calculated as a function of heights of the maxima, and the average density of 'upcrossing' points on density contour surfaces is computed. The number density of peaks subject to the constraint that the large-scale density field be fixed is determined and used to discuss the segregation of high peaks from the underlying mass distribution. The machinery to calculate n-point peak-peak correlation functions is determined, as are the shapes of the profiles about maxima.

Molecular simulation of CO chemisorption on Co(0001) in presence of supercritical fluid solvent: A potential of mean force study

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

Asiaee, Alireza; Benjamin, Kenneth M., E-mail: kenneth.benjamin@sdsmt.edu

2016-08-28

For several decades, heterogeneous catalytic processes have been improved through utilizing supercritical fluids (SCFs) as solvents. While numerous experimental studies have been established across a range of chemistries, such as oxidation, pyrolysis, amination, and Fischer-Tropsch synthesis, still there is little fundamental, molecular-level information regarding the role of the SCF on elementary heterogeneous catalytic steps. In this study, the influence of hexane solvent on the adsorption of carbon monoxide on Co(0001), as the first step in the reaction mechanism of many processes involving syngas conversion, is probed. Simulations are performed at various bulk hexane densities, ranging from ideal gas conditions (nomore » SCF hexane) to various near- and super-critical hexane densities. For this purpose, both density functional theory and molecular dynamics simulations are employed to determine the adsorption energy and free energy change during CO chemisorption. Potential of mean force calculations, utilizing umbrella sampling and the weighted histogram analysis method, provide the first commentary on SCF solvent effects on the energetic aspects of the chemisorption process. Simulation results indicate an enhanced stability of CO adsorption on the catalyst surface in the presence of supercritical hexane within the reduced pressure range of 1.0–1.5 at a constant temperature of 523 K. Furthermore, it is shown that the maximum stability of CO in the adsorbed state as a function of supercritical hexane density at 523 K nearly coincides with the maximum isothermal compressibility of bulk hexane at this temperature.« less

Quasi-optical design for systems to diagnose the electron temperature and density fluctuations on EAST

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

Cao, Qifo; Liu, Yong; Zhao, Hailin, E-mail: zhaohailin@ipp.ac.cn

A system to simultaneously diagnose the electron temperature and density fluctuations is proposed for Experimental Advanced Superconducting Tokamak device. This system includes a common quasi-optical antenna, a correlation electron cyclotron emission (CECE) system that is used to measure the electron temperature fluctuations and a Doppler backscattering (DBS) system that is used to measure the electron density fluctuations. The frequency range of the proposed CECE system is 108-120 GHz, and this corresponds to a radial coverage of normalized radius ((R − R{sub 0})/a, R{sub 0} = 1850 mm, a = 450 mm) from 0.2 to 0.67 for the plasma operation withmore » a toroidal magnetic field of 2.26 T. This paper focuses on the design of the quasi-optical antenna and aims at optimizing the poloidal resolution for different frequency bands. An optimum result gives the beam radius for the CECE system of 13-15 mm and this corresponds to a wave number range of k{sub θ} < 2.4 cm{sup −1}. The beam radius is 20-30 mm for V band (50-75 GHz) and 15-20 mm for W band (75-110 GHz).« less

Effects of trap density on drain current LFN and its model development for E-mode GaN MOS-HEMT

NASA Astrophysics Data System (ADS)

Panda, D. K.; Lenka, T. R.

2017-12-01

In this paper the drain current low-frequency noise (LFN) of E-mode GaN MOS-HEMT is investigated for different gate insulators such as SiO2, Al2O3/Ga2O3/GdO3, HfO2/SiO2, La2O3/SiO2 and HfO2 with different trap densities by IFM based TCAD simulation. In order to analyze this an analytical model of drain current low frequency noise is developed. The model is developed by considering 2DEG carrier fluctuations, mobility fluctuations and the effects of 2DEG charge carrier fluctuations on the mobility. In the study of different gate insulators it is observed that carrier fluctuation is the dominant low frequency noise source and the non-uniform exponential distribution is critical to explain LFN behavior, so the analytical model is developed by considering uniform distribution of trap density. The model is validated with available experimental data from literature. The effect of total number of traps and gate length scaling on this low frequency noise due to different gate dielectrics is also investigated.

A molecular dynamics study of intramolecular proton transfer reaction of malonaldehyde in solution based upon a mixed quantum-classical approximation. II. Proton transfer reaction in non-polar solvent

NASA Astrophysics Data System (ADS)

Kojima, H.; Yamada, A.; Okazaki, S.

2015-05-01

The intramolecular proton transfer reaction of malonaldehyde in neon solvent has been investigated by mixed quantum-classical molecular dynamics (QCMD) calculations and fully classical molecular dynamics (FCMD) calculations. Comparing these calculated results with those for malonaldehyde in water reported in Part I [A. Yamada, H. Kojima, and S. Okazaki, J. Chem. Phys. 141, 084509 (2014)], the solvent dependence of the reaction rate, the reaction mechanism involved, and the quantum effect therein have been investigated. With FCMD, the reaction rate in weakly interacting neon is lower than that in strongly interacting water. However, with QCMD, the order of the reaction rates is reversed. To investigate the mechanisms in detail, the reactions were categorized into three mechanisms: tunneling, thermal activation, and barrier vanishing. Then, the quantum and solvent effects were analyzed from the viewpoint of the reaction mechanism focusing on the shape of potential energy curve and its fluctuations. The higher reaction rate that was found for neon in QCMD compared with that found for water solvent arises from the tunneling reactions because of the nearly symmetric double-well shape of the potential curve in neon. The thermal activation and barrier vanishing reactions were also accelerated by the zero-point energy. The number of reactions based on these two mechanisms in water was greater than that in neon in both QCMD and FCMD because these reactions are dominated by the strength of solute-solvent interactions.

Characterizing pixel and point patterns with a hyperuniformity disorder length

NASA Astrophysics Data System (ADS)

Chieco, A. T.; Dreyfus, R.; Durian, D. J.

2017-09-01

We introduce the concept of a "hyperuniformity disorder length" h that controls the variance of volume fraction fluctuations for randomly placed windows of fixed size. In particular, fluctuations are determined by the average number of particles within a distance h from the boundary of the window. We first compute special expectations and bounds in d dimensions, and then illustrate the range of behavior of h versus window size L by analyzing several different types of simulated two-dimensional pixel patterns—where particle positions are stored as a binary digital image in which pixels have value zero if empty and one if they contain a particle. The first are random binomial patterns, where pixels are randomly flipped from zero to one with probability equal to area fraction. These have long-ranged density fluctuations, and simulations confirm the exact result h =L /2 . Next we consider vacancy patterns, where a fraction f of particles on a lattice are randomly removed. These also display long-range density fluctuations, but with h =(L /2 )(f /d ) for small f , and h =L /2 for f →1 . And finally, for a hyperuniform system with no long-range density fluctuations, we consider "Einstein patterns," where each particle is independently displaced from a lattice site by a Gaussian-distributed amount. For these, at large L ,h approaches a constant equal to about half the root-mean-square displacement in each dimension. Then we turn to gray-scale pixel patterns that represent simulated arrangements of polydisperse particles, where the volume of a particle is encoded in the value of its central pixel. And we discuss the continuum limit of point patterns, where pixel size vanishes. In general, we thus propose to quantify particle configurations not just by the scaling of the density fluctuation spectrum but rather by the real-space spectrum of h (L ) versus L . We call this approach "hyperuniformity disorder length spectroscopy".

Characterizing pixel and point patterns with a hyperuniformity disorder length.

PubMed

Chieco, A T; Dreyfus, R; Durian, D J

2017-09-01

We introduce the concept of a "hyperuniformity disorder length" h that controls the variance of volume fraction fluctuations for randomly placed windows of fixed size. In particular, fluctuations are determined by the average number of particles within a distance h from the boundary of the window. We first compute special expectations and bounds in d dimensions, and then illustrate the range of behavior of h versus window size L by analyzing several different types of simulated two-dimensional pixel patterns-where particle positions are stored as a binary digital image in which pixels have value zero if empty and one if they contain a particle. The first are random binomial patterns, where pixels are randomly flipped from zero to one with probability equal to area fraction. These have long-ranged density fluctuations, and simulations confirm the exact result h=L/2. Next we consider vacancy patterns, where a fraction f of particles on a lattice are randomly removed. These also display long-range density fluctuations, but with h=(L/2)(f/d) for small f, and h=L/2 for f→1. And finally, for a hyperuniform system with no long-range density fluctuations, we consider "Einstein patterns," where each particle is independently displaced from a lattice site by a Gaussian-distributed amount. For these, at large L,h approaches a constant equal to about half the root-mean-square displacement in each dimension. Then we turn to gray-scale pixel patterns that represent simulated arrangements of polydisperse particles, where the volume of a particle is encoded in the value of its central pixel. And we discuss the continuum limit of point patterns, where pixel size vanishes. In general, we thus propose to quantify particle configurations not just by the scaling of the density fluctuation spectrum but rather by the real-space spectrum of h(L) versus L. We call this approach "hyperuniformity disorder length spectroscopy".

Mapping current fluctuations of stochastic pumps to nonequilibrium steady states.

PubMed

Rotskoff, Grant M

2017-03-01

We show that current fluctuations in a stochastic pump can be robustly mapped to fluctuations in a corresponding time-independent nonequilibrium steady state. We thus refine a recently proposed mapping so that it ensures equivalence of not only the averages, but also optimal representation of fluctuations in currents and density. Our mapping leads to a natural decomposition of the entropy production in stochastic pumps similar to the "housekeeping" heat. As a consequence of the decomposition of entropy production, the current fluctuations in weakly perturbed stochastic pumps are shown to satisfy a universal bound determined by the steady state entropy production.

Physicochemical properties and ion-solvent interactions in aqueous sodium, ammonium, and lead acetate solution

NASA Astrophysics Data System (ADS)

Deosarkar, S. D.; Mendkudle, M. S.

2014-09-01

Densities (ρ), viscosities (η) and refractive indices ( n D) of aqueous sodium acetate (SA), ammonium acetate (AA), and lead acetate (LA) solutions have been measured for different concentrations of salts at 302.15 K. Apparent molar volumes (φv) for studied solutions were calculated from density data, and fitted to Masson's relation and partial molar volume (φ{v/o}) was determined. Viscosity data were fitted to Jones-Dole equation and viscosity A- and B-coefficients were determined. Refractive index and density data were fitted to Lorentz and Lorenz equation and specific refraction ( R D) were calculated. Behavior of various physicochemical properties indicated presence of strong ion-solvent interactions in present systems and the acetate salts structure maker in water.

Linear response coupled cluster theory with the polarizable continuum model within the singles approximation for the solvent response.

PubMed

Caricato, Marco

2018-04-07

We report the theory and the implementation of the linear response function of the coupled cluster (CC) with the single and double excitations method combined with the polarizable continuum model of solvation, where the correlation solvent response is approximated with the perturbation theory with energy and singles density (PTES) scheme. The singles name is derived from retaining only the contribution of the CC single excitation amplitudes to the correlation density. We compare the PTES working equations with those of the full-density (PTED) method. We then test the PTES scheme on the evaluation of excitation energies and transition dipoles of solvated molecules, as well as of the isotropic polarizability and specific rotation. Our results show a negligible difference between the PTED and PTES schemes, while the latter affords a significantly reduced computational cost. This scheme is general and can be applied to any solvation model that includes mutual solute-solvent polarization, including explicit models. Therefore, the PTES scheme is a competitive approach to compute response properties of solvated systems using CC methods.

Linear response coupled cluster theory with the polarizable continuum model within the singles approximation for the solvent response

NASA Astrophysics Data System (ADS)

Caricato, Marco

2018-04-01

We report the theory and the implementation of the linear response function of the coupled cluster (CC) with the single and double excitations method combined with the polarizable continuum model of solvation, where the correlation solvent response is approximated with the perturbation theory with energy and singles density (PTES) scheme. The singles name is derived from retaining only the contribution of the CC single excitation amplitudes to the correlation density. We compare the PTES working equations with those of the full-density (PTED) method. We then test the PTES scheme on the evaluation of excitation energies and transition dipoles of solvated molecules, as well as of the isotropic polarizability and specific rotation. Our results show a negligible difference between the PTED and PTES schemes, while the latter affords a significantly reduced computational cost. This scheme is general and can be applied to any solvation model that includes mutual solute-solvent polarization, including explicit models. Therefore, the PTES scheme is a competitive approach to compute response properties of solvated systems using CC methods.

Solvent effects on adsorption of CO over CuCl(1 1 1) surface: A density functional theory study

NASA Astrophysics Data System (ADS)

Zhang, Riguang; Ling, Lixia; Wang, Baojun; Huang, Wei

2010-09-01

DFT calculations have been performed to investigate the effect of dielectric responses of the solvent environment on the CO adsorption over CuCl(1 1 1) surface by using COSMO (conductor-like solvent model) model in Dmol 3. Different dielectric constants, including vacuum, liquid paraffin, methylene chloride, methanol and water solution, are considered. The effects of solvent model on the structural parameters, adsorption energies and vibrational frequency of CO adsorption over CuCl(1 1 1) surface have been investigated. The calculation results suggest that solvent effects can improve the stability of CO adsorption and reduce the intensity of C-O bond, which might mean that solvent is in favor of C-O bond activation and improve the reaction activity of oxidative carbonylation in a slurry reactor.

Nonlinear effects of climate and density in the dynamics of a fluctuating population of reindeer.

PubMed

Tyler, Nicholas J C; Forchhammer, Mads C; Øritsland, Nils Are

2008-06-01

Nonlinear and irregular population dynamics may arise as a result of phase dependence and coexistence of multiple attractors. Here we explore effects of climate and density in the dynamics of a highly fluctuating population of wild reindeer (Rangifer tarandus platyrhynchus) on Svalbard observed over a period of 29 years. Time series analyses revealed that density dependence and the effects of local climate (measured as the degree of ablation [melting] of snow during winter) on numbers were both highly nonlinear: direct negative density dependence was found when the population was growing (Rt > 0) and during phases of the North Atlantic Oscillation (NAO) characterized by winters with generally high (1979-1995) and low (1996-2007) indices, respectively. A growth-phase-dependent model explained the dynamics of the population best and revealed the influence of density-independent processes on numbers that a linear autoregressive model missed altogether. In particular, the abundance of reindeer was enhanced by ablation during phases of growth (Rt > 0), an observation that contrasts with the view that periods of mild weather in winter are normally deleterious for reindeer owing to icing of the snowpack. Analyses of vital rates corroborated the nonlinearity described in the population time series and showed that both starvation mortality in winter and fecundity were nonlinearly related to fluctuations in density and the level of ablation. The erratic pattern of growth of the population of reindeer in Adventdalen seems, therefore, to result from a combination of the effects of nonlinear density dependence, strong density-dependent mortality, and variable density independence related to ablation in winter.

On the characterization of inhomogeneity of the density distribution in supercritical fluids via molecular dynamics simulation and data mining analysis.

PubMed

Idrissi, Abdenacer; Vyalov, Ivan; Georgi, Nikolaj; Kiselev, Michael

2013-10-10

We combined molecular dynamics simulation and DBSCAN algorithm (Density Based Spatial Clustering of Application with Noise) in order to characterize the local density inhomogeneity distribution in supercritical fluids. The DBSCAN is an algorithm that is capable of finding arbitrarily shaped density domains, where domains are defined as dense regions separated by low-density regions. The inhomogeneity of density domain distributions of Ar system in sub- and supercritical conditions along the 50 bar isobar is associated with the occurrence of a maximum in the fluctuation of number of particles of the density domains. This maximum coincides with the temperature, Tα, at which the thermal expansion occurs. Furthermore, using Voronoi polyhedral analysis, we characterized the structure of the density domains. The results show that with increasing temperature below Tα, the increase of the inhomogeneity is mainly associated with the density fluctuation of the border particles of the density domains, while with increasing temperature above Tα, the decrease of the inhomogeneity is associated with the core particles.

From density to interface fluctuations: The origin of wavelength dependence in surface tension

NASA Astrophysics Data System (ADS)

Hiester, Thorsten

2008-12-01

The height-height correlation function for a fluctuating interface between two coexisting bulk phases is derived by means of general equilibrium properties of the corresponding density-density correlation function. A wavelength-dependent surface tension γ(q) can be defined and expressed in terms of the direct correlation function c(r,r') , the equilibrium density profile ρ0(r) , and an operator which relates density to surface configurations. Neither the concept of an effective interface Hamiltonian nor the difference in pressure is needed to determine the general structure of the height-height correlations or γ(q) , respectively. This result generalizes the Mecke-Dietrich surface tension γMD(q) [Phys. Rev. E 59, 6766 (1999)] and modifies recently published criticism concerning γMD(q) [Tarazona, Checa, and Chacón, Phys. Rev. Lett. 99, 196101 (2007)].

