Molecular mechanics and structure of the fluid-solid interface in simple fluids
Wang, Gerald J.; Hadjiconstantinou, Nicolas G.
2017-09-01
Near a fluid-solid interface, the fluid spatial density profile is highly nonuniform at the molecular scale. This nonuniformity can have profound effects on the dynamical behavior of the fluid and has been shown to play an especially important role when modeling a wide variety of nanoscale heat and momentum transfer phenomena. We use molecular-mechanics arguments and molecular-dynamics (MD) simulations to develop a better understanding of the structure of the first fluid layer directly adjacent to the solid in the layering regime, as delineated by a nondimensional number that compares the effects of wall-fluid interaction to thermal energy. Using asymptotic analysis of the Nernst-Planck equation, we show that features of the fluid density profile close to the wall, such as the areal density of the first layer ΣFL (defined as the number of atoms in this layer per unit of fluid-solid interfacial area), can be expressed as polynomial functions of the fluid average density ρave. This is found to be in agreement with MD simulations, which also show that the width of the first layer hFL is a linear function of the average density and only a weak function of the temperature T . These results can be combined to show that, for system average densities corresponding to a dense fluid (ρave≥0.7 ), the ratio C ≡ΣFLρavehFL, representing a density enhancement with respect to the bulk fluid, depends only weakly on temperature and is essentially independent of density. Further MD simulations suggest that the above results, nominally valid for large systems (solid in contact with semi-infinite fluid), also describe fluid-solid interfaces under considerable nanoconfinement, provided ρave is appropriately defined.
Fluids density functional theory and initializing molecular dynamics simulations of block copolymers
Brown, Jonathan R.; Seo, Youngmi; Maula, Tiara Ann D.; Hall, Lisa M.
2016-03-01
Classical, fluids density functional theory (fDFT), which can predict the equilibrium density profiles of polymeric systems, and coarse-grained molecular dynamics (MD) simulations, which are often used to show both structure and dynamics of soft materials, can be implemented using very similar bead-based polymer models. We aim to use fDFT and MD in tandem to examine the same system from these two points of view and take advantage of the different features of each methodology. Additionally, the density profiles resulting from fDFT calculations can be used to initialize the MD simulations in a close to equilibrated structure, speeding up the simulations. Here, we show how this method can be applied to study microphase separated states of both typical diblock and tapered diblock copolymers in which there is a region with a gradient in composition placed between the pure blocks. Both methods, applied at constant pressure, predict a decrease in total density as segregation strength or the length of the tapered region is increased. The predictions for the density profiles from fDFT and MD are similar across materials with a wide range of interfacial widths.
Quantum molecular dynamics simulations of thermophysical properties of fluid ethane.
Zhang, Yujuan; Wang, Cong; Zheng, Fawei; Zhang, Ping
2012-12-01
We have performed first-principles molecular-dynamics simulations based on density-functional theory to study the thermophysical properties of ethane under extreme conditions. We present results for the equation of state of fluid ethane in the warm dense region. The optical conductivity is calculated via the Kubo-Greenwood formula from which the dc conductivity and optical reflectivity are derived. The close correlation between the nonmetal-metal transition of ethane and its decomposition, that ethane dissociates significantly into molecular and/or atomic hydrogen and some long alkane chains, has been systematically studied by analyzing the optical conductivity spectra, pair correlation functions, electronic density of states, and charge density distribution of fluid ethane.
Donkov, Sava; Stefanov, Ivan Z.
2018-03-01
We have set ourselves the task of obtaining the probability distribution function of the mass density of a self-gravitating isothermal compressible turbulent fluid from its physics. We have done this in the context of a new notion: the molecular clouds ensemble. We have applied a new approach that takes into account the fractal nature of the fluid. Using the medium equations, under the assumption of steady state, we show that the total energy per unit mass is an invariant with respect to the fractal scales. As a next step we obtain a non-linear integral equation for the dimensionless scale Q which is the third root of the integral of the probability distribution function. It is solved approximately up to the leading-order term in the series expansion. We obtain two solutions. They are power-law distributions with different slopes: the first one is -1.5 at low densities, corresponding to an equilibrium between all energies at a given scale, and the second one is -2 at high densities, corresponding to a free fall at small scales.
Density and Phase State of a Confined Nonpolar Fluid
Kienle, Daniel F.; Kuhl, Tonya L.
2016-07-01
Measurements of the mean refractive index of a spherelike nonpolar fluid, octamethytetracylclosiloxane (OMCTS), confined between mica sheets, demonstrate direct and conclusive experimental evidence of the absence of a first-order liquid-to-solid phase transition in the fluid when confined, which has been suggested to occur from previous experimental and simulation results. The results also show that the density remains constant throughout confinement, and that the fluid is incompressible. This, along with the observation of very large increases (many orders of magnitude) in viscosity during confinement from the literature, demonstrate that the molecular motion is limited by the confining wall and not the molecular packing. In addition, the recently developed refractive index profile correction method, which enables the structural perturbation inherent at a solid-liquid interface and that of a liquid in confinement to be determined independently, was used to show that there was no measurable excess or depleted mass of OMCTS near the mica surface in bulk films or confined films of only two molecular layers.
The force distribution probability function for simple fluids by density functional theory.
Rickayzen, G; Heyes, D M
2013-02-28
Classical density functional theory (DFT) is used to derive a formula for the probability density distribution function, P(F), and probability distribution function, W(F), for simple fluids, where F is the net force on a particle. The final formula for P(F) ∝ exp(-AF(2)), where A depends on the fluid density, the temperature, and the Fourier transform of the pair potential. The form of the DFT theory used is only applicable to bounded potential fluids. When combined with the hypernetted chain closure of the Ornstein-Zernike equation, the DFT theory for W(F) agrees with molecular dynamics computer simulations for the Gaussian and bounded soft sphere at high density. The Gaussian form for P(F) is still accurate at lower densities (but not too low density) for the two potentials, but with a smaller value for the constant, A, than that predicted by the DFT theory.
International Nuclear Information System (INIS)
Pourali, Meisam; Maghari, Ali; Meloni, Simone; Magaletti, Francesco; Casciola, Carlo Massimo; Ciccotti, Giovanni
2014-01-01
We compare dynamical nonequilibrium molecular dynamics and continuum simulations of the dynamics of relaxation of a fluid system characterized by a non-uniform density profile. Results match quite well as long as the lengthscale of density nonuniformities are greater than the molecular scale (∼10 times the molecular size). In presence of molecular scale features some of the continuum fields (e.g., density and momentum) are in good agreement with atomistic counterparts, but are smoother. On the contrary, other fields, such as the temperature field, present very large difference with respect to reference (atomistic) ones. This is due to the limited accuracy of some of the empirical relations used in continuum models, the equation of state of the fluid in the present example
Physical Properties of Low-Molecular Weight Polydimethylsiloxane Fluids
Energy Technology Data Exchange (ETDEWEB)
Roberts, Christine Cardinal [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Graham, Alan [Univ. of Colorado, Denver, CO (United States); Nemer, Martin [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Phinney, Leslie M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Garcia, Robert M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Soehnel, Melissa Marie [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Stirrup, Emily Kate [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
2017-02-01
Physical property measurements including viscosity, density, thermal conductivity, and heat capacity of low-molecular weight polydimethylsiloxane (PDMS) fluids were measured over a wide temperature range (-50°C to 150°C when possible). Properties of blends of 1 cSt and 20 cSt PDMS fluids were also investigated. Uncertainties in the measurements are cited. These measurements will provide greater fidelity predictions of environmental sensing device behavior in hot and cold environments.