An association of magnetospheric whistler dispersion characteristics with changes in local plasma density.

NASA Technical Reports Server (NTRS)

Scarf, F. L.; Chappell, C. R.

1973-01-01

We use OGO 5 measurements made within the plasmapause on May 15, 1969, to investigate the possible association between changes in lightning whistler dispersion characteristics and local density fluctuations. It is shown that groups of whistlers with relatively constant dispersions tended to be detected in regions where the local ion concentration was significantly enhanced. It is assumed that these local density fluctuations represent characteristics of large-scale field-aligned variations. The results are then compared with ray refraction estimates appropriate for low-frequency whistler mode propagation (wave components with frequencies comparable to the local lower hybrid frequency) in a nonuniform medium.

On the large scale structure of X-ray background sources

NASA Technical Reports Server (NTRS)

Bi, H. G.; Meszaros, A.; Meszaros, P.

1991-01-01

The large scale clustering of the sources responsible for the X-ray background is discussed, under the assumption of a discrete origin. The formalism necessary for calculating the X-ray spatial fluctuations in the most general case where the source density contrast in structures varies with redshift is developed. A comparison of this with observational limits is useful for obtaining information concerning various galaxy formation scenarios. The calculations presented show that a varying density contrast has a small impact on the expected X-ray fluctuations. This strengthens and extends previous conclusions concerning the size and comoving density of large scale structures at redshifts 0.5 between 4.0.

Measurement of turbulence decorrelation during transport barrier evolution in a high-temperature fusion plasma.

PubMed

Nazikian, R; Shinohara, K; Kramer, G J; Valeo, E; Hill, K; Hahm, T S; Rewoldt, G; Ide, S; Koide, Y; Oyama, Y; Shirai, H; Tang, W

2005-04-08

A low power polychromatic beam of microwaves is used to diagnose the behavior of turbulent fluctuations in the core of the JT-60U tokamak during the evolution of the internal transport barrier. A continuous reduction in the size of turbulent structures is observed concomitant with the reduction of the density scale length during the evolution of the internal transport barrier. The density correlation length decreases to the order of the ion gyroradius, in contrast with the much longer scale lengths observed earlier in the discharge, while the density fluctuation level remain similar to the level before transport barrier formation.

Beyond Poisson-Boltzmann: Fluctuation effects and correlation functions

NASA Astrophysics Data System (ADS)

Netz, R. R.; Orland, H.

2000-02-01

We formulate the exact non-linear field theory for a fluctuating counter-ion distribution in the presence of a fixed, arbitrary charge distribution. The Poisson-Boltzmann equation is obtained as the saddle-point of the field-theoretic action, and the effects of counter-ion fluctuations are included by a loop-wise expansion around this saddle point. The Poisson equation is obeyed at each order in this loop expansion. We explicitly give the expansion of the Gibbs potential up to two loops. We then apply our field-theoretic formalism to the case of a single impenetrable wall with counter ions only (in the absence of salt ions). We obtain the fluctuation corrections to the electrostatic potential and the counter-ion density to one-loop order without further approximations. The relative importance of fluctuation corrections is controlled by a single parameter, which is proportional to the cube of the counter-ion valency and to the surface charge density. The effective interactions and correlation functions between charged particles close to the charged wall are obtained on the one-loop level.

Solvent/co-solvent effects on the electronic properties and adsorption mechanism of anticancer drug Thioguanine on Graphene oxide surface as a nanocarrier: Density functional theory investigation and a molecular dynamics

NASA Astrophysics Data System (ADS)

Hasanzade, Zohre; Raissi, Heidar

2017-11-01

In this work, the adsorption of Thioguanine (TG) anticancer drug on the surface of Graphene oxide (GO) nanosheet has investigated using density functional theory (DFT) and molecular dynamics simulation (MDs). Quantum mechanics calculations by two methods including M06-2X/6-31G**and ωB97X-D/6-31G** have been employed to calculate the details of energetic, geometric, and electronic properties of the TG molecule interacting with Graphene oxide nanosheet (GONS). DFT calculations confirmed that the strongest adsorption is observed when hydrogen bond interactions between TG molecule and the functional groups of Graphene oxide nanosheet are predominate. In all calculations, solvent effects have been considered in water using the PCM method. It is found that TG molecule can be adsorbed on Graphene oxide with negative solvation energy, indicating the TG adsorption on Graphene oxide surfaces is thermodynamically favored. Moreover, MD simulations are examined to understand the solvent/co-solvent effect (water, ethanol, nicotine) on the Thioguanine drug delivery through Graphene oxide. The results of RDF patterns and the van der Waals energy calculations show that interaction between TG drugs and the Graphene oxide surface is stronger in water solvent compared to the other co-solvent. The obtained MD results illustrate that when nicotine and ethanol exist in the system, the drug takes longer time to bind with GO nanosheet and the system becomes unstable. It can be concluded that Graphene oxide can be a promising candidate in water media for delivery the TG molecule.

40 CFR 63.5746 - How do I demonstrate compliance with the emission limits for aluminum wipedown solvents and...

Code of Federal Regulations, 2011 CFR

2011-07-01

...) to determine the density of each aluminum surface coating and wipedown solvent. (d) Compliance is... Hazardous Air Pollutants for Boat Manufacturing Standards for Aluminum Recreational Boat Surface Coating... of solids per liter of coating, or volume fraction) of each aluminum surface coating, including...

Detailed solvent, structural, quantum chemical study and antimicrobial activity of isatin Schiff base

NASA Astrophysics Data System (ADS)

Brkić, Dominik R.; Božić, Aleksandra R.; Marinković, Aleksandar D.; Milčić, Miloš K.; Prlainović, Nevena Ž.; Assaleh, Fathi H.; Cvijetić, Ilija N.; Nikolić, Jasmina B.; Drmanić, Saša Ž.

2018-05-01

The ratios of E/Z isomers of sixteen synthesized 1,3-dihydro-3-(substituted phenylimino)-2H-indol-2-one were studied using experimental and theoretical methodology. Linear solvation energy relationships (LSER) rationalized solvent influence of the solvent-solute interactions on the UV-Vis absorption maxima shifts (νmax) of both geometrical isomers using the Kamlet-Taft equation. Linear free energy relationships (LFER) in the form of single substituent parameter equation (SSP) was used to analyze substituent effect on pKa, NMR chemical shifts and νmax values. Electron charge density was obtained by the use of Quantum Theory of Atoms in Molecules, i.e. Bader's analysis. The substituent and solvent effect on intramolecular charge transfer (ICT) were interpreted with the aid of time-dependent density functional (TD-DFT) method. Additionally, the results of TD-DFT calculations quantified the efficiency of ICT from the calculated charge-transfer distance (DCT) and amount of transferred charge (QCT). The antimicrobial activity was evaluated using broth microdilution method. 3D QSAR modeling was used to demonstrate the influence of substituents effect as well as molecule geometry on antimicrobial activity.

Interactions between Nanoparticles and Polymer Brushes: Molecular Dynamics Simulations and Self-consistent Field Theory Calculations

NASA Astrophysics Data System (ADS)

Cheng, Shengfeng; Wen, Chengyuan; Egorov, Sergei

2015-03-01

Molecular dynamics simulations and self-consistent field theory calculations are employed to study the interactions between a nanoparticle and a polymer brush at various densities of chains grafted to a plane. Simulations with both implicit and explicit solvent are performed. In either case the nanoparticle is loaded to the brush at a constant velocity. Then a series of simulations are performed to compute the force exerted on the nanoparticle that is fixed at various distances from the grafting plane. The potential of mean force is calculated and compared to the prediction based on a self-consistent field theory. Our simulations show that the explicit solvent leads to effects that are not captured in simulations with implicit solvent, indicating the importance of including explicit solvent in molecular simulations of such systems. Our results also demonstrate an interesting correlation between the force on the nanoparticle and the density profile of the brush. We gratefully acknowledge the support of NVIDIA Corporation with the donation of the Tesla K40 GPU used for this research.

Multiscale modeling of electroosmotic flow: Effects of discrete ion, enhanced viscosity, and surface friction

NASA Astrophysics Data System (ADS)

Bhadauria, Ravi; Aluru, N. R.

2017-05-01

We propose an isothermal, one-dimensional, electroosmotic flow model for slit-shaped nanochannels. Nanoscale confinement effects are embedded into the transport model by incorporating the spatially varying solvent and ion concentration profiles that correspond to the electrochemical potential of mean force. The local viscosity is dependent on the solvent local density and is modeled using the local average density method. Excess contributions to the local viscosity are included using the Onsager-Fuoss expression that is dependent on the local ionic strength. A Dirichlet-type boundary condition is provided in the form of the slip velocity that is dependent on the macroscopic interfacial friction. This solvent-surface specific interfacial friction is estimated using a dynamical generalized Langevin equation based framework. The electroosmotic flow of Na+ and Cl- as single counterions and NaCl salt solvated in Extended Simple Point Charge (SPC/E) water confined between graphene and silicon slit-shaped nanochannels are considered as examples. The proposed model yields a good quantitative agreement with the solvent velocity profiles obtained from the non-equilibrium molecular dynamics simulations.

Dispersive liquid-liquid microextraction based on the solidification of floating organic droplet for the determination of polychlorinated biphenyls in aqueous samples.

PubMed

Dai, Liping; Cheng, Jing; Matsadiq, Guzalnur; Liu, Lu; Li, Jun-Kai

2010-08-03

In the proposed method, an extraction solvent with a lower toxicity and density than the solvents typically used in dispersive liquid-liquid microextraction was used to extract seven polychlorinated biphenyls (PCBs) from aqueous samples. Due to the density and melting point of the extraction solvent, the extract which forms a layer on top of aqueous sample can be collected by solidifying it at low temperatures, which form a layer on top of the aqueous sample. Furthermore, the solidified phase can be easily removed from the aqueous phase. Based on preliminary studies, 1-undecanol was selected as the extraction solvent, and a series of parameters that affect the extraction efficiency were systematically investigated. Under the optimized conditions, enrichment factors for PCBs ranged between 494 and 606. Based on a signal-to-noise ratio of 3, the limit of detection for the method ranged between 3.3 and 5.4 ng L(-1). Good linearity, reproducibility and recovery were also obtained. 2010 Elsevier B.V. All rights reserved.

Global financial crisis making a V-shaped fluctuation in NO2 pollution over the Yangtze River Delta

NASA Astrophysics Data System (ADS)

Du, Yin; Xie, Zhiqing

2017-04-01

The Yangtze River Delta (YRD), China's main cultural and economic center, has become one of the most seriously polluted areas in the world with respect to nitrogen oxides (NOx), owing to its rapid industrialization and urbanization, as well as substantial coal consumption. On the basis of nitrogen dioxide (NO2) density data from ozone monitoring instrument (OMI) and ground-based observations, the effects of industrial fluctuations due to the financial crisis on local NO2 pollution were quantitatively assessed. The results were as follows. (1) A distinct V-shaped fluctuation of major industrial products, thermal generating capacity, electricity consumption, and tropospheric NO2 densities was associated with the global financial crisis from May 2007 to December 2009, with the largest anomalies 1.5 times more than standard deviations at the height of the crisis period from November 2008 to February 2009. (2) Among all industrial sectors, thermal power plants were mainly responsible for fluctuations in local NO2 pollution during the crisis period. Thermal generating capacity had its greatest decrease of 12.10% at the height of the crisis compared with that during November 2007-February 2008, leading to local tropospheric NO2 density decreasing by 16.97%. As the crisis appeased, thermal generating capacity increased by 29.63% from November 2009 to February 2010, and tropospheric NO2 densities correspondingly increased by 30.07%. (3) Among all industrial sectors in the YRD, the thermal power sector has the greatest coal consumption of about 65.96%. A decline in thermal power of about 10% can induce a decrease of about 30% in NOx emissions and NO2 densities, meaning that a relative small fluctuation in industrial production can lead to a large decrease in tropospheric NO2 densities over industrially developed areas like the YRD region. Since electricity is mainly obtained from local coal-burning thermal plants without NOx-processing equipment, installing NOx-removal devices for all thermal power plants is an important and feasible way of controlling local NOx pollution at present.

Non scale-invariant density perturbations from chaotic extended inflation

NASA Technical Reports Server (NTRS)

Mollerach, Silvia; Matarrese, Sabino

1991-01-01

Chaotic inflation is analyzed in the frame of scalar-tensor theories of gravity. Fluctuations in the energy density arise from quantum fluctuations of the Brans-Dicke field and of the inflation field. The spectrum of perturbations is studied for a class of models: it is non scale-invarient and, for certain values of the parameters, it has a peak. If the peak appears at astrophysically interesting scales, it may help to reconcile the Cold Dark Matter scenario for structure formation with large scale observations.

Experimental analysis of drift waves destabilization in a toroidal plasma

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

Riccardi, C.; Xuantong, D.; Salierno, M.

1997-11-01

This paper concerns the study of the development of turbulence in a toroidal magnetoplasma [C. Riccardi {ital et al.}, Plasma Phys. {bold 36}, 1791 (1994)]. This analysis has been performed by evaluating wave number, frequency spectra, and bicoherence coefficients of density fluctuations associated to drift wave propagation. Plasma parameters have been changed over a wide range, in order to identify and characterize density fluctuations both in absence and in presence of nonlinear phenomena. {copyright} {ital 1997 American Institute of Physics.}

Simulations of fluorescence solvatochromism in substituted PPV oligomers from excited state molecular dynamics with implicit solvent

DOE PAGES

Bjorgaard, J. A.; Nelson, T.; Kalinin, K.; ...

2015-04-28

In this study, an efficient method of treating solvent effects in excited state molecular dynamics (ESMD) is implemented and tested by exploring the solvatochromic effects in substituted p-phenylene vinylene oligomers. A continuum solvent model is used which has very little computational overhead. This allows simulations of ESMD with solvent effects on the scale of hundreds of picoseconds for systems of up to hundreds of atoms. At these time scales, solvatochromic shifts in fluoresence spectra can be described. Solvatochromic shifts in absorption and fluorescence spectra from ESMD are compared with time-dependent density functional theory calculations and experiments.

Correlations and fluctuations: Generalized factorial moments

NASA Astrophysics Data System (ADS)

Bialas, A.

2007-02-01

A systematic study of the relations between fluctuations of the extensive multiparticle variables and integrals of the inclusive multiparticle densities is presented. The generalized factorial moments are introduced and their physical meaning discussed. The effects of the additive conservation laws are analyzed.

Influence of electrolyte ion-solvent interactions on the performances of supercapacitors porous carbon electrodes

NASA Astrophysics Data System (ADS)

Decaux, C.; Matei Ghimbeu, C.; Dahbi, M.; Anouti, M.; Lemordant, D.; Béguin, F.; Vix-Guterl, C.; Raymundo-Piñero, E.

2014-10-01

The development of advanced and safe electrochemical supercapacitors or hybrid supercapacitors combining a battery electrode material such as graphite and a porous carbon electrode implies the use of new electrolytes containing a tetra-alkylammonium or lithium salt dissolved preferentially in a safe and environmentally friendly solvent such as alkylcarbonates. In those systems, the carbon porosity of the activated carbon electrode controls the electrochemical behavior of the whole device. In this work, it is demonstrated that electrolytes containing highly polarizing ions such as Li+ dissolved in polar solvents such as alkylcarbonates do not completely loss their solvation shell at the opposite of what is observed for poorly solvated cations like TEABF4. As a consequence, the optimal carbon pore size for obtaining the largest energy density, while keeping a high power density, is wider when strongly solvated cations, like Li+ are used than for conventional organic electrolytes using acetonitrile as solvent and TEA+ as salt cations. TEA+ cations are easily desolvated and hence are able to penetrate in small pores matching the dimensions of bare ions. The dissimilarity of behavior of alkylcarbonates and acetonitrile based electrolytes highlights the importance of ion-solvent interactions when searching the optimal porous texture for the electrode material.

Nature of Kinetic Scale Fluctuations in Solar Wind Turbulence

NASA Astrophysics Data System (ADS)

Salem, C. S.; Chen, C. H.; Sundkvist, D. J.; Chaston, C. C.; Bale, S. D.; Mozer, F.