Travelling waves of density for a fourth-gradient model of fluids
Gouin, Henri; Saccomandi, Giuseppe
2016-09-01
In mean-field theory, the non-local state of fluid molecules can be taken into account using a statistical method. The molecular model combined with a density expansion in Taylor series of the fourth order yields an internal energy value relevant to the fourth-gradient model, and the equation of isothermal motions takes then density's spatial derivatives into account for waves travelling in both liquid and vapour phases. At equilibrium, the equation of the density profile across interfaces is more precise than the Cahn and Hilliard equation, and near the fluid's critical point, the density profile verifies an Extended Fisher-Kolmogorov equation, allowing kinks, which converges towards the Cahn-Hillard equation when approaching the critical point. Nonetheless, we also get pulse waves oscillating and generating critical opalescence.
Measurement bias of fluid velocity in molecular simulations
International Nuclear Information System (INIS)
Tysanner, Martin W.; Garcia, Alejandro L.
2004-01-01
In molecular simulations of fluid flow, the measurement of mean fluid velocity is considered to be a straightforward computation, yet there is some ambiguity in its definition. We show that in systems far from equilibrium, such as those with large temperature or velocity gradients, two commonly used definitions give slightly different results. Specifically, a bias can arise when computing the mean fluid velocity by measuring the mean particle velocity in a cell and averaging this mean over samples. We show that this bias comes from the correlation of momentum and density fluctuations in non-equilibrium fluids, obtain an analytical expression for predicting it, and discuss what system characteristics (e.g., number of particles per cell, temperature gradients) reduce or magnify the error. The bias has a physical origin so although we demonstrate it by direct simulation Monte Carlo (DSMC) computations, the same effect will be observed with other particle-based simulation methods, such as molecular dynamics and lattice gases
Molecular Dynamics Simulation of Binary Fluid in a Nanochannel
International Nuclear Information System (INIS)
Mullick, Shanta; Ahluwalia, P. K.; Pathania, Y.
2011-01-01
This paper presents the results from a molecular dynamics simulation of binary fluid (mixture of argon and krypton) in the nanochannel flow. The computational software LAMMPS is used for carrying out the molecular dynamics simulations. Binary fluids of argon and krypton with varying concentration of atom species were taken for two densities 0.65 and 0.45. The fluid flow takes place between two parallel plates and is bounded by horizontal walls in one direction and periodic boundary conditions are imposed in the other two directions. To drive the flow, a constant force is applied in one direction. Each fluid atom interacts with other fluid atoms and wall atoms through Week-Chandler-Anderson (WCA) potential. The velocity profile has been looked at for three nanochannel widths i.e for 12σ, 14σ and 16σ and also for the different concentration of two species. The velocity profile of the binary fluid predicted by the simulations agrees with the quadratic shape of the analytical solution of a Poiseuille flow in continuum theory.
Cattes, Stefanie M.; Gubbins, Keith E.; Schoen, Martin
2016-05-01
In this work, we employ classical density functional theory (DFT) to investigate for the first time equilibrium properties of a Heisenberg fluid confined to nanoscopic slit pores of variable width. Within DFT pair correlations are treated at modified mean-field level. We consider three types of walls: hard ones, where the fluid-wall potential becomes infinite upon molecular contact but vanishes otherwise, and hard walls with superimposed short-range attraction with and without explicit orientation dependence. To model the distance dependence of the attractions, we employ a Yukawa potential. The orientation dependence is realized through anchoring of molecules at the substrates, i.e., an energetic discrimination of specific molecular orientations. If the walls are hard or attractive without specific anchoring, the results are "quasi-bulk"-like in that they can be linked to a confinement-induced reduction of the bulk mean field. In these cases, the precise nature of the walls is completely irrelevant at coexistence. Only for specific anchoring nontrivial features arise, because then the fluid-wall interaction potential affects the orientation distribution function in a nontrivial way and thus appears explicitly in the Euler-Lagrange equations to be solved for minima of the grand potential of coexisting phases.
Magnetization of High Density Hadronic Fluid
DEFF Research Database (Denmark)
Bohr, Henrik; Providencia, Constanca; da Providencia, João
2012-01-01
In the present paper the magnetization of a high density relativistic fluid of elementary particles is studied. At very high densities, such as may be found in the interior of a neutron star, when the external magnetic field is gradually increased, the energy of the normal phase of the fluid...... in the particle fluid. For nuclear densities above 2 to 3 rho(0), where rho(0) is the equilibrium nuclear density, the resulting magnetic field turns out to be rather huge, of the order of 10(17) Gauss....
Pressure Enhancement in Confined Fluids: Effect of Molecular Shape and Fluid-Wall Interactions.
Srivastava, Deepti; Santiso, Erik E; Gubbins, Keith E
2017-10-24
Recently, several experimental and simulation studies have found that phenomena that normally occur at extremely high pressures in a bulk phase can occur in nanophases confined within porous materials at much lower bulk phase pressures, thus providing an alternative route to study high-pressure phenomena. In this work, we examine the effect on the tangential pressure of varying the molecular shape, strength of the fluid-wall interactions, and pore width, for carbon slit-shaped pores. We find that, for multisite molecules, the presence of additional rotational degrees of freedom leads to unique changes in the shape of the tangential pressure profile, especially in larger pores. We show that, due to the direct relationship between the molecular density and the fluid-wall interactions, the latter have a large impact on the pressure tensor. The molecular shape and pore size have a notable impact on the layering of molecules in the pore, greatly influencing both the shape and scale of the tangential pressure profile.
Simulations of vibrational relaxation in dense molecular fluids
International Nuclear Information System (INIS)
Holian, B.L.
1985-07-01
In the understanding of high-temperatre and -pressure chemistry in explosives, first step is the study of the transfer of energy from translational degrees of freedom into internal vibrations of the molecules. We present new methods using nonequilibrium molecular dynamics (NEMD) for measuring vibrational relaxation in a diatomic fluid, where we expect a classical treatment of many-body collisions to be relevant because of the high densities (2 to 3 times compressed compared to the normal fluid) and high temperatures (2000 to 4000 K) involved behind detonation waves. NEMD techniques are discussed, including their limitations, and qualitative results presented
Molecular thermodynamics of nonideal fluids
Lee, Lloyd L
2013-01-01
Molecular Thermodynamics of Nonideal Fluids serves as an introductory presentation for engineers to the concepts and principles behind and the advances in molecular thermodynamics of nonideal fluids. The book covers related topics such as the laws of thermodynamics; entropy; its ensembles; the different properties of the ideal gas; and the structure of liquids. Also covered in the book are topics such as integral equation theories; theories for polar fluids; solution thermodynamics; and molecular dynamics. The text is recommended for engineers who would like to be familiarized with the concept
Molecular dynamics studies of fluid/oil interfaces for improved oil recovery processes.
de Lara, Lucas S; Michelon, Mateus F; Miranda, Caetano R
2012-12-20
In our paper, we study the interface wettability, diffusivity, and molecular orientation between crude oil and different fluids for applications in improved oil recovery (IOR) processes through atomistic molecular dynamics (MD). The salt concentration, temperature, and pressure effects on the physical chemistry properties of different interfaces between IOR agents [brine (H(2)O + % NaCl), CO(2), N(2), and CH(4)] and crude oil have been determined. From the interfacial density profiles, an accumulation of aromatic molecules near the interface has been observed. In the case of brine interfaced with crude oil, our calculations indicate an increase in the interfacial tension with increasing pressure and salt concentration, which favors oil displacement. On the other hand, with the other fluids studied (CO(2), N(2), and CH(4)), the interfacial tension decreases with increasing pressure and temperature. With interfacial tension reduction, an increase in fluid diffusivity in the oil phase is observed. We also studied the molecular orientation properties of the hydrocarbon and fluids molecules in the interface region. We perceived that the molecular orientation could be affected by changes in the interfacial tension and diffusivity of the molecules in the interface region with the increased pressure and temperature: pressure (increasing) → interfacial tension (decreasing) → diffusion (increasing) → molecular ordering. From a molecular point of view, the combination of low interfacial tension and high diffusion of molecules in the oil phase gives the CO(2) molecules unique properties as an IOR fluid compared with other fluids studied here.