2012-12-01

We present an investigation of the nature of small-scale turbulent fluctuations in the solar wind. The nature of the dissipation range fluctuations of solar wind turbulence remains a major open question in heliospheric physics. The steepening of the observed (magnetic field) spectra at ion scales was originally attributed to ion cyclotron damping, but it was later suggested that it could well be due to the dispersive nature of fluctuations at these scales. The nature of the dispersive cascade at and below the ion scales is still debated, two leading hypothesis being that these fluctuations have characteristics of Kinetic Alfven Waves (KAW) or whistler waves. Other possible contributions from current sheets and/or kinetic instabilities have been suggested. There is mounting evidence that the fluctuations at these scales are KAW-like. In this study, we analyze several carefully selected unperturbed solar wind intervals, using magnetic field, electric field as well as density measurements from the Cluster spacecraft in order to identify the nature of the wave modes present, how frequent they are and try to determine whether one or more wave modes at different times. We examine the electric to magnetic field fluctuation ratio (δ E/δd B), the magnetic compressibility (δ B∥ /δ B) as well as density fluctuations using newly developed diagnostic techniques by Salem et al (2012) and Chen et al (2012). We look for variations of the nature and properties of these kinetic scale fluctuations with solar wind conditions, such as the plasma beta and the angle between the magnetic field and the flow velocity which controls the measured (spacecraft frame) frequency of the fluctuations. We discuss how these results would impact how the solar wind plasma is heated.

Density enhancement mechanism of upwind schemes for low Mach number flows

NASA Astrophysics Data System (ADS)

Lin, Bo-Xi; Yan, Chao; Chen, Shu-Sheng

2018-06-01

Many all-speed Roe schemes have been proposed to improve performance in terms of low speeds. Among them, the F-Roe and T-D-Roe schemes have been found to get incorrect density fluctuation in low Mach flows, which is expected to be with the square of Mach number. Asymptotic analysis presents the mechanism of how the density fluctuation problem relates to the incorrect order of terms in the energy equation \\tilde{ρ {\\tilde{a}} {\\tilde{U}}Δ U}. It is known that changing the upwind scheme coefficients of the pressure-difference dissipation term D^P and the velocity-difference dissipation term in the momentum equation D^{ρ U} to the order of O(c^{-1}) and O(c0) can improve the level of pressure and velocity accuracy at low speeds. This paper shows that corresponding changes in energy equation can also improve the density accuracy in low speeds. We apply this modification to a recently proposed scheme, TV-MAS, to get a new scheme, TV-MAS2. Unsteady Gresho vortex flow, double shear-layer flow, low Mach number flows over the inviscid cylinder, and NACA0012 airfoil show that energy equation modification in these schemes can obtain the expected square Ma scaling of density fluctuations, which is in good agreement with corresponding asymptotic analysis. Therefore, this density correction is expected to be widely implemented into all-speed compressible flow solvers.

Solvent sensitivity of smart 3D-printed nanocomposite liquid sensor

NASA Astrophysics Data System (ADS)

Aliheidari, Nahal; Ameli, Amir; Pötschke, Petra

2018-03-01

Fused deposition modeling (FDM) is one of the 3D printing methods that has attracted significant attention. In this method, small and complex samples with nearly no limitation in geometry can be fabricated layer by layer to form end-use parts. This work investigates the liquid sensing behavior of FDM printed flexible thermoplastic polyurethane, TPU filled with multiwalled carbon nanotubes, MWCNTs. The sensing capability of printed TPU-MWCNT was studied as a function of MWCNT content and infill density in response to different solvents, i.e., ethanol, acetone and toluene. The solvents were selected based on their widespread use and importance in medical and industrial applications. U-shaped liquid sensors with 2, 3 and 4wt.% MWCNT content were printed at three different infill densities of 50, 75 and 100%. Solvent sensitivity was then characterized by immersing the sensors in the solvents and measuring the resistance evolution over 25s. The results indicated a sensitivity order of acetone > toluene > ethanol, which was in agreement with the predictions of FloryHiggins solubility equation. For all the solvents, the sensitivity was enhanced as the infill density of the printed samples was decreased. This was attributed to the increased surface area to volume ratio and shortened diffusion paths. The MWCNT content was also observed to have a profound effect on the sensitivity; in samples with partial infill, the sensitivity was found to be inversely proportional to the MWCNT content, such that the highest resistance change was obtained for nanocomposites with the lowest MWCNT content of 2wt.%. For instance, a resistance increase of more than 10 times was obtained in 25 s once TPU-2wt.%MWCNT with 50% infill was tested against acetone. The results of this work reveals that highly sensitive liquid sensors can be fabricated with the aid of 3D printing without the need for complex processing methods.

Scattering of electromagnetic wave by the layer with one-dimensional random inhomogeneities

NASA Astrophysics Data System (ADS)

Kogan, Lev; Zaboronkova, Tatiana; Grigoriev, Gennadii., IV.

A great deal of attention has been paid to the study of probability characteristics of electro-magnetic waves scattered by one-dimensional fluctuations of medium dielectric permittivity. However, the problem of a determination of a density of a probability and average intensity of the field inside the stochastically inhomogeneous medium with arbitrary extension of fluc-tuations has not been considered yet. It is the purpose of the present report to find and to analyze the indicated functions for the plane electromagnetic wave scattered by the layer with one-dimensional fluctuations of permittivity. We assumed that the length and the amplitude of individual fluctuations as well the interval between them are random quantities. All of indi-cated fluctuation parameters are supposed as independent random values possessing Gaussian distribution. We considered the stationary time cases both small-scale and large-scale rarefied inhomogeneities. Mathematically such problem can be reduced to the solution of integral Fred-holm equation of second kind for Hertz potential (U). Using the decomposition of the field into the series of multiply scattered waves we obtained the expression for a probability density of the field of the plane wave and determined the moments of the scattered field. We have shown that all odd moments of the centered field (U-¡U¿) are equal to zero and the even moments depend on the intensity. It was obtained that the probability density of the field possesses the Gaussian distribution. The average field is small compared with the standard fluctuation of scattered field for all considered cases of inhomogeneities. The value of average intensity of the field is an order of a standard of fluctuations of field intensity and drops with increases the inhomogeneities length in the case of small-scale inhomogeneities. The behavior of average intensity is more complicated in the case of large-scale medium inhomogeneities. The value of average intensity is the oscillating function versus the average fluctuations length if the standard of fluctuations of inhomogeneities length is greater then the wave length. When the standard of fluctuations of medium inhomogeneities extension is smaller then the wave length, the av-erage intensity value weakly depends from the average fluctuations extension. The obtained results may be used for analysis of the electromagnetic wave propagation into the media with the fluctuating parameters caused by such factors as leafs of trees, cumulus, internal gravity waves with a chaotic phase and etc. Acknowledgment: This work was supported by the Russian Foundation for Basic Research (projects 08-02-97026 and 09-05-00450).

Effect of wave localization on plasma instabilities

NASA Astrophysics Data System (ADS)

Levedahl, William Kirk

1987-10-01

The Anderson model of wave localization in random media is involved to study the effect of solar wind density turbulence on plasma processes associated with the solar type III radio burst. ISEE-3 satellite data indicate that a possible model for the type III process is the parametric decay of Langmuir waves excited by solar flare electron streams into daughter electromagnetic and ion acoustic waves. The threshold for this instability, however, is much higher than observed Langmuir wave levels because of rapid wave convection of the transverse electromagnetic daughter wave in the case where the solar wind is assumed homogeneous. Langmuir and transverse waves near critical density satisfy the Ioffe-Reigel criteria for wave localization in the solar wind with observed density fluctuations -1 percent. Numerical simulations of wave propagation in random media confirm the localization length predictions of Escande and Souillard for stationary density fluctations. For mobile density fluctuations localized wave packets spread at the propagation velocity of the density fluctuations rather than the group velocity of the waves. Computer simulations using a linearized hybrid code show that an electron beam will excite localized Langmuir waves in a plasma with density turbulence. An action principle approach is used to develop a theory of non-linear wave processes when waves are localized. A theory of resonant particles diffusion by localized waves is developed to explain the saturation of the beam-plasma instability. It is argued that localization of electromagnetic waves will allow the instability threshold to be exceeded for the parametric decay discussed above.

Novel analysis technique for measuring edge density fluctuation profiles with reflectometry in the Large Helical Device.

PubMed

Creely, A J; Ida, K; Yoshinuma, M; Tokuzawa, T; Tsujimura, T; Akiyama, T; Sakamoto, R; Emoto, M; Tanaka, K; Michael, C A

2017-07-01

A new method for measuring density fluctuation profiles near the edge of plasmas in the Large Helical Device (LHD) has been developed utilizing reflectometry combined with pellet-induced fast density scans. Reflectometer cutoff location was calculated by proportionally scaling the cutoff location calculated with fast far infrared laser interferometer (FIR) density profiles to match the slower time resolution results of the ray-tracing code LHD-GAUSS. Plasma velocity profile peaks generated with this reflectometer mapping were checked against velocity measurements made with charge exchange spectroscopy (CXS) and were found to agree within experimental uncertainty once diagnostic differences were accounted for. Measured density fluctuation profiles were found to peak strongly near the edge of the plasma, as is the case in most tokamaks. These measurements can be used in the future to inform inversion methods of phase contrast imaging (PCI) measurements. This result was confirmed with both a fixed frequency reflectometer and calibrated data from a multi-frequency comb reflectometer, and this method was applied successfully to a series of discharges. The full width at half maximum of the turbulence layer near the edge of the plasma was found to be only 1.5-3 cm on a series of LHD discharges, less than 5% of the normalized minor radius.

Novel analysis technique for measuring edge density fluctuation profiles with reflectometry in the Large Helical Device

NASA Astrophysics Data System (ADS)

Creely, A. J.; Ida, K.; Yoshinuma, M.; Tokuzawa, T.; Tsujimura, T.; Akiyama, T.; Sakamoto, R.; Emoto, M.; Tanaka, K.; Michael, C. A.

2017-07-01

A new method for measuring density fluctuation profiles near the edge of plasmas in the Large Helical Device (LHD) has been developed utilizing reflectometry combined with pellet-induced fast density scans. Reflectometer cutoff location was calculated by proportionally scaling the cutoff location calculated with fast far infrared laser interferometer (FIR) density profiles to match the slower time resolution results of the ray-tracing code LHD-GAUSS. Plasma velocity profile peaks generated with this reflectometer mapping were checked against velocity measurements made with charge exchange spectroscopy (CXS) and were found to agree within experimental uncertainty once diagnostic differences were accounted for. Measured density fluctuation profiles were found to peak strongly near the edge of the plasma, as is the case in most tokamaks. These measurements can be used in the future to inform inversion methods of phase contrast imaging (PCI) measurements. This result was confirmed with both a fixed frequency reflectometer and calibrated data from a multi-frequency comb reflectometer, and this method was applied successfully to a series of discharges. The full width at half maximum of the turbulence layer near the edge of the plasma was found to be only 1.5-3 cm on a series of LHD discharges, less than 5% of the normalized minor radius.

Vibrational correlation between conjugated carbonyl and diazo modes studied by single- and dual-frequency two-dimensional infrared spectroscopy

NASA Astrophysics Data System (ADS)

Maekawa, Hiroaki; Sul, Soohwan; Ge, Nien-Hui

2013-08-01

We have applied infrared three-pulse photon echo and single- and dual-frequency 2D IR spectroscopy to the ester Cdbnd O and diazo Ndbnd N stretching modes in ethyl diazoacetate (EDA), and investigated their vibrational frequency fluctuations and correlation. The two modes exhibit different vibrational dynamics and 2D lineshape, which are well simulated by frequency-frequency correlation functions (FFCFs) with two decaying components. Although the FT IR spectrum shows a single Cdbnd O band, absolute magnitude 2D IR nonrephasing spectrum displays spectral signatures supporting the presence of cis and trans conformations. The cross-peak inclined toward the anti-diagonal in the dual-frequency 2D IR spectrum, indicating that the frequency fluctuations of the two modes are anticorrelated. This behavior is attributed to anticorrelated change in the bond orders when solvent and structural fluctuations causes EDA to adopt a different mixture of the two dominant resonance structures. The effects of cross FFCF on the cross-peak line shape are discussed.

Exploring cavity-mediated long-range interactions in a dilute quantum gas

NASA Astrophysics Data System (ADS)

Landig, Renate; Mottl, Rafael; Brennecke, Ferdinand; Baumann, Kristian; Donner, Tobias; Esslinger, Tilman

2013-05-01

We report on the observation of a characteristic change in the excitation spectrum of a Bose-Einstein condensate and increased density fluctuations due to cavity-mediated atom-atom interactions. Increasing the strength of the interaction leads to a softening of an excitation mode at finite momentum, preceding a superfluid to supersolid phase transition. The observed behavior is reminiscent of a roton minimum, as predicted for quantum gases with long-range interactions. We create long-range interactions in the BEC using a non-resonant transverse pump beam which induces virtual photon exchange via the vacuum field of an optical cavity. The mode softening is spectroscopically studied across the phase transition using a variant of Bragg spectroscopy. At the phase transition a diverging density response is observed which is linked to increased density fluctuations. Using the cavity dissipation channel we monitor these fluctuations in real-time and identify the influence of measurement backaction onto the critical behavior of the system.

Fluid dynamic propagation of initial baryon number perturbations on a Bjorken flow background

DOE PAGES

Floerchinger, Stefan; Martinez, Mauricio

2015-12-11

Baryon number density perturbations offer a possible route to experimentally measure baryon number susceptibilities and heat conductivity of the quark gluon plasma. We study the fluid dynamical evolution of local and event-by-event fluctuations of baryon number density, flow velocity, and energy density on top of a (generalized) Bjorken expansion. To that end we use a background-fluctuation splitting and a Bessel-Fourier decomposition for the fluctuating part of the fluid dynamical fields with respect to the azimuthal angle, the radius in the transverse plane, and rapidity. Here, we examine how the time evolution of linear perturbations depends on the equation of statemore » as well as on shear viscosity, bulk viscosity, and heat conductivity for modes with different azimuthal, radial, and rapidity wave numbers. Finally we discuss how this information is accessible to experiments in terms of the transverse and rapidity dependence of correlation functions for baryonic particles in high energy nuclear collisions.« less

Unsteady density and velocity measurements in the 6 foot x 6 foot wind tunnel

NASA Technical Reports Server (NTRS)

Rose, W. C.; Johnson, D. A.

1980-01-01

The methods used and the results obtained in four aero-optic tests are summarized. It is concluded that the rather large values of density fluctuation appear to be the result of much higher Mach number than freestream and the violent turbulence in the flow as it separates from the turret. A representative comparison of fairing on-fairing off rms density fluctuation indicates essentially no effect at M = 0.62 and a small effect at M = 0.95. These data indicate that some slight improvement in optical quality can be expected with the addition of a fairing, although at M = 0.62 its effect would be nil. Fairings are very useful in controlling pressure loads on turrets, but will not have first order effects on optical quality. Scale sizes increase dramatically with increasing azimuth angle for a reprensentative condition. Since both scale sizes and fluctuation levels increase (total turbulence path length also increases) with azimuth angle, substantial optical degradation might be expected. For shorter wave lengths, large degradations occur.

Characterization of nonGaussian atmospheric turbulence for prediction of aircraft response statistics

NASA Technical Reports Server (NTRS)

Mark, W. D.

1977-01-01

Mathematical expressions were derived for the exceedance rates and probability density functions of aircraft response variables using a turbulence model that consists of a low frequency component plus a variance modulated Gaussian turbulence component. The functional form of experimentally observed concave exceedance curves was predicted theoretically, the strength of the concave contribution being governed by the coefficient of variation of the time fluctuating variance of the turbulence. Differences in the functional forms of response exceedance curves and probability densities also were shown to depend primarily on this same coefficient of variation. Criteria were established for the validity of the local stationary assumption that is required in the derivations of the exceedance curves and probability density functions. These criteria are shown to depend on the relative time scale of the fluctuations in the variance, the fluctuations in the turbulence itself, and on the nominal duration of the relevant aircraft impulse response function. Metrics that can be generated from turbulence recordings for testing the validity of the local stationary assumption were developed.

Density Fluctuation in Aqueous Solutions and Molecular Origin of Salting-Out Effect for CO 2

DOE PAGES

Ho, Tuan Anh; Ilgen, Anastasia

2017-10-26

Using molecular dynamics simulation, we studied the density fluctuations and cavity formation probabilities in aqueous solutions and their effect on the hydration of CO 2. With increasing salt concentration, we report an increased probability of observing a larger than the average number of species in the probe volume. Our energetic analyses indicate that the van der Waals and electrostatic interactions between CO 2 and aqueous solutions become more favorable with increasing salt concentration, favoring the solubility of CO 2 (salting in). However, due to the decreasing number of cavities forming when salt concentration is increased, the solubility of CO 2more » decreases. The formation of cavities was found to be the primary control on the dissolution of gas, and is responsible for the observed CO 2 salting-out effect. Finally, our results provide the fundamental understanding of the density fluctuation in aqueous solutions and the molecular origin of the salting-out effect for real gas.« less

Influence of container shape on scaling of turbulent fluctuations in convection

NASA Astrophysics Data System (ADS)

Foroozani, N.; Niemela, J. J.; Armenio, V.; Sreenivasan, K. R.