Shang, Barry Z; Voulgarakis, Nikolaos K; Chu, Jhih-Wei
2012-07-28
This work illustrates that fluctuating hydrodynamics (FHD) simulations can be used to capture the thermodynamic and hydrodynamic responses of molecular fluids at the nanoscale, including those associated with energy and heat transfer. Using all-atom molecular dynamics (MD) trajectories as the reference data, the atomistic coordinates of each snapshot are mapped onto mass, momentum, and energy density fields on Eulerian grids to generate a corresponding field trajectory. The molecular length-scale associated with finite molecule size is explicitly imposed during this coarse-graining by requiring that the variances of density fields scale inversely with the grid volume. From the fluctuations of field variables, the response functions and transport coefficients encoded in the all-atom MD trajectory are computed. By using the extracted fluid properties in FHD simulations, we show that the fluctuations and relaxation of hydrodynamic fields quantitatively match with those observed in the reference all-atom MD trajectory, hence establishing compatibility between the atomistic and field representations. We also show that inclusion of energy transfer in the FHD equations can more accurately capture the thermodynamic and hydrodynamic responses of molecular fluids. The results indicate that the proposed MD-to-FHD mapping with explicit consideration of finite molecule size provides a robust framework for coarse-graining the solution phase of complex molecular systems.
The density functional theory and the charged fluid molecular dynamics
International Nuclear Information System (INIS)
Hansen, J.P.; Zerah, G.
1993-01-01
Car and Parrinello had the idea of combining the density functional theory (Hohenberg, Kohn and Sham) to the 'molecular dynamics' numerical modelling method, in order to simulate metallic or co-valent solids and liquids from the first principles. The objective of this paper is to present a simplified version of this method ab initio, applicable to classical and quantal charged systems. The method is illustrated with recent results on charged colloidal suspensions and highly correlated electron-proton plasmas. 1 fig., 21 refs
Oulebsir, Fouad; Vermorel, Romain; Galliero, Guillaume
2018-01-16
With the advent of graphene material, membranes based on single-layer nanoporous solids appear as promising devices for fluid separation, be it liquid or gaseous mixtures. The design of such architectured porous materials would greatly benefit from accurate models that can predict their transport and separation properties. More specifically, there is no universal understanding of how parameters such as temperature, fluid loading conditions, or the ratio of the pore size to the fluid molecular diameter influence the permeation process. In this study, we address the problem of pure supercritical fluids diffusing through simplified models of single-layer porous materials. Basically, we investigate a toy model that consists of a single-layer lattice of Lennard-Jones interaction sites with a slit gap of controllable width. We performed extensive equilibrium and biased molecular dynamics simulations to document the physical mechanisms involved at the molecular scale. We propose a general constitutive equation for the diffusional transport coefficient derived from classical statistical mechanics and kinetic theory, which can be further simplified in the ideal gas limit. This transport coefficient relates the molecular flux to the fluid density jump across the single-layer membrane. It is found to be proportional to the accessible surface porosity of the single-layer porous solid and to a thermodynamic factor accounting for the inhomogeneity of the fluid close to the pore entrance. Both quantities directly depend on the potential of mean force that results from molecular interactions between solid and fluid atoms. Comparisons with the simulations data show that the kinetic model captures how narrowing the pore size below the fluid molecular diameter lowers dramatically the value of the transport coefficient. Furthermore, we demonstrate that our general constitutive equation allows for a consistent interpretation of the intricate effects of temperature and fluid loading
Bazhenov, Alexiev M.; Heyes, David M.
1990-01-01
The thermodynamics, structure, and transport coefficients, as defined by the Green-Kubo integrals, of the one-dimensional Lennard-Jones fluid are evaluated for a wide range of state points by molecular dynamics computer simulation. These calculations are performed for the first time for thermal conductivity and the viscosity. We observe a transition from hard-rod behavior at low number density to harmonic-spring fluid behavior in the close-packed limit. The self-diffusion coefficient decays with increasing density to a finite limiting value. The thermal conductivity increases with density, tending to ∞ in the close-packed limit. The viscosity in contrast maximizes at intermediate density, tending to zero in the zero density and close-packed limits.
Directory of Open Access Journals (Sweden)
Shen Min
2016-01-01
Full Text Available Magnetrohelogical fluids (MRFs represent a class of smart materials whose rheological properties change in response to the magnetic field, which resulting in the drastic change of the acoustic impedance. This paper presents an acoustic propagation model that approximates a fluid-saturated porous medium as a fluid with a bulk modulus and effective density (EDFM to study the acoustic propagation in the MRF materials under magnetic field. The effective density fluid model derived from the Biot’s theory. Some minor changes to the theory had to be applied, modeling both fluid-like and solid-like state of the MRF material. The attenuation and velocity variation of the MRF are numerical calculated. The calculated results show that for the MRF material the attenuation and velocity predicted with this effective density fluid model are close agreement with the previous predictions by Biot’s theory. We demonstrate that for the MRF material acoustic prediction the effective density fluid model is an accurate alternative to full Biot’s theory and is much simpler to implement.
Phase space density representations in fluid dynamics
International Nuclear Information System (INIS)
Ramshaw, J.D.
1989-01-01
Phase space density representations of inviscid fluid dynamics were recently discussed by Abarbanel and Rouhi. Here it is shown that such representations may be simply derived and interpreted by means of the Liouville equation corresponding to the dynamical system of ordinary differential equations that describes fluid particle trajectories. The Hamiltonian and Poisson bracket for the phase space density then emerge as immediate consequences of the corresponding structure of the dynamics. For barotropic fluids, this approach leads by direct construction to the formulation presented by Abarbanel and Rouhi. Extensions of this formulation to inhomogeneous incompressible fluids and to fluids in which the state equation involves an additional transported scalar variable are constructed by augmenting the single-particle dynamics and phase space to include the relevant additional variable
Self-diffusion in monodisperse three-dimensional magnetic fluids by molecular dynamics simulations
Energy Technology Data Exchange (ETDEWEB)
Dobroserdova, A.B. [Ural Federal University, Lenin Av. 51, Ekaterinburg (Russian Federation); Kantorovich, S.S., E-mail: alla.dobroserdova@urfu.ru [Ural Federal University, Lenin Av. 51, Ekaterinburg (Russian Federation); University of Vienna, Sensengasse 8, Vienna (Austria)
2017-06-01
In the present work we study the self-diffusion behaviour in the three-dimensional monodisperse magnetic fluids using the Molecular Dynamics Simulation and Density Functional Theory. The peculiarity of computer simulation is to study two different systems: dipolar and soft sphere ones. In the theoretical method, it is important to choose the approximation for the main structures, which are chains. We compare the theoretical results and the computer simulation data for the self-diffusion coefficient as a function of the particle volume fraction and magnetic dipole-dipole interaction parameter and find the qualitative and quantitative agreement to be good. - Highlights: • The paper deals with the study of the self-diffusion in monodisperse three-dimensional magnetic fluids. • The theoretical approach contains the free energy density functional minimization. • Computer simulations are performed by the molecular dynamics method. • We have a good qualitative and quantitative agreement between the theoretical results and computer simulation data.
Structure and properties of simple molecular systems at very high density
International Nuclear Information System (INIS)
LeSar, R.