2014-12-01

We perform large-eddy simulations of turbulent convection in a cubic cell for Rayleigh numbers, Ra, between 106 and 1010 and the molecular Prandtl number, Pr=0.7 . The simulations were carried out using a second-order-accurate finite-difference method in which subgrid-scale fluxes of momentum and heat were both parametrized using a Lagrangian and dynamic Smagorinsky model. The scaling of the root-mean-square fluctuations of density (temperature) and velocity measured in the cell center are in excellent agreement with the scaling measured in the laboratory experiments of Daya and Ecke [Phys. Rev. Lett. 87, 184501 (2001), 10.1103/PhysRevLett.87.184501] and differ substantially from that observed in cylindrical cells. We also observe the time-averaged spatial distributions of the local heat flux and density fluctuations, and find that they are strongly inhomogeneous in the horizontal midplane, with the largest density gradients occurring at the corners at the midheight, where hot and cold plumes mix in the form of strong counter-rotating eddies.

Density Fluctuation in Aqueous Solutions and Molecular Origin of Salting-Out Effect for CO 2

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

Ho, Tuan Anh; Ilgen, Anastasia

Using molecular dynamics simulation, we studied the density fluctuations and cavity formation probabilities in aqueous solutions and their effect on the hydration of CO 2. With increasing salt concentration, we report an increased probability of observing a larger than the average number of species in the probe volume. Our energetic analyses indicate that the van der Waals and electrostatic interactions between CO 2 and aqueous solutions become more favorable with increasing salt concentration, favoring the solubility of CO 2 (salting in). However, due to the decreasing number of cavities forming when salt concentration is increased, the solubility of CO 2more » decreases. The formation of cavities was found to be the primary control on the dissolution of gas, and is responsible for the observed CO 2 salting-out effect. Finally, our results provide the fundamental understanding of the density fluctuation in aqueous solutions and the molecular origin of the salting-out effect for real gas.« less

Cosmological density fluctuations produced by vacuum strings

NASA Astrophysics Data System (ADS)

Vilenkin, A.

1981-04-01

Consideration is given to the possible role of vacuum domain strings produced in the grand unification phase transition in the early universe in the generation of the density fluctuations giving rise to galaxies. The cosmological evolution of the strings formed in the grand unification phase transition is analyzed, with attention given to possible mechanisms for the damping out of oscillations produced by tension in convoluted strings and closed loops. The cosmological density fluctuations introduced by infinite strings and closed loops smaller than the horizon are then shown to be capable of giving rise to mass condensations on a scale of approximately 10 to the 9th solar masses at the time of the decoupling of radiation from matter, around which the galaxies condense. Differences between the present theory and that suggested by Zel'dovich (1980) are pointed out, and it is noted that string formation at the grand unification phase transition is possible only if the manifold of the degenerate vacua of the gauge theory is not simply connected.

Multiparticle collision simulations of two-dimensional one-component plasmas: Anomalous transport and dimensional crossovers

NASA Astrophysics Data System (ADS)

Di Cintio, Pierfrancesco; Livi, Roberto; Lepri, Stefano; Ciraolo, Guido

2017-04-01

By means of hybrid multiparticle collsion-particle-in-cell (MPC-PIC) simulations we study the dynamical scaling of energy and density correlations at equilibrium in moderately coupled two-dimensional (2D) and quasi-one-dimensional (1D) plasmas. We find that the predictions of nonlinear fluctuating hydrodynamics for the structure factors of density and energy fluctuations in 1D systems with three global conservation laws hold true also for 2D systems that are more extended along one of the two spatial dimensions. Moreover, from the analysis of the equilibrium energy correlators and density structure factors of both 1D and 2D neutral plasmas, we find that neglecting the contribution of the fluctuations of the vanishing self-consistent electrostatic fields overestimates the interval of frequencies over which the anomalous transport is observed. Such violations of the expected scaling in the currents correlation are found in different regimes, hindering the observation of the asymptotic scaling predicted by the theory.

Influence of container shape on scaling of turbulent fluctuations in convection.

PubMed

Foroozani, N; Niemela, J J; Armenio, V; Sreenivasan, K R

2014-12-01

We perform large-eddy simulations of turbulent convection in a cubic cell for Rayleigh numbers, Ra, between 10(6) and 10(10) and the molecular Prandtl number, Pr=0.7. The simulations were carried out using a second-order-accurate finite-difference method in which subgrid-scale fluxes of momentum and heat were both parametrized using a Lagrangian and dynamic Smagorinsky model. The scaling of the root-mean-square fluctuations of density (temperature) and velocity measured in the cell center are in excellent agreement with the scaling measured in the laboratory experiments of Daya and Ecke [Phys. Rev. Lett. 87, 184501 (2001)] and differ substantially from that observed in cylindrical cells. We also observe the time-averaged spatial distributions of the local heat flux and density fluctuations, and find that they are strongly inhomogeneous in the horizontal midplane, with the largest density gradients occurring at the corners at the midheight, where hot and cold plumes mix in the form of strong counter-rotating eddies.

Opening Furan for Tailoring Properties of Bio-based Poly(Furfuryl Alcohol) Thermoset.

PubMed

Falco, Guillaume; Guigo, Nathanael; Vincent, Luc; Sbirrazzuoli, Nicolas

2018-06-11

This work shows how furan ring-opening reactions were controlled by polymerization conditions to tune the cross-link density in bio-based poly(furfuryl alcohol) (PFA). The influence of water and isopropyl alcohol (IPA) on the polymerization of furfuryl alcohol, and particularly on furan ring-opening, was investigated by means of 13 C NMR and FT-IR spectroscopy. Results indicated that formation of open structures were favored in the presence of solvents, thus leading to modification of the thermo-mechanical properties compared to PFA cross-linked without solvent. Dynamic mechanical analyses showed that when slightly more open structures were present in PFA it resulted in an important decrease of the cross-link density. Despite lower glass-transition temperature and lower elastic modulus for PFA polymerized with solvent, the thermal stability remains very high (>350 °C) even with more open structures in PFA. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stochastic thermodynamics of fluctuating density fields: Non-equilibrium free energy differences under coarse-graining

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

Leonard, T.; Lander, B.; Seifert, U.

2013-11-28

We discuss the stochastic thermodynamics of systems that are described by a time-dependent density field, for example, simple liquids and colloidal suspensions. For a time-dependent change of external parameters, we show that the Jarzynski relation connecting work with the change of free energy holds if the time evolution of the density follows the Kawasaki-Dean equation. Specifically, we study the work distributions for the compression and expansion of a two-dimensional colloidal model suspension implementing a practical coarse-graining scheme of the microscopic particle positions. We demonstrate that even if coarse-grained dynamics and density functional do not match, the fluctuation relations for themore » work still hold albeit for a different, apparent, change of free energy.« less

Volumetric Properties of the Ionic Liquid, 1-Butyl-3-methylimidazolium Tetrafluoroborate, in Organic Solvents at T = 298.15K

NASA Astrophysics Data System (ADS)

Shekaari, Hemayat; Zafarani-Moattar, Mohammed Taghi

2008-04-01

Apparent molar volumes, V_φ , and compressibilities, kappa _φ , of 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) have been determined from precise density and speed-of-sound measurements in organic solvents, methanol (MeOH), acetonitrile (MeCN), tetrahydrofuran (THF), N, N-dimethylacetamide (DMA), and dimethylsulfoxide (DMSO) in the dilute region of the ionic liquid. Corresponding values at infinite dilution are estimated by the Redlich-Mayer and Pitzer equations. The results have been interpreted by the interaction of the [BMIm][BF4] in the organic solvents. Results show that the structure and dielectric constant of the organic solvents play an important role for the ion-solvent interactions in these mixtures. It was found that the strength of interaction between [BMIm][BF4] with the studied organic solvents has the order DMSO > DMA > MeOH > MeCN > THF.

Adsorption behavior of acetone solvent at the HMX crystal faces: A molecular dynamics study.

PubMed

Liu, Yingzhe; Yu, Tao; Lai, Weipeng; Ma, Yiding; Kang, Ying; Ge, Zhongxue

2017-06-01

Molecular dynamics simulations have been performed to understand the adsorption behavior of acetone (AC) solvent at the three surfaces of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctan (HMX) crystal, i.e. (011), (110), and (020) faces. The simulation results show that the structural features and electrostatic potentials of crystal faces are determined by the HMX molecular packing, inducing distinct mass density distribution, dipole orientation, and diffusion of solvent molecules in the interfacial regions. The solvent adsorption is mainly governed by the van der Waals forces, and the crystal-solvent interaction energies among three systems are ranked as (020)≈(110)>(011). The adsorption sites for solvent incorporation at the crystal surface were found and visualized with the aid of occupancy analysis. A uniform arrangement of adsorption sites is observed at the rough (020) surface as a result of ordered adsorption motif. Copyright © 2017 Elsevier Inc. All rights reserved.

Observational Signatures of Parametric Instability at 1AU

NASA Astrophysics Data System (ADS)

Bowen, T. A.; Bale, S. D.; Badman, S.

2017-12-01

Observations and simulations of inertial compressive turbulence in the solar wind are characterized by density structures anti-correlated with magnetic fluctuations parallel to the mean field. This signature has been interpreted as observational evidence for non-propagating pressure balanced structures (PBS), kinetic ion acoustic waves, as well as the MHD slow mode. Recent work, specifically Verscharen et al. (2017), has highlighted the unexpected fluid like nature of the solar wind. Given the high damping rates of parallel propagating compressive fluctuations, their ubiquity in satellite observations is surprising and suggests the presence of a driving process. One possible candidate for the generation of compressive fluctuations in the solar wind is the parametric instability, in which large amplitude Alfvenic fluctuations decay into parallel propagating compressive waves. This work employs 10 years of WIND observations in order to test the parametric decay process as a source of compressive waves in the solar wind through comparing collisionless damping rates of compressive fluctuations with growth rates of the parametric instability. Preliminary results suggest that generation of compressive waves through parametric decay is overdamped at 1 AU. However, the higher parametric decay rates expected in the inner heliosphere likely allow for growth of the slow mode-the remnants of which could explain density fluctuations observed at 1AU.

Mapping current fluctuations of stochastic pumps to nonequilibrium steady states.

NASA Astrophysics Data System (ADS)

Rotskoff, Grant

We show that current fluctuations in stochastic pumps can be robustly mapped to fluctuations in a corresponding time-independent non-equilibrium steady state. We thus refine a recently proposed mapping so that it ensures equivalence of not only the averages, but also the optimal representation of fluctuations in currents and density. Our mapping leads to a natural decomposition of the entropy production in stochastic pumps, similar to the ``housekeeping'' heat. As a consequence of the decomposition of entropy production, the current fluctuations in weakly perturbed stochastic pumps satisfy a universal bound determined by the steady state entropy production. National Science Foundation Graduate Research Fellowship.

Testing the Use of Implicit Solvent in the Molecular Dynamics Modelling of DNA Flexibility

NASA Astrophysics Data System (ADS)

Mitchell, J.; Harris, S.

DNA flexibility controls packaging, looping and in some cases sequence specific protein binding. Molecular dynamics simulations carried out with a computationally efficient implicit solvent model are potentially a powerful tool for studying larger DNA molecules than can be currently simulated when water and counterions are represented explicitly. In this work we compare DNA flexibility at the base pair step level modelled using an implicit solvent model to that previously determined from explicit solvent simulations and database analysis. Although much of the sequence dependent behaviour is preserved in implicit solvent, the DNA is considerably more flexible when the approximate model is used. In addition we test the ability of the implicit solvent to model stress induced DNA disruptions by simulating a series of DNA minicircle topoisomers which vary in size and superhelical density. When compared with previously run explicit solvent simulations, we find that while the levels of DNA denaturation are similar using both computational methodologies, the specific structural form of the disruptions is different.

Structural and thermodynamic properties of the Cm III ion solvated by water and methanol

DOE PAGES

Kelley, Morgan P.; Yang, Ping; Clark, Sue B.; ...

2016-04-27

The geometric and electronic structures of the 9-coordinate Cm 3+ ion solvated with both water and methanol are systematically investigated in the gas phase at each possible solvent-shell composition and configuration using density functional theory and second-order Møller–Plesset perturbation theory. Ab initio molecular dynamics simulations are employed to assess the effects of second and third solvent shells on the gas-phase structure. The ion–solvent dissociation energy for methanol is greater than that of water, potentially because of increased charge donation to the ion made possible by the electron-rich methyl group. Further, the ion–solvent dissociation energy and the ion–solvent distance are shownmore » to be dependent on the solvent-shell composition. Furthermore, this has implications for solvent exchange, which is generally the rate-limiting step in complexation reactions utilized in the separation of curium from complex metal mixtures that derive from the advanced nuclear fuel cycle.« less

Low-density resin impregnated ceramic article and method for making the same

NASA Technical Reports Server (NTRS)

Tran, Huy K. (Inventor); Henline, William D. (Inventor); Hsu, Ming-ta S. (Inventor); Rasky, Daniel J. (Inventor); Riccitiello, Salvatore R. (Inventor)

1997-01-01

A low-density resin impregnated ceramic article advantageously employed as a structural ceramic ablator comprising a matrix of ceramic fibers. The fibers of the ceramic matrix are coated with an organic resin film. The organic resin can be a thermoplastic resin or a cured thermosetting resin. In one embodiment, the resin is uniformly distributed within the ceramic article. In a second embodiment, the resin is distributed so as to provide a density gradient along at least one direction of the ceramic article. The resin impregnated ceramic article is prepared by providing a matrix of ceramic fibers; immersing the matrix of ceramic fibers in a solution of a solvent and an organic resin infiltrant; and removing the solvent to form a resin film on the ceramic fibers.

Advanced dielectric continuum model of preferential solvation

NASA Astrophysics Data System (ADS)

Basilevsky, Mikhail; Odinokov, Alexey; Nikitina, Ekaterina; Grigoriev, Fedor; Petrov, Nikolai; Alfimov, Mikhail

2009-01-01

A continuum model for solvation effects in binary solvent mixtures is formulated in terms of the density functional theory. The presence of two variables, namely, the dimensionless solvent composition y and the dimensionless total solvent density z, is an essential feature of binary systems. Their coupling, hidden in the structure of the local dielectric permittivity function, is postulated at the phenomenological level. Local equilibrium conditions are derived by a variation in the free energy functional expressed in terms of the composition and density variables. They appear as a pair of coupled equations defining y and z as spatial distributions. We consider the simplest spherically symmetric case of the Born-type ion immersed in the benzene/dimethylsulfoxide (DMSO) solvent mixture. The profiles of y(R ) and z(R ) along the radius R, which measures the distance from the ion center, are found in molecular dynamics (MD) simulations. It is shown that for a given solute ion z(R ) does not depend significantly on the composition variable y. A simplified solution is then obtained by inserting z(R ), found in the MD simulation for the pure DMSO, in the single equation which defines y(R ). In this way composition dependences of the main solvation effects are investigated. The local density augmentation appears as a peak of z(R ) at the ion boundary. It is responsible for the fine solvation effects missing when the ordinary solvation theories, in which z =1, are applied. These phenomena, studied for negative ions, reproduce consistently the simulation results. For positive ions the simulation shows that z ≫1 (z =5-6 at the maximum of the z peak), which means that an extremely dense solvation shell is formed. In such a situation the continuum description fails to be valid within a consistent parametrization.

Ionic Asymmetry and Solvent Excluded Volume Effects on Spherical Electric Double Layers: A Density Functional Approach

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

Medasani, Bharat; Ovanesyan, Zaven; Thomas, Dennis G.

In this article we present a classical density functional theory for electrical double layers of spherical macroions that extends the capabilities of conventional approaches by accounting for electrostatic ion correlations, size asymmetry and excluded volume effects. The approach is based on a recent approximation introduced by Hansen-Goos and Roth for the hard sphere excess free energy of inhomogeneous fluids (J. Chem. Phys. 124, 154506). It accounts for the proper and efficient description of the effects of ionic asymmetry and solvent excluded volume, especially at high ion concentrations and size asymmetry ratios including those observed in experimental studies. Additionally, we utilizemore » a leading functional Taylor expansion approximation of the ion density profiles. In addition, we use the Mean Spherical Approximation for multi-component charged hard sphere fluids to account for the electrostatic ion correlation effects. These approximations are implemented in our theoretical formulation into a suitable decomposition of the excess free energy which plays a key role in capturing the complex interplay between charge correlations and excluded volume effects. We perform Monte Carlo simulations in various scenarios to validate the proposed approach, obtaining a good compromise between accuracy and computational cost. We use the proposed computational approach to study the effects of ion size, ion size asymmetry and solvent excluded volume on the ion profiles, integrated charge, mean electrostatic potential, and ionic coordination number around spherical macroions in various electrolyte mixtures. Our results show that both solvent hard sphere diameter and density play a dominant role in the distribution of ions around spherical macroions, mainly for experimental water molarity and size values where the counterion distribution is characterized by a tight binding to the macroion, similar to that predicted by the Stern model.« less

40 CFR 63.5746 - How do I demonstrate compliance with the emission limits for aluminum wipedown solvents and...

Code of Federal Regulations, 2014 CFR

2014-07-01

...) to determine the density of each aluminum surface coating and wipedown solvent. (d) Compliance is... Surface Coating Operations § 63.5746 How do I demonstrate compliance with the emission limits for aluminum... (liters of solids per liter of coating, or volume fraction) of each aluminum surface coating, including...

40 CFR 63.5746 - How do I demonstrate compliance with the emission limits for aluminum wipedown solvents and...

Code of Federal Regulations, 2013 CFR

2013-07-01

...) to determine the density of each aluminum surface coating and wipedown solvent. (d) Compliance is... Surface Coating Operations § 63.5746 How do I demonstrate compliance with the emission limits for aluminum... (liters of solids per liter of coating, or volume fraction) of each aluminum surface coating, including...

Evidence for the presence of quasi-two-dimensional nearly incompressible fluctuations in the solar wind

NASA Technical Reports Server (NTRS)

Matthaeus, William H.; Goldstein, Melvyn L.; Roberts, D. Aaron

1990-01-01

Assuming that the slab and isotropic models of solar wind turbulence need modification (largely due to the observed anisotropy of the interplanetary fluctuations and the results of laboratory plasma experiments), this paper proposes a model of the solar wind. The solar wind is seen as a fluid which contains both classical transverse Alfvenic fluctuations and a population of quasi-transverse fluctuations. In quasi-two-dimensional turbulence, the pitch angle scattering by resonant wave-particle interactions is suppressed, and the direction of minimum variance of interplanetary fluctuations is parallel to the mean magnetic field. The assumed incompressibility is consistent with the fact that the density fluctuations are small and anticorrelated, and that the total pressure at small scales is nearly constant.

Enhanced performance of dicationic ionic liquid electrolytes by organic solvents.

PubMed

Li, Song; Zhang, Pengfei; Fulvio Pasquale, F; Hillesheim Patrick, C; Feng, Guang; Dai, Sheng; Cummings Peter, T

2014-07-16

The use of dicationic ionic liquid (DIL) electrolytes in supercapacitors is impeded by the slow dynamics of DILs, whereas the addition of organic solvents into DIL electrolytes improves ion transport and then enhances the power density of supercapacitors. In this work, the influences of organic solvents on the conductivity of DILs and the electrical double layer (EDL) of DIL-based supercapacitors are investigated using classical molecular dynamics simulation. Two types of organic solvents, acetonitrile (ACN) and propylene carbonate (PC), were used to explore the effects of different organic solvents on the EDL structure and capacitance of DIL/organic solvent-based supercapacitors. Firstly, it was found that the conductivity of DIL electrolytes was greatly enhanced in the presence of the organic solvent ACN. Secondly, a stronger adsorption of PC on graphite results in different EDL structures formed by DIL/ACN and DIL/PC electrolytes. The expulsion of co-ions from EDLs was observed in DIL/organic solvent electrolytes rather than neat DILs and this feature is more evident in DIL/PC. Furthermore, the bell-shaped differential capacitance-electric potential curve was not essentially changed by the presence of organic solvents. Comparing DIL/organic solvent electrolytes with neat DILs, the capacitance is slightly increased by organic solvents, which is in agreement with experimental observation.

Double inflation - A possible resolution of the large-scale structure problem

NASA Technical Reports Server (NTRS)

Turner, Michael S.; Villumsen, Jens V.; Vittorio, Nicola; Silk, Joseph; Juszkiewicz, Roman

1987-01-01

A model is presented for the large-scale structure of the universe in which two successive inflationary phases resulted in large small-scale and small large-scale density fluctuations. This bimodal density fluctuation spectrum in an Omega = 1 universe dominated by hot dark matter leads to large-scale structure of the galaxy distribution that is consistent with recent observational results. In particular, large, nearly empty voids and significant large-scale peculiar velocity fields are produced over scales of about 100 Mpc, while the small-scale structure over less than about 10 Mpc resembles that in a low-density universe, as observed. Detailed analytical calculations and numerical simulations are given of the spatial and velocity correlations.

Quantum time crystal by decoherence: Proposal with an incommensurate charge density wave ring

NASA Astrophysics Data System (ADS)

Nakatsugawa, K.; Fujii, T.; Tanda, S.

2017-09-01

We show that time translation symmetry of a ring system with a macroscopic quantum ground state is broken by decoherence. In particular, we consider a ring-shaped incommensurate charge density wave (ICDW ring) threaded by a fluctuating magnetic flux: the Caldeira-Leggett model is used to model the fluctuating flux as a bath of harmonic oscillators. We show that the charge density expectation value of a quantized ICDW ring coupled to its environment oscillates periodically. The Hamiltonians considered in this model are time independent unlike "Floquet time crystals" considered recently. Our model forms a metastable quantum time crystal with a finite length in space and in time.

Thomson scattering measurements from asymmetric interpenetrating plasma flows

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

Ross, J. S., E-mail: ross36@llnl.gov; Moody, J. D.; Fiuza, F.

2014-11-15

Imaging Thomson scattering measurements of collective ion-acoustic fluctuations have been utilized to determine ion temperature and density from laser produced counter-streaming asymmetric flows. Two foils are heated with 8 laser beams each, 500 J per beam, at the Omega Laser facility. Measurements are made 4 mm from the foil surface using a 60 J 2ω probe laser with a 200 ps pulse length. Measuring the electron density and temperature from the electron-plasma fluctuations constrains the fit of the multi-ion species, asymmetric flows theoretical form factor for the ion feature such that the ion temperatures, ion densities, and flow velocities formore » each plasma flow are determined.« less

New insights on boundary plasma turbulence and the Quasi-Coherent Mode in Alcator C-Mod using a Mirror Langmuir Probe

NASA Astrophysics Data System (ADS)

Labombard, Brian

2013-10-01

A ``Mirror Langmuir Probe'' (MLP) diagnostic has been used to interrogate edge plasma profiles and turbulence in Alcator C-Mod with unprecedented detail, yielding fundamental insights on the Quasi-Coherent Mode (QCM) - a mode that regulates plasma density and impurities in EDA H-modes without ELMs. The MLP employs a fast-switching, self-adapting bias scheme, recording density, electron temperature and plasma potential simultaneously at high bandwidth (~1 MHz) on each of four separate electrodes on a scanning probe. Temporal dynamics are followed in detail; wavenumber-frequency spectra and phase relationships are readily deduced. Poloidal field fluctuations are recorded separately with a two-coil, scanning probe. Results from ohmic L-mode and H-mode plasmas are reported, including key observations of the QCM: The QCM lives in a region of positive radial electric field, with a mode width (~3 mm) that spans open and closed field line regions. Remarkably large amplitude (~30%), sinusoidal bursts in density, electron temperature and plasma potential fluctuations are observed that are in phase; potential lags density by at most 10 degrees. Propagation velocity of the mode corresponds to the sum of local E × B and electron diamagnetic drift velocities - quantities that are deduced directly from time-averaged profiles. Poloidal magnetic field fluctuations project to parallel current densities of ~5 amps/cm2 in the mode layer, with significant parallel electromagnetic induction. Electron force balance is examined, unambiguously identifying the mode type. It is found that fluctuations in parallel electron pressure gradient are roughly balanced by the sum of electrostatic and electromotive forces. Thus the primary mode structure of the QCM is that of a drift-Alfven wave. Work supported by US DoE award DE-FC02-99ER54512.

Turbulent fluctuations during pellet injection into a dipole confined plasma torus

NASA Astrophysics Data System (ADS)

Garnier, D. T.; Mauel, M. E.; Roberts, T. M.; Kesner, J.; Woskov, P. P.

2017-01-01

We report measurements of the turbulent evolution of the plasma density profile following the fast injection of lithium pellets into the Levitated Dipole Experiment (LDX) [Boxer et al., Nat. Phys. 6, 207 (2010)]. As the pellet passes through the plasma, it provides a significant internal particle source and allows investigation of density profile evolution, turbulent relaxation, and turbulent fluctuations. The total electron number within the dipole plasma torus increases by more than a factor of three, and the central density increases by more than a factor of five. During these large changes in density, the shape of the density profile is nearly "stationary" such that the gradient of the particle number within tubes of equal magnetic flux vanishes. In comparison to the usual case, when the particle source is neutral gas at the plasma edge, the internal source from the pellet causes the toroidal phase velocity of the fluctuations to reverse and changes the average particle flux at the plasma edge. An edge particle source creates an inward turbulent pinch, but an internal particle source increases the outward turbulent particle flux. Statistical properties of the turbulence are measured by multiple microwave interferometers and by an array of probes at the edge. The spatial structures of the largest amplitude modes have long radial and toroidal wavelengths. Estimates of the local and toroidally averaged turbulent particle flux show intermittency and a non-Gaussian probability distribution function. The measured fluctuations, both before and during pellet injection, have frequency and wavenumber dispersion consistent with theoretical expectations for interchange and entropy modes excited within a dipole plasma torus having warm electrons and cool ions.

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

Kung, C. C.; Kramer, G. J.; Johnson, E.

Reflectometry, which uses the microwave radar technique to probe the magnetically confined fusion plasmas, is a very powerful tool to observe the density fluctuations in the fusion plasmas. Typically, two or more microwave beams of different frequencies are used to study the plasma density fluctuations. The frequency separation between these two beams of the PPPL designed reflectometer system upgrade on the DIII-D tokamak can be varied over 18 GHz. Due to the performance of the associated electronics, the local oscillator (LO) power level at the LO port of the I/Q demodulator suffers more than 12 dB of power fluctuations whenmore » the frequency separation is varied. Thus, the I/Q demodulator performance is impaired. In order to correct this problem, a power leveling circuit is introduced in the PPPL upgrade. According to the test results, the LO power fluctuation was regulated to be within 1 dB for greater than 16 dB of input power variation over the full dynamic bandwidth of the receiver.« less

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

Li, Rong; Wu, Yongquan, E-mail: yqwu@shu.edu.cn; Xiao, Junjiang

We observed homogeneous nucleation process of supercooled liquid Fe by molecular dynamics simulations. Using bond-orientational order parameters together with Voronoi polyhedron method, we characterized local structure, calculated the volume of Voronoi polyhedra of atoms and identified the structure and density fluctuations. We monitored the formation of nucleus and analyzed its inner structure. The birth and growth of the pre-nucleus and nucleus are accompanied with aggregating and disaggregating processes in the time scale of femtosecond. Only the initial solid-like clusters (ISLC), ranging from 1 to 7 atoms, pop up directly from liquid. The relation between the logarithm of number of clustersmore » and the cluster size was found to be linear for ISLCs and was observed to be parabolic for all solid-like clusters (SLC) due to aggregating and disaggregating effects. The nucleus and pre-nuclei mainly consist of body centered cubic (BCC) and hexagonal close packed atoms, while the BCC atoms tend to be located at the surface. Medium-range structure fluctuations induce the birth of ISLCs, benefit the aggregation of embryos and remarkably promote the nucleation. But density fluctuations contribute little to nucleation. The lifetime of most icosahedral-like atoms (ICO) is shorter than 0.7 ps. No obvious relationship was found between structure/density fluctuations and the appearance of ICO atoms.« less

Quantifying Density Fluctuations in Volumes of All Shapes and Sizes Using Indirect Umbrella Sampling

NASA Astrophysics Data System (ADS)

Patel, Amish J.; Varilly, Patrick; Chandler, David; Garde, Shekhar

2011-10-01

Water density fluctuations are an important statistical mechanical observable and are related to many-body correlations, as well as hydrophobic hydration and interactions. Local water density fluctuations at a solid-water surface have also been proposed as a measure of its hydrophobicity. These fluctuations can be quantified by calculating the probability, P v ( N), of observing N waters in a probe volume of interest v. When v is large, calculating P v ( N) using molecular dynamics simulations is challenging, as the probability of observing very few waters is exponentially small, and the standard procedure for overcoming this problem (umbrella sampling in N) leads to undesirable impulsive forces. Patel et al. (J. Phys. Chem. B 114:1632, 2010) have recently developed an indirect umbrella sampling (INDUS) method, that samples a coarse-grained particle number to obtain P v ( N) in cuboidal volumes. Here, we present and demonstrate an extension of that approach to volumes of other basic shapes, like spheres and cylinders, as well as to collections of such volumes. We further describe the implementation of INDUS in the NPT ensemble and calculate P v ( N) distributions over a broad range of pressures. Our method may be of particular interest in characterizing the hydrophobicity of interfaces of proteins, nanotubes and related systems.

Hydrodynamic Flow Fluctuations in √sNN = 5:02 TeV PbPbCollisions

NASA Astrophysics Data System (ADS)

Castle, James R.

The collective, anisotropic expansion of the medium created in ultrarelativistic heavy-ion collisions, known as flow, is characterized through a Fourier expansion of the final-state azimuthal particle density. In the Fourier expansion, flow harmonic coefficients vn correspond to shape components in the final-state particle density, which are a consequence of similar spatial anisotropies in the initial-state transverse energy density of a collision. Flow harmonic fluctuations are studied for PbPb collisions at √sNN = 5.02 TeV using the CMS detector at the CERN LHC. Flow harmonic probability distributions p( vn) are obtained using particles with 0.3 < pT < 3.0 GeV/c and ∥eta∥ < 1.0 by removing finite-multiplicity resolution effects from the observed azimuthal particle density through an unfolding procedure. Cumulant elliptic flow harmonics (n = 2) are determined from the moments of the unfolded p(v2) distributions and used to construct observables in 5% wide centrality bins up to 60% that relate to the initial-state spatial anisotropy. Hydrodynamic models predict that fluctuations in the initial-state transverse energy density will lead to a non-Gaussian component in the elliptic flow probability distributions that manifests as a negative skewness. A statistically significant negative skewness is observed for all centrality bins as evidenced by a splitting between the higher-order cumulant elliptic flow harmonics. The unfolded p (v2) distributions are transformed assuming a linear relationship between the initial-state spatial anisotropy and final-state flow and are fitted with elliptic power law and Bessel Gaussian parametrizations to infer information on the nature of initial-state fluctuations. The elliptic power law parametrization is found to provide a more accurate description of the fluctuations than the Bessel-Gaussian parametrization. In addition, the event-shape engineering technique, where events are further divided into classes based on an observed ellipticity, is used to study fluctuation-driven differences in the initial-state spatial anisotropy for a given collision centrality that would otherwise be destroyed by event-averaging techniques. Correlations between the first and second moments of p( vn) distributions and event ellipticity are measured for harmonic orders n = 2 - 4 by coupling event-shape engineering to the unfolding technique.

Biodiesel production from ethanolysis of DPO using deep eutectic solvent (DES) based choline chloride - ethylene glycol as co-solvent

NASA Astrophysics Data System (ADS)

Taslim, Indra, Leonardo; Manurung, Renita; Winarta, Agus; Ramadhani, Debbie Aditia

2017-03-01

Biodiesel is usually produced from transesterification using methanol or ethanol as alcohol. However, biodiesel produced using methanol has several disadvantages because methanol is toxic and not entirely bio-based as it is generally produced from petroleum, natural gas and coal. On the other hand, ethanol also has several disadvantages such as lower reactivity in transesterification process and formation of stable emulsion between ester and glycerol. To improve ethanolysis process, deep eutectic solvent (DES) was prepared from choline chloride and ethylene glycol to be used as co-solvent in ethanolysis. Deep eutectic solvent was prepared by mixing choline chloride and ethylene glycol at molar ratio of 1:2, temperature of 80 °C, and stirring speed of 300 rpm for 1 hour. The DES was characterized by its density and viscosity. The ethanolysis of DPO / Degummed Palm Oil was performed at 70 °C, ethanol to oil molar ratio of 9:1, catalyst (potassium hydroxide) concentration of 0.75 wt.% concentration, co-solvent (DES) concentration of 1, 2, 3, 4, 5 and 6 wt.%, stirring speed of 600 rpm, and reaction time of 1 hour. The obtained biodiesel was then characterized by its density, viscosity and ester content. The oil - ethanol phase condition was observed in reaction tube. The oil - ethanol phase with DES tends to form meniscus compared to that without DES. Which implied that oil and ethanol become more slightly miscible, which favours the reaction. Using DES as co-solvent in ethanolysis resulted in an increase in yield and easier purification. The esters properties met the international standards ASTM D6751, with highest yield achieved at 81.72 % with 99.35 % ethyl ester contents at 4% DES concentration.

A molecular dynamics study of intramolecular proton transfer reaction of malonaldehyde in solution based upon a mixed quantum–classical approximation. II. Proton transfer reaction in non-polar solvent

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

Kojima, H.; Yamada, A.; Okazaki, S., E-mail: okazaki@apchem.nagoya-u.ac.jp

2015-05-07

The intramolecular proton transfer reaction of malonaldehyde in neon solvent has been investigated by mixed quantum–classical molecular dynamics (QCMD) calculations and fully classical molecular dynamics (FCMD) calculations. Comparing these calculated results with those for malonaldehyde in water reported in Part I [A. Yamada, H. Kojima, and S. Okazaki, J. Chem. Phys. 141, 084509 (2014)], the solvent dependence of the reaction rate, the reaction mechanism involved, and the quantum effect therein have been investigated. With FCMD, the reaction rate in weakly interacting neon is lower than that in strongly interacting water. However, with QCMD, the order of the reaction rates ismore » reversed. To investigate the mechanisms in detail, the reactions were categorized into three mechanisms: tunneling, thermal activation, and barrier vanishing. Then, the quantum and solvent effects were analyzed from the viewpoint of the reaction mechanism focusing on the shape of potential energy curve and its fluctuations. The higher reaction rate that was found for neon in QCMD compared with that found for water solvent arises from the tunneling reactions because of the nearly symmetric double-well shape of the potential curve in neon. The thermal activation and barrier vanishing reactions were also accelerated by the zero-point energy. The number of reactions based on these two mechanisms in water was greater than that in neon in both QCMD and FCMD because these reactions are dominated by the strength of solute–solvent interactions.« less

Metal reduction at point-of-use filtration

NASA Astrophysics Data System (ADS)

Umeda, Toru; Daikoku, Shusaku; Varanasi, Rao; Tsuzuki, Shuichi

2016-03-01

We explored the metal removal efficiency of Nylon 6,6 and HDPE (High Density Polyethylene) membrane based filters, in solvents of varying degree of polarity such as Cyclohexanone and 70:30 mixture of PGME (Propylene Glycol Monomethyl Ether) and PGMEA (Propylene Glycol Monomethyl Ether), In all the solvents tested, Nylon 6,6 membrane filtration was found to be significantly more effective in removing metals than HDPE membranes, regardless of their respective membrane pore sizes. Hydrophilic interaction chromatography (HILIC) mechanism was invoked to rationalize metal removal efficiency dependence on solvent hydrophobicity.

Charge Equilibration Force Fields for Lipid Environments: Applications to Fully Hydrated DPPC Bilayers and DMPC-Embedded Gramicidin A

PubMed Central

Davis, Joseph E.; Patel, Sandeep

2009-01-01

Polarizable force fields for lipid and solvent environments are used for molecular dynamics simulations of a fully hydrated dipalmitoylphosphatidylcholine (DPPC) bilayer and gramicidin A (gA) dimer embedded in a dimyristoylphosphatidylcholine (DMPC) bilayer. The lipid bilayer is modelled using the CHARMM charge equilibration (CHEQ) polarizable force field for lipids and the TIP4P-FQ force field to represent solvent. For the DPPC bilayer system, results are compared to the same system simulated using the nonpolarizable CHARMM27r (C27r) force field and TIP3P water. Calculated atomic and electron density profiles, headgroup orientations as measured by the phosphorus-nitrogen vector orientation, and deuterium order parameters are found to be consistent with previous simulations and with experiment. The CHEQ model exhibits greater water penetration into the bilayer interior, as demonstrated by the potential of mean force calculated from the water density profile. This is a result of the variation of the water molecular dipole from 2.55 D in the bulk to 1.88 D in the interior. We discuss this finding in the context of previous studies (both simulation and experiment) that have investigated the extent of penetration of water into DPPC bilayers. We also discuss the effects of including explicit polarization on the water dipole moment variation as a function of distance from the bilayer. We show distributions of atomic charges over the course of the simulation, since the CHEQ model allows the charges to fluctuate. We have calculated the interfacial dipole potential, which the CHEQ model predicts to be 0.95 V compared to 0.86 V as predicted by the C27r model. We also discuss dielectric permittivity profiles and the differences arising between the two models. We obtain bulk values of 72.77 for the CHEQ model (TIP4P-FQ water) and 91.22 for C27r (TIP3P), and values approaching unity in the membrane interior. Finally, we present results of simulations of gA embedded in a DMPC bilayer using the CHEQ model and discuss structural properties. PMID:19526999

Predicting fluctuations-caused regime shifts in a time delayed dynamics of an invading species

NASA Astrophysics Data System (ADS)

Xie, Qingshuang; Wang, Tonghuan; Zeng, Chunhua; Dong, Xiaohui; Guan, Lin

2018-03-01

In this paper, we investigate early warning signals (EWS) of regime shifts in a density-dependent invading population model with time delay, in which the population density is assumed to be disturbed by intrinsic and extrinsic fluctuations. It is shown that the time delay and noises can cause the regime shifts between low and high population density states. The regime shift time (RST) as a function of noise intensity exhibits a maximum, which identifies the signature of the noise-enhanced stability of the low density state, while the time delay weakens the stability of the low density state. Applying the Kramers time technique, we also discuss the intersection point of the RST between low and high population density states, i.e., a critical point in the RST is found. Therefore, the critical point may give an EWS of regime shifts from one alternative state to another one for the changes in the noise parameters and time delay.

Long-range fluctuations and multifractality in connectivity density time series of a wind speed monitoring network

NASA Astrophysics Data System (ADS)

Laib, Mohamed; Telesca, Luciano; Kanevski, Mikhail

2018-03-01

This paper studies the daily connectivity time series of a wind speed-monitoring network using multifractal detrended fluctuation analysis. It investigates the long-range fluctuation and multifractality in the residuals of the connectivity time series. Our findings reveal that the daily connectivity of the correlation-based network is persistent for any correlation threshold. Further, the multifractality degree is higher for larger absolute values of the correlation threshold.

Chlorinated solvents in groundwater of the United States

USGS Publications Warehouse

Moran, M.J.; Zogorski, J.S.; Squillace, P.J.

2007-01-01

Four chlorinated solvents-methylene chloride, perchloroethene (PCE), 1,1,1-trichloroethane, and trichloroethene (TCE)-were analyzed in samples of groundwater taken throughout the conterminous United States by the U.S. Geological Survey. The samples were collected between 1985 and 2002 from more than 5,000 wells. Of 55 volatile organic compounds (VOCs) analyzed in groundwater samples, solvents were among the most frequently detected. Mixtures of solvents in groundwater were common and may be the result of common usage of solvents or degradation of one solvent to another. Relative to other VOCs with Maximum Contaminant Levels (MCLs), PCE and TCE ranked high in terms of the frequencies of concentrations greater than or near MCLs. The probability of occurrence of solvents in groundwater was associated with dissolved oxygen content of groundwater, sources such as urban land use and population density, and hydraulic properties of the aquifer. The results reinforce the importance of understanding the redox conditions of aquifers and the hydraulic properties of the saturated and vadose zones in determining the intrinsic susceptibility of groundwater to contamination by solvents. The results also reinforce the importance of controlling sources of solvents to groundwater. ?? 2007 American Chemical Society.

Exact analytic solution for non-linear density fluctuation in a ΛCDM universe

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

Yoo, Jaiyul; Gong, Jinn-Ouk, E-mail: jyoo@physik.uzh.ch, E-mail: jinn-ouk.gong@apctp.org

We derive the exact third-order analytic solution of the matter density fluctuation in the proper-time hypersurface in a ΛCDM universe, accounting for the explicit time-dependence and clarifying the relation to the initial condition. Furthermore, we compare our analytic solution to the previous calculation in the comoving gauge, and to the standard Newtonian perturbation theory by providing Fourier kernels for the relativistic effects. Our results provide an essential ingredient for a complete description of galaxy bias in the relativistic context.

Synthesis and characterization of ion containing polymers

NASA Astrophysics Data System (ADS)

Dou, Shichen

Two types of ion-containing polymers are included in this dissertation. The first was focused on the rheology, solvation, and correlation length of polyelectrolyte solutions in terms of charge density, solvent dielectric constant, and solvent quality. The second was focused on the PEO-based polyester ionomers as single ion conductors. A series of polyelectrolytes with varied charge density (0.03 < alpha < 0.6) and counterions (Cl- and I-) were investigated in good solvent (EG, NMF, and GC) and poor solvent (DW and F). The concentration dependence of the specific viscosity and relaxation time of polyelectrolytes in solution agrees with Dobrynin's theoretical predictions at c < c**. Effective charge density greatly impacts the viscosity of polyelectrolyte semidilute solutions, while residual salt significantly reduces the viscosity of polyelectrolyte solutions at concentrations c < 2cs/f. For polyelectrolyte solutions with less condensed counterions, the correlation length obtained from SAXS and rheology perfectly matches and agrees with de Gennes prediction. Dobrynin scaling model successfully predicts the rheology of polyelectrolyte solutions in all cases: without salt, with low residual salt, and with high residual salt concentration. PEO-based polyester ionomers were synthesized by melt polycondensation. Mn was determined using the 1H NMR of ionomers. No ion-cluster was observed from the DSC, SAXS, and rheology measurements. Ionic conductivity greatly depends on the Tg, T-T g and ion content of the ionomers. PEG600-PTMO650 (z)-Li copolyester ionomers show microphase separation and much lower ionic conductivity, compared to that of PE600-Li. PTMO650-Li shows nonconductor behavior.

Formalism for calculation of polymer-solvent-mediated potential

NASA Astrophysics Data System (ADS)

Zhou, Shiqi

2006-07-01

A simple theoretical approach is proposed for calculation of a solvent-mediated potential (SMP) between two colloid particles immersed in a polymer solvent bath in which the polymer is modeled as a chain with intramolecular degrees of freedom. The present recipe is only concerned with the estimation of the density profile of a polymer site around a single solute colloid particle instead of two solute colloid particles separated by a varying distance as done in existing calculational methods for polymer-SMP. Therefore the present recipe is far simpler for numerical implementation than the existing methods. The resultant predictions for the polymer-SMP and polymer solvent-mediated mean force (polymer-SMMF) are in very good agreement with available simulation data. With the present recipe, change tendencies of the contact value and second virial coefficiency of the SMP as a function of size ratio between the colloid particle and polymer site, the number of sites per chain, and the polymer concentration are investigated in detail. The metastable critical polymer concentration as a function of size ratio and the number of sites per chain is also reported for the first time. To yield the numerical solution of the present recipe at less than 1min on a personal computer, a rapid and accurate algorithm for the numerical solution of the classical density functional theory is proposed to supply rapid and accurate estimation of the density profile of the polymer site as an input into the present formalism.

Exact solution of the Lifshitz equations governing the growth of fluctuations in cosmology

NASA Technical Reports Server (NTRS)

Adams, P. J.; Canuto, V.

1975-01-01

The exact solution of the Lifshitz equations governing the cosmological evolution of an initial fluctuation is presented. Lifshitz results valid for squares of the sound velocity equal to zero and 1/3 are extended in closed form to any equation of state where the pressure equals the total energy density times the square of the sound velocity. The solutions embody all the results found previously for special cases of the square of the sound velocity. It is found that the growth of any initial fluctuation is only an exponential function of time with an exponent of not more than 4/3 and is insufficient to produce galaxies unless the initial fluctuation is very large. A possible way to produce very large initial fluctuations by modifying the equation of state by including gravitational interactions is also examined. It is found that a phase transition can occur at baryonic density of 1 nucleon per cubic Planck length or equivalently, at a time of about 10 to the -43rd power sec. At those early times, the masses allowed by causality requirements are too small to be of interest in galaxy formation.

Propagation of radio frequency waves through density fluctuations

NASA Astrophysics Data System (ADS)

Valvis, S. I.; Papagiannis, P.; Papadopoulos, A.; Hizanidis, K.; Glytsis, E.; Bairaktaris, F.; Zisis, A.; Tigelis, I.; Ram, A. K.

2017-10-01

On their way to the core of a tokamak plasma, radio frequency (RF) waves, excited in the vacuum region, have to propagate through a variety of density fluctuations in the edge region. These fluctuations include coherent structures, like blobs that can be field aligned or not, as well as turbulent and filamentary structures. We have been studying the effect of fluctuations on RF propagation using both theoretical (analytical) and computational models. The theoretical results are being compared with those obtained by two different numerical codes ``a Finite Difference Frequency Domain code and the commercial COMSOL package. For plasmas with arbitrary distribution of coherent and turbulent fluctuations, we have formulated an effective dielectric permittivity of the edge plasma. This permittivity tensor is then used in numerical simulations to study the effect of multi-scale turbulence on RF waves. We not only consider plane waves but also Gaussian beams in the electron cyclotron and lower hybrid range of frequencies. The analytical theory and results from simulations on the propagation of RF waves will be presented. Supported in part by the Hellenic National Programme on Controlled Thermonuclear Fusion associated with the EUROfusion Consortium and by DoE Grant DE-FG02-91ER-54109.

Low density microcellular foams

DOEpatents

LeMay, James D.

1992-01-01

Disclosed is a process of producing microcellular from which comprises the steps of: (a) selecting a multifunctional epoxy oligomer resin; (b) mixing said epoxy resin with a non-reactive diluent to form a resin-diluent mixture; (c) forming a diluent containing cross-linked epoxy gel from said resin-diluent mixture; (d) replacing said diluent with a solvent therefore; (e) replacing said solvent with liquid carbon dioxide; and (f) vaporizing off said liquid carbon dioxide under supercritical conditions, whereby a foam having a density in the range of 35-150 mg/cc and cell diameters less than about 1 .mu.m is produced. Also disclosed are the foams produced by the process.

Low density microcellular foams

DOEpatents

LeMay, J.D.

1991-11-19

Disclosed is a process of producing microcellular foam which comprises the steps of: (a) selecting a multifunctional epoxy oligomer resin; (b) mixing said epoxy resin with a non-reactive diluent to form a resin-diluent mixture; (c) forming a diluent containing cross-linked epoxy gel from said resin-diluent mixture; (d) replacing said diluent with a solvent therefore; (e) replacing said solvent with liquid carbon dioxide; and (f) vaporizing off said liquid carbon dioxide under supercritical conditions, whereby a foam having a density in the range of 35-150 mg/cc and cell diameters less than about 1 [mu]m is produced. Also disclosed are the foams produced by the process. 8 figures.

Low density microcellular foams

DOEpatents

LeMay, James D.

1991-01-01

Disclosed is a process of producing microcellular foam which comprises the steps of: (a) selecting a multifunctional epoxy oligomer resin; (b) mixing said epoxy resin with a non-reactive diluent to form a resin-diluent mixture; (c) forming a diluent containing cross-linked epoxy gel from said resin-diluent mixture; (d) replacing said diluent with a solvent therefore; (e) replacing said solvent with liquid carbon dioxide; and (f) vaporizing off said liquid carbon dioxide under supercritical conditions, whereby a foam having a density in the range of 35-150 mg/cc and cell diameters less than about 1 .mu.m is produced. Also disclosed are the foams produced by the process.

On the ability of trehalose to offset the denaturing activity of urea

NASA Astrophysics Data System (ADS)

Graziano, Giuseppe

2013-01-01

Experimental and computational studies indicate that trehalose offsets the denaturing activity of urea. According to a statistical thermodynamic model, the fundamental stabilizing contribution arises from the difference in the work to create a cavity suitable to host the D-state and the N-state, respectively. The magnitude of this solvent-excluded volume effect increases with aqueous solution density. Trehalose and urea addition to water leads to a density increase, that translates in an increase in the magnitude of the solvent-excluded volume effect which is so large to overwhelm the destabilizing contribution arising from the energetic attractions of urea with protein surface groups.

Multiply Reduced Oligofluorenes: Their Nature and Pairing with THF-Solvated Sodium Ions

DOE PAGES

Wu, Qin; Zaikowski, Lori; Kaur, Parmeet; ...

2016-07-01

Conjugated oligofluorenes are chemically reduced up to five charges in tetrahydrofuran solvent and confirmed with clear spectroscopic evidence. Stimulated by these experimental results, we have conducted a comprehensive computational study of the electronic structure and the solvation structure of representative oligofluorene anions with a focus on the pairing between sodium ions and these multianions. In addition, using density functional theory (DFT) methods and a solvation model of both explicit solvent molecules and implicit polarizable continuum, we first elucidate the structure of tightly solvated free sodium ions, and then explore the pairing of sodium ions either in contact with reduced oligofluorenesmore » or as solvent-separated ion pairs. Computed time-dependent-DFT absorption spectra are compared with experiments to assign the dominant ion pairing structure for each multianion. Computed ion pair binding energies further support our assignment. Lastly, the availability of different length and reducing level of oligofluorenes enables us to investigate the effects of total charge and charge density on the binding with sodium ions, and our results suggest both factors play important roles in ion pairing for small molecules. However, as the oligofluorene size grows, its charge density determines the binding strength with the sodium ion.« less

Relativistic Zeroth-Order Regular Approximation Combined with Nonhybrid and Hybrid Density Functional Theory: Performance for NMR Indirect Nuclear Spin-Spin Coupling in Heavy Metal Compounds.

PubMed

Moncho, Salvador; Autschbach, Jochen

2010-01-12

A benchmark study for relativistic density functional calculations of NMR spin-spin coupling constants has been performed. The test set contained 47 complexes with heavy metal atoms (W, Pt, Hg, Tl, Pb) with a total of 88 coupling constants involving one or two heavy metal atoms. One-, two-, three-, and four-bond spin-spin couplings have been computed at different levels of theory (nonhybrid vs hybrid DFT, scalar vs two-component relativistic). The computational model was based on geometries fully optimized at the BP/TZP scalar relativistic zeroth-order regular approximation (ZORA) and the conductor-like screening model (COSMO) to include solvent effects. The NMR computations also employed the continuum solvent model. Computations in the gas phase were performed in order to assess the importance of the solvation model. The relative median deviations between various computational models and experiment were found to range between 13% and 21%, with the highest-level computational model (hybrid density functional computations including scalar plus spin-orbit relativistic effects, the COSMO solvent model, and a Gaussian finite-nucleus model) performing best.

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

Wu, Qin; Zaikowski, Lori; Kaur, Parmeet

Conjugated oligofluorenes are chemically reduced up to five charges in tetrahydrofuran solvent and confirmed with clear spectroscopic evidence. Stimulated by these experimental results, we have conducted a comprehensive computational study of the electronic structure and the solvation structure of representative oligofluorene anions with a focus on the pairing between sodium ions and these multianions. In addition, using density functional theory (DFT) methods and a solvation model of both explicit solvent molecules and implicit polarizable continuum, we first elucidate the structure of tightly solvated free sodium ions, and then explore the pairing of sodium ions either in contact with reduced oligofluorenesmore » or as solvent-separated ion pairs. Computed time-dependent-DFT absorption spectra are compared with experiments to assign the dominant ion pairing structure for each multianion. Computed ion pair binding energies further support our assignment. Lastly, the availability of different length and reducing level of oligofluorenes enables us to investigate the effects of total charge and charge density on the binding with sodium ions, and our results suggest both factors play important roles in ion pairing for small molecules. However, as the oligofluorene size grows, its charge density determines the binding strength with the sodium ion.« less

Grid inhomogeneous solvation theory: hydration structure and thermodynamics of the miniature receptor cucurbit[7]uril.

PubMed

Nguyen, Crystal N; Young, Tom Kurtzman; Gilson, Michael K

2012-07-28

The displacement of perturbed water upon binding is believed to play a critical role in the thermodynamics of biomolecular recognition, but it is nontrivial to unambiguously define and answer questions about this process. We address this issue by introducing grid inhomogeneous solvation theory (GIST), which discretizes the equations of inhomogeneous solvation theory (IST) onto a three-dimensional grid situated in the region of interest around a solute molecule or complex. Snapshots from explicit solvent simulations are used to estimate localized solvation entropies, energies, and free energies associated with the grid boxes, or voxels, and properly summing these thermodynamic quantities over voxels yields information about hydration thermodynamics. GIST thus provides a smoothly varying representation of water properties as a function of position, rather than focusing on hydration sites where solvent is present at high density. It therefore accounts for full or partial displacement of water from sites that are highly occupied by water, as well as for partly occupied and water-depleted regions around the solute. GIST can also provide a well-defined estimate of the solvation free energy and therefore enables a rigorous end-states analysis of binding. For example, one may not only use a first GIST calculation to project the thermodynamic consequences of displacing water from the surface of a receptor by a ligand, but also account, in a second GIST calculation, for the thermodynamics of subsequent solvent reorganization around the bound complex. In the present study, a first GIST analysis of the molecular host cucurbit[7]uril is found to yield a rich picture of hydration structure and thermodynamics in and around this miniature receptor. One of the most striking results is the observation of a toroidal region of high water density at the center of the host's nonpolar cavity. Despite its high density, the water in this toroidal region is disfavored energetically and entropically, and hence may contribute to the known ability of this small receptor to bind guest molecules with unusually high affinities. Interestingly, the toroidal region of high water density persists even when all partial charges of the receptor are set to zero. Thus, localized regions of high solvent density can be generated in a binding site without strong, attractive solute-solvent interactions.

Grid inhomogeneous solvation theory: Hydration structure and thermodynamics of the miniature receptor cucurbit[7]uril

PubMed Central

Nguyen, Crystal N.; Kurtzman Young, Tom; Gilson, Michael K.

2012-01-01

The displacement of perturbed water upon binding is believed to play a critical role in the thermodynamics of biomolecular recognition, but it is nontrivial to unambiguously define and answer questions about this process. We address this issue by introducing grid inhomogeneous solvation theory (GIST), which discretizes the equations of inhomogeneous solvation theory (IST) onto a three-dimensional grid situated in the region of interest around a solute molecule or complex. Snapshots from explicit solvent simulations are used to estimate localized solvation entropies, energies, and free energies associated with the grid boxes, or voxels, and properly summing these thermodynamic quantities over voxels yields information about hydration thermodynamics. GIST thus provides a smoothly varying representation of water properties as a function of position, rather than focusing on hydration sites where solvent is present at high density. It therefore accounts for full or partial displacement of water from sites that are highly occupied by water, as well as for partly occupied and water-depleted regions around the solute. GIST can also provide a well-defined estimate of the solvation free energy and therefore enables a rigorous end-states analysis of binding. For example, one may not only use a first GIST calculation to project the thermodynamic consequences of displacing water from the surface of a receptor by a ligand, but also account, in a second GIST calculation, for the thermodynamics of subsequent solvent reorganization around the bound complex. In the present study, a first GIST analysis of the molecular host cucurbit[7]uril is found to yield a rich picture of hydration structure and thermodynamics in and around this miniature receptor. One of the most striking results is the observation of a toroidal region of high water density at the center of the host's nonpolar cavity. Despite its high density, the water in this toroidal region is disfavored energetically and entropically, and hence may contribute to the known ability of this small receptor to bind guest molecules with unusually high affinities. Interestingly, the toroidal region of high water density persists even when all partial charges of the receptor are set to zero. Thus, localized regions of high solvent density can be generated in a binding site without strong, attractive solute-solvent interactions. PMID:22852591

Lid opening and conformational stability of T1 Lipase is mediated by increasing chain length polar solvents

PubMed Central

Mohamad Ali, Mohd Shukuri; Salleh, Abu Bakar; Rahman, Raja Noor Zaliha Raja Abd; Normi, Yahaya M.; Mohd Shariff, Fairolniza

2017-01-01

The dynamics and conformational landscape of proteins in organic solvents are events of potential interest in nonaqueous process catalysis. Conformational changes, folding transitions, and stability often correspond to structural rearrangements that alter contacts between solvent molecules and amino acid residues. However, in nonaqueous enzymology, organic solvents limit stability and further application of proteins. In the present study, molecular dynamics (MD) of a thermostable Geobacillus zalihae T1 lipase was performed in different chain length polar organic solvents (methanol, ethanol, propanol, butanol, and pentanol) and water mixture systems to a concentration of 50%. On the basis of the MD results, the structural deviations of the backbone atoms elucidated the dynamic effects of water/organic solvent mixtures on the equilibrium state of the protein simulations in decreasing solvent polarity. The results show that the solvent mixture gives rise to deviations in enzyme structure from the native one simulated in water. The drop in the flexibility in H2O, MtOH, EtOH and PrOH simulation mixtures shows that greater motions of residues were influenced in BtOH and PtOH simulation mixtures. Comparing the root mean square fluctuations value with the accessible solvent area (SASA) for every residue showed an almost correspondingly high SASA value of residues to high flexibility and low SASA value to low flexibility. The study further revealed that the organic solvents influenced the formation of more hydrogen bonds in MtOH, EtOH and PrOH and thus, it is assumed that increased intraprotein hydrogen bonding is ultimately correlated to the stability of the protein. However, the solvent accessibility analysis showed that in all solvent systems, hydrophobic residues were exposed and polar residues tended to be buried away from the solvent. Distance variation of the tetrahedral intermediate packing of the active pocket was not conserved in organic solvent systems, which could lead to weaknesses in the catalytic H-bond network and most likely a drop in catalytic activity. The conformational variation of the lid domain caused by the solvent molecules influenced its gradual opening. Formation of additional hydrogen bonds and hydrophobic interactions indicates that the contribution of the cooperative network of interactions could retain the stability of the protein in some solvent systems. Time-correlated atomic motions were used to characterize the correlations between the motions of the atoms from atomic coordinates. The resulting cross-correlation map revealed that the organic solvent mixtures performed functional, concerted, correlated motions in regions of residues of the lid domain to other residues. These observations suggest that varying lengths of polar organic solvents play a significant role in introducing dynamic conformational diversity in proteins in a decreasing order of polarity. PMID:28533982

Effective temperatures of hot Brownian motion.

PubMed

Falasco, G; Gnann, M V; Rings, D; Kroy, K

2014-09-01

We derive generalized Langevin equations for the translational and rotational motion of a heated Brownian particle from the fluctuating hydrodynamics of its nonisothermal solvent. The temperature gradient around the particle couples to the hydrodynamic modes excited by the particle itself so that the resulting noise spectrum is governed by a frequency-dependent temperature. We show how the effective temperatures at which the particle coordinates and (angular) velocities appear to be thermalized emerge from this central quantity.

Molecular Rayleigh Scattering Techniques Developed for Measuring Gas Flow Velocity, Density, Temperature, and Turbulence

NASA Technical Reports Server (NTRS)

Mielke, Amy F.; Seasholtz, Richard G.; Elam, Kristie A.; Panda, Jayanta

2005-01-01

Nonintrusive optical point-wise measurement techniques utilizing the principles of molecular Rayleigh scattering have been developed at the NASA Glenn Research Center to obtain time-averaged information about gas velocity, density, temperature, and turbulence, or dynamic information about gas velocity and density in unseeded flows. These techniques enable measurements that are necessary for validating computational fluid dynamics (CFD) and computational aeroacoustic (CAA) codes. Dynamic measurements allow the calculation of power spectra for the various flow properties. This type of information is currently being used in jet noise studies, correlating sound pressure fluctuations with velocity and density fluctuations to determine noise sources in jets. These nonintrusive techniques are particularly useful in supersonic flows, where seeding the flow with particles is not an option, and where the environment is too harsh for hot-wire measurements.

HOW THE DENSITY ENVIRONMENT CHANGES THE INFLUENCE OF THE DARK MATTER–BARYON STREAMING VELOCITY ON COSMOLOGICAL STRUCTURE FORMATION

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

Ahn, Kyungjin, E-mail: kjahn@chosun.ac.kr

We study the dynamical effect of the relative velocity between dark matter and baryonic fluids, which remained supersonic after the epoch of recombination. The impact of this supersonic motion on the formation of cosmological structures was first formulated by Tseliakhovich and Hirata, in terms of the linear theory of small-scale fluctuations coupled to large-scale, relative velocities in mean-density regions. In their formalism, they limited the large-scale density environment to be that of the global mean density. We improve on their formulation by allowing variation in the density environment as well as the relative velocities. This leads to a new typemore » of coupling between large-scale and small-scale modes. We find that the small-scale fluctuation grows in a biased way: faster in the overdense environment and slower in the underdense environment. We also find that the net effect on the global power spectrum of the density fluctuation is to boost its overall amplitude from the prediction by Tseliakhovich and Hirata. Correspondingly, the conditional mass function of cosmological halos and the halo bias parameter are both affected in a similar way. The discrepancy between our prediction and that of Tseliakhovich and Hirata is significant, and therefore, the related cosmology and high-redshift astrophysics should be revisited. The mathematical formalism of this study can be used for generating cosmological initial conditions of small-scale perturbations in generic, overdense (underdense) background patches.« less

Optimization of flavanones extraction by modulating differential solvent densities and centrifuge temperatures.

PubMed

Chebrolu, Kranthi K; Jayaprakasha, G K; Jifon, J; Patil, Bhimanagouda S

2011-07-15

Understanding the factors influencing flavonone extraction is critical for the knowledge in sample preparation. The present study was focused on the extraction parameters such as solvent, heat, centrifugal speed, centrifuge temperature, sample to solvent ratio, extraction cycles, sonication time, microwave time and their interactions on sample preparation. Flavanones were analyzed in a high performance liquid chromatography (HPLC) and later identified by liquid chromatography and mass spectrometry (LC-MS). The five flavanones were eluted by a binary mobile phase with 0.03% phosphoric acid and acetonitrile in 20 min and detected at 280 nm, and later identified by mass spectral analysis. Dimethylsulfoxide (DMSO) and dimethyl formamide (DMF) had optimum extraction levels of narirutin, naringin, neohesperidin, didymin and poncirin compared to methanol (MeOH), ethanol (EtOH) and acetonitrile (ACN). Centrifuge temperature had a significant effect on flavanone distribution in the extracts. The DMSO and DMF extracts had homogeneous distribution of flavanones compared to MeOH, EtOH and ACN after centrifugation. Furthermore, ACN showed clear phase separation due to differential densities in the extracts after centrifugation. The number of extraction cycles significantly increased the flavanone levels during extraction. Modulating the sample to solvent ratio increased naringin quantity in the extracts. Current research provides critical information on the role of centrifuge temperature, extraction solvent and their interactions on flavanone distribution in extracts. Published by Elsevier B.V.

Stretch-collapse transition of polyelectrolyte brushes in a poor solvent

NASA Astrophysics Data System (ADS)

von Goeler, F.; Muthukumar, M.

1996-12-01

This paper describes the behavior of charged, polymer brushes in electrolyte solutions of varying solvent quality. The brush height, d, dependence on the chain length, L (=Nl, where l is the Kuhn length), the grafting density σ, and solvent conditions is determined. We consider a monomer-monomer potential consisting of three components: (1) a long-ranged, screened Coulombic component of strength v¯/l (l is the Kuhn length) and range κ-1; (2) a short-ranged, two-body component of strength w¯l; and (3) a short-ranged, three-body component of strength ūl3. In particular, we examine the transition from a stretched state to a collapsed state in a poor solvent (w¯<0) as the solvent quality is decreased. Using dimensional analysis, Monte Carlo methods, and a variational technique, a first order transition is observed as predicted by the scaling arguments of Ross et al. and Borisov et al. for high charge/grafting densities. Using a variational procedure, we derive an analytical expression for the brush size and determine, quantitatively, the critical conditions for a first order transition in terms of key dimensionless variables, vN5/2, κlN1/2, wN3/2, and uN2 (where v=2πσl2v¯, w=σl2w¯, and u=σ2l4ū).

Effect of wave localization on plasma instabilities. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Levedahl, William Kirk

1987-01-01

The Anderson model of wave localization in random media is involved to study the effect of solar wind density turbulence on plasma processes associated with the solar type III radio burst. ISEE-3 satellite data indicate that a possible model for the type III process is the parametric decay of Langmuir waves excited by solar flare electron streams into daughter electromagnetic and ion acoustic waves. The threshold for this instability, however, is much higher than observed Langmuir wave levels because of rapid wave convection of the transverse electromagnetic daughter wave in the case where the solar wind is assumed homogeneous. Langmuir and transverse waves near critical density satisfy the Ioffe-Reigel criteria for wave localization in the solar wind with observed density fluctuations -1 percent. Numerical simulations of wave propagation in random media confirm the localization length predictions of Escande and Souillard for stationary density fluctations. For mobile density fluctuations localized wave packets spread at the propagation velocity of the density fluctuations rather than the group velocity of the waves. Computer simulations using a linearized hybrid code show that an electron beam will excite localized Langmuir waves in a plasma with density turbulence. An action principle approach is used to develop a theory of non-linear wave processes when waves are localized. A theory of resonant particles diffusion by localized waves is developed to explain the saturation of the beam-plasma instability. It is argued that localization of electromagnetic waves will allow the instability threshold to be exceeded for the parametric decay discussed above.

Solvent effect on the conformation of Benzil

NASA Astrophysics Data System (ADS)

Pawelka, Z.; Koll, A.; Zeegers-Huyskens, Th.

2001-10-01

The conformation of benzil is investigated by PM3 and density functional theory (B3LYP) combined with the 6-31G(d,p) basis set. The variation of the relative energy with the Odbnd C-Cdbnd O torsion angle indicates only one rather flat minimum, reflecting the flexibility of the benzil molecule. The dipole moment is measured in several organic solvents of various polarity and the IR and Raman spectra investigated in the Cdbnd O stretching region in the same solvents. The torsional Odbnd C-Cdbnd O angle is evaluated from the dipolar and vibrational data. The results indicate that, in all the solvents, benzil is in a skewed conformation, the cisoid conformation being slightly favoured when the polarity of the solvent increases. The contribution of electrostatic and specific interactions to the reduction of the torsional angle is discussed.

Conformation and Dynamics of a Flexible Sheet in Solvent Media by Monte Carlo Simulations

NASA Astrophysics Data System (ADS)

Pandey, Ras; Anderson, Kelly; Heinz, Hendrik; Farmer, Barry

2005-03-01

Flexibility of the clay sheet is limited even in the ex-foliated state in some solvent media. A coarse grained model is used to investigate dynamics and conformation of a flexible sheet to model such a clay platelet in an effective solvent medium on a cubic lattice of size L^3 with lattice constant a. The undeformed sheet is described by a square lattice of size Ls^2, where, each node of the sheet is represented by the unit cube of the cubic lattice and 2a is the minimum distance between the nearest neighbor nodes to incorporate the excluded volume constraints. Additionally, each node interacts with neighboring nodes and solvent (empty) sites within a range ri. Each node execute their stochastic motion with the Metropolis algorithm subject to bond length fluctuation and excluded volume constraints. Mean square displacements of the center node and that of its center of mass are investigated as a function of time step for a set of these parameters. The radius of gyration (Rg) is also examined concurrently to understand its relaxation. Multi-scale segmental dynamics of the sheet is studied by identifying the power-law dependence in various time regimes. Relaxation of Rg and its dependence of temperature are planned to be discussed.

Conformation Analysis of T1 Lipase on Alcohols Solvent using Molecular Dynamics Simulation

NASA Astrophysics Data System (ADS)

Putri, A. M.; Sumaryada, T.; Wahyudi, S. T.

2017-07-01

Biodiesel usually is produced commercially via a transesterification reaction of vegetable oil with alcohol and alkali catalyst. The alkali catalyst has some drawbacks, such as the soap formation during the reaction. T1 Lipase enzyme had been known as a thermostable biocatalyst which is able to produce biodiesel through a cleaner process. In this paper the performance of T1 lipase enzyme as catalyst for transesterification reaction in pure ethanol, methanol, and water solvents were studied using a Molecular Dynamics (MD) Simulation at temperature of 300 K for 10 nanoseconds. The results have shown that in general the conformation of T1 lipase enzyme in methanol is more dynamics as shown by the value of root mean square deviation (RMSD), root mean squared fluctuation (RMSF), and radius of gyration. The highest solvent accessible surface area (SASA) total was also found in methanol due to the contribution of non-polar amino acid in the interior of the protein. Analysis of MD simulation has also revealed that the enzyme structure tend to be more rigid in ethanol environment. The analysis of electrostatic interactions have shown that Glu359-Arg270 salt-bridge pair might hold the key of thermostability of T1 lipase enzyme as shown by its strong and stable binding in all three solvents.

Critical fluctuations of the proton density in A+A collisions at 158A GeV

DOE PAGES

Anticic, T.; Baatar, B.; Bartke, J.; ...

2015-12-12

Here, we look for fluctuations expected for the QCD critical point using an intermittency analysis in the transverse momentum phase space of protons produced around midrapidity in the 12.5 % most central C+C, Si+Si and Pb+Pb collisions at the maximum SPS energy of 158A GeV. We find evidence of power-law fluctuations for the Si+Si data. The fitted power-law exponent Φ 2=0.96 +0.38 –0.25 (stat.) ± 0.16 (syst.) is consistent with the value expected for critical fluctuations. Power-law fluctuations had previously also been observed in low-mass π +π – pairs in the same Si+Si collisions.

Radiation processed polychloroprene-co-ethylene-propene diene terpolymer blends: Effect of radiation vulcanization on solvent transport kinetics

NASA Astrophysics Data System (ADS)

Dubey, K. A.; Bhardwaj, Y. K.; Chaudhari, C. V.; Kumar, Virendra; Goel, N. K.; Sabharwal, S.

2009-03-01

Blends of polychloroprene rubber (PCR) and ethylene propylene diene terpolymer rubber (EPDM) of different compositions were made and exposed to different gamma radiation doses. The radiation sensitivity and radiation vulcanization efficiency of blends was estimated by gel-content analysis, Charlesby-Pinner parameter determination and crosslinking density measurements. Gamma radiation induced crosslinking was most efficient for EPDM ( p0/ q0 ˜ 0.08), whereas it was the lowest for blends containing 40% PCR ( p0/ q0 ˜ 0.34). The vulcanized blends were characterized for solvent diffusion characteristics by following the swelling dynamics. Blends with higher PCR content showed anomalous swelling. The sorption and permeability of the solvent were not strictly in accordance with each other and the extent of variation in two parameters was found to be a function of blend composition. The Δ G values for solvent diffusion were in the range -2.97 to -9.58 kJ/mol and indicated thermodynamically favorable sorption for all blends. These results were corroborated by dynamic swelling, experimental as well as simulated profiles and have been explained on the basis of correlation between crosslinking density, diffusion kinetics, thermodynamic parameters and polymer-polymer interaction parameter.

Effect of binder liquid type on spherical crystallization.

PubMed

Maghsoodi, Maryam; Hajipour, Ali

2014-11-01

Spherical crystallization is a process of formation of agglomerates of crystals held together by binder liquid. This research focused on understanding the effect of type of solvents used as binder liquid on the agglomeration of crystals. Carbamazepine and ethanol/water were used respectively as a model drug and crystallization system. Eight solvents as binder liquid including chloroform, dichloromethane, isopropyl acetate, ethyl acetate, n-hexane, dimethyl aniline, benzene and toluene were examined to better understand the relationship between the physical properties of the binder liquid and its ability to bring about the formation of the agglomerates. Moreover, the agglomerates obtained from effective solvents as binder liquid were evaluated in term of size, apparent particle density and compressive strength. In this study the clear trend was observed experimentally in the agglomerate formation as a function of physical properties of the binder liquid such as miscibility with crystallization system. Furthermore, the properties of obtained agglomerates such as size, apparent particle density and compressive strength were directly related to physical properties of effective binder liquids. RESULTS of this study offer a useful starting point for a conceptual framework to guide the selection of solvent systems for spherical crystallization.

UV-Vis spectroscopy and density functional study of solvent effect on the charge transfer band of the n → σ* complexes of 2-Methylpyridine and 2-Chloropyridine with molecular iodine

NASA Astrophysics Data System (ADS)

Gogoi, Pallavi; Mohan, Uttam; Borpuzari, Manash Protim; Boruah, Abhijit; Baruah, Surjya Kumar

2017-03-01

UV-Vis spectroscopy has established that Pyridine substitutes form n→σ* charge transfer (CT) complexes with molecular Iodine. This study is a combined approach of purely experimental UV-Vis spectroscopy, Multiple linear regression theory and Computational chemistry to analyze the effect of solvent upon the charge transfer band of 2-Methylpyridine-I2 and 2-Chloropyridine-I2 complexes. Regression analysis verifies the dependence of the CT band upon different solvent parameters. Dielectric constant and refractive index are considered among the bulk solvent parameters and Hansen, Kamlet and Catalan parameters are taken into consideration at the molecular level. Density Functional Theory results explain well the blue shift of the CT bands in polar medium as an outcome of stronger donor acceptor interaction. A logarithmic relation between the bond length of the bridging atoms of the donor and the acceptor with the dielectric constant of the medium is established. Tauc plot and TDDFT study indicates a non-vertical electronic transition in the complexes. Buckingham and Lippert Mataga equations are applied to check the Polarizability effect on the CT band.

Effect of solvent polarity on the vibrational dephasing dynamics of the nitrosyl stretch in an Fe(II) complex revealed by 2D IR spectroscopy.

PubMed

Brookes, Jennifer F; Slenkamp, Karla M; Lynch, Michael S; Khalil, Munira

2013-07-25

The vibrational dephasing dynamics of the nitrosyl stretching vibration (ν(NO)) in sodium nitroprusside (SNP, Na2[Fe(CN)5NO]·2H2O) are investigated using two-dimensional infrared (2D IR) spectroscopy. The ν(NO) in SNP acts as a model system for the nitrosyl ligand found in metalloproteins which play an important role in the transportation and detection of nitric oxide (NO) in biological systems. We perform a 2D IR line shape study of the ν(NO) in the following solvents: water, deuterium oxide, methanol, ethanol, ethylene glycol, formamide, and dimethyl sulfoxide. The frequency of the ν(NO) exhibits a large vibrational solvatochromic shift of 52 cm(-1), ranging from 1884 cm(-1) in dimethyl sulfoxide to 1936 cm(-1) in water. The vibrational anharmonicity of the ν(NO) varies from 21 to 28 cm(-1) in the solvents used in this study. The frequency-frequency correlation functions (FFCFs) of the ν(NO) in SNP in each of the seven solvents are obtained by fitting the experimentally obtained 2D IR spectra using nonlinear response theory. The fits to the 2D IR line shape reveal that the spectral diffusion time scale of the ν(NO) in SNP varies from 0.8 to 4 ps and is negatively correlated with the empirical solvent polarity scales. We compare our results with the experimentally determined FFCFs of other charged vibrational probes in polar solvents and in the active sites of heme proteins. Our results suggest that the vibrational dephasing dynamics of the ν(NO) in SNP reflect the fluctuations of the nonhomogeneous electric field created by the polar solvents around the nitrosyl and cyanide ligands. The solute solvent interactions occurring at the trans-CN ligand are sensed through the π-back-bonding network along the Fe-NO bond in SNP.

Characterizing hydrophobicity at the nanoscale: a molecular dynamics simulation study.

PubMed

Bandyopadhyay, Dibyendu; Choudhury, Niharendu

2012-06-14

We use molecular dynamics (MD) simulations of water near nanoscopic surfaces to characterize hydrophobic solute-water interfaces. By using nanoscopic paraffin like plates as model solutes, MD simulations in isothermal-isobaric ensemble have been employed to identify characteristic features of such an interface. Enhanced water correlation, density fluctuations, and position dependent compressibility apart from surface specific hydrogen bond distribution and molecular orientations have been identified as characteristic features of such interfaces. Tetrahedral order parameter that quantifies the degree of tetrahedrality in the water structure and an orientational order parameter, which quantifies the orientational preferences of the second solvation shell water around a central water molecule, have also been calculated as a function of distance from the plate surface. In the vicinity of the surface these two order parameters too show considerable sensitivity to the surface hydrophobicity. The potential of mean force (PMF) between water and the surface as a function of the distance from the surface has also been analyzed in terms of direct interaction and induced contribution, which shows unusual effect of plate hydrophobicity on the solvent induced PMF. In order to investigate hydrophobic nature of these plates, we have also investigated interplate dewetting when two such plates are immersed in water.

Calculation of boron-isotope fractionation between B(OH) 3(aq) and B(OH)4-(aq)

NASA Astrophysics Data System (ADS)

Rustad, James R.; Bylaska, Eric J.; Jackson, Virgil E.; Dixon, David A.

2010-05-01

Density functional and correlated molecular orbital calculations (MP2) are carried out on B(OH) 3· nH 2O clusters ( n = 0, 6, 32), and B(OH)4-· nH 2O ( n = 0, 8, 11, 32) to estimate the equilibrium distribution of 10B and 11B isotopes between boric acid and borate in aqueous solution. For the large 32-water clusters, multiple conformations are generated from ab initio molecular dynamics simulations to account for the effect of solvent fluctuations on the isotopic fractionation. We provide an extrapolated value of the equilibrium constant α34 for the isotope exchange reaction 10B(OH) 3(aq) + 11B(OH)4- (aq) = 11B(OH) 3(aq) + 11B(OH)4- (aq) of 1.026-1.028 near the MP2 complete basis set limit with 32 explicit waters of solvation. With some exchange-correlation functionals we find potentially important contributions from a tetrahedral neutral B(OH) 3·H 2O Lewis acid-base complex. The extrapolations presented here suggest that DFT calculations give a value for 10 3ln α34 about 15% higher than the MP2 calculations.

Adiabatic electron thermal pressure fluctuations in tokamak plasmas.

PubMed

Meier, M A; Bengtson, R D; Hallock, G A; Wootton, A J

2001-08-20

Electron thermal pressure fluctuations measured in the edge plasma of the Texas Experimental Tokamak Upgrade are a fundamental component of plasma turbulence on both sides of the velocity shear layer. The ratio of specific heats, estimated from fluctuations in electron temperature and electron number density measured simultaneously at the same electrode, indicates that observed fluctuations are adiabatic. The observations are made by means of a novel Langmuir probe technique, the time domain triple-probe method, which concurrently measures multiple plasma properties at each of two electrodes with the temporal and the spatial resolution required to estimate thermodynamic properties in a turbulent plasma.

Fluctuations in microwave background radiation due to secondary ionization of the intergalactic gas in the universe

NASA Technical Reports Server (NTRS)

Sunyayev, R. A.

1979-01-01

Secondary heating and ionization of the intergalactic gas at redshifts z approximately 10-30 could lead to the large optical depth of the Universe for Thomson scattering and could smooth the primordial fluctuations formed at z approximately 1500. It is shown that the gas motions connected with the large scale density perturbations at z approximately 10-15 must lead to the generation of secondary fluctuations of microwave background. The contribution of the rich clusters of galaxies and young galaxies to the fluctuations of microwave background is also estimated.

Relationship between symbiont density and photosynthetic carbon acquisition in the temperate coral Cladocora caespitosa

NASA Astrophysics Data System (ADS)

Hoogenboom, M.; Beraud, E.; Ferrier-Pagès, C.

2010-03-01

This study quantified variation in net photosynthetic carbon gain in response to natural fluctuations in symbiont density for the Mediterranean coral Cladocora caespitosa, and evaluated which density maximized photosynthetic carbon acquisition. To do this, carbon acquisition was modeled as an explicit function of symbiont density. The model was parameterized using measurements of rates of photosynthesis and respiration for small colonies with a broad range of zooxanthella concentrations. Results demonstrate that rates of net photosynthesis increase asymptotically with symbiont density, whereas rates of respiration increase linearly. In combination, these functional responses meant that colony energy acquisition decreased at both low and at very high zooxanthella densities. However, there was a wide range of symbiont densities for which net daily photosynthesis was approximately equivalent. Therefore, significant changes in symbiont density do not necessarily cause a change in autotrophic energy acquisition by the colony. Model estimates of the optimal range of cell densities corresponded well with independent observations of symbiont concentrations obtained from field and laboratory studies of healthy colonies. Overall, this study demonstrates that the seasonal fluctuations, in symbiont numbers observed in healthy colonies of the Mediterranean coral investigated, do not have a strong effect on photosynthetic energy acquisition.

Solute-Solvent Charge-Transfer Excitations and Optical Absorption of Hydrated Hydroxide from Time-Dependent Density-Functional Theory.

PubMed

Opalka, Daniel; Sprik, Michiel

2014-06-10

The electronic structure of simple hydrated ions represents one of the most challenging problems in electronic-structure theory. Spectroscopic experiments identified the lowest excited state of the solvated hydroxide as a charge-transfer-to-solvent (CTTS) state. In the present work we report computations of the absorption spectrum of the solvated hydroxide ion, treating both solvent and solute strictly at the same level of theory. The average absorption spectrum up to 25 eV has been computed for samples taken from periodic ab initio molecular dynamics simulations. The experimentally observed CTTS state near the onset of the absorption threshold has been analyzed at the generalized-gradient approximation (GGA) and with a hybrid density-functional. Based on results for the lowest excitation energies computed with the HSE hybrid functional and a Davidson diagonalization scheme, the CTTS transition has been found 0.6 eV below the first absorption band of liquid water. The transfer of an electron to the solvent can be assigned to an excitation from the solute 2pπ orbitals, which are subject to a small energetic splitting due to the asymmetric solvent environment, to the significantly delocalized lowest unoccupied orbital of the solvent. The distribution of the centers of the excited state shows that CTTS along the OH(-) axis of the hydroxide ion is avoided. Furthermore, our simulations indicate that the systematic error arising in the calculated spectrum at the GGA originates from a poor description of the valence band energies in the solution.