1989-01-01
The use of computer simulations in the study of molecular systems at very high density is reviewed. Applications to the thermodynamics of dense fluid nitrogen and phase transitions in solid oxygen are presented. The effects of changes in the atomic electronic structure on the equation of state of very dense helium are discussed. 19 refs., 2 figs
International Nuclear Information System (INIS)
Singh, Ram Chandra
2007-01-01
We have used the density-functional theory to study the effect of varying temperature on the isotropic-nematic transition of a fluid of molecules interacting via the Gay-Berne intermolecular potential. The nematic phase is found to be stable with respect to isotropic phase in the temperature range 0.80≤T*≤1.25. Pair correlation functions needed as input information in density-functional theory is calculated using the Percus-Yevick integral equation theory. We find that the density-functional theory is good for studying the isotropic-nematic transition in molecular fluids if the values of the pair-correlation functions in the isotropic phase are known accurately. We have also compared our results with computer simulation results wherever they are available
Time-dependent quantum fluid density functional theory of hydrogen ...
Indian Academy of Sciences (India)
WINTEC
density functional theory; quantum fluid dynamics. 1. Introduction ... dynamics of strongly non-linear interaction of atoms with intense ... theory and quantum fluid dynamics in real space. .... clear evidence of bond softening since density in the.
Skarmoutsos, Ioannis; Samios, Jannis
2006-11-02
Molecular dynamics atomistic simulations in the canonical ensemble (NVT-MD) have been used to investigate the "Local Density Inhomogeneities and their Dynamics" in pure supercritical water. The simulations were carried out along a near-critical isotherm (Tr = T/Tc = 1.03) and for a wide range of densities below and above the critical one (0.2 rho(c) - 2.0 rho(c)). The results obtained reveal the existence of significant local density augmentation effects, which are found to be sufficiently larger in comparison to those reported for nonassociated fluids. The time evolution of the local density distribution around each molecule was studied in terms of the appropriate time correlation functions C(Delta)rhol(t). It is found that the shape of these functions changes significantly by increasing the density of the fluid. Finally, the local density reorganization times for the first and second coordination shell derived from these correlations exhibit a decreasing behavior by increasing the density of the system, signifying the density effect upon the dynamics of the local environment around each molecule.
Quantum molecular dynamics simulations of thermophysical properties of fluid ethane
Zhang, Yujuan; Wang, Cong; Zheng, Fawei; Zhang, Ping
2012-01-01
We have performed first-principles molecular-dynamics simulations based on density-functional theory to study the thermophysical properties of ethane under extreme conditions. We present new results for the equation of state of fluid ethane in the warm dense region. The optical conductivity is calculated via the Kubo-Greenwood formula from which the dc conductivity and optical reflectivity are derived. The close correlation between the nonmetal-metal transition of ethane and its decomposition...
International Nuclear Information System (INIS)
Ghobadi, Ahmadreza F.; Elliott, J. Richard
2014-01-01
In this work, a new classical density functional theory is developed for group-contribution equations of state (EOS). Details of implementation are demonstrated for the recently-developed SAFT-γ WCA EOS and selective applications are studied for confined fluids and vapor-liquid interfaces. The acronym WCA (Weeks-Chandler-Andersen) refers to the characterization of the reference part of the third-order thermodynamic perturbation theory applied in formulating the EOS. SAFT-γ refers to the particular form of “statistical associating fluid theory” that is applied to the fused-sphere, heteronuclear, united-atom molecular models of interest. For the monomer term, the modified fundamental measure theory is extended to WCA-spheres. A new chain functional is also introduced for fused and soft heteronuclear chains. The attractive interactions are taken into account by considering the structure of the fluid, thus elevating the theory beyond the mean field approximation. The fluctuations of energy are also included via a non-local third-order perturbation theory. The theory includes resolution of the density profiles of individual groups such as CH 2 and CH 3 and satisfies stoichiometric constraints for the density profiles. New molecular simulations are conducted to demonstrate the accuracy of each Helmholtz free energy contribution in reproducing the microstructure of inhomogeneous systems at the united-atom level of coarse graining. At each stage, comparisons are made to assess where the present theory stands relative to the current state of the art for studying inhomogeneous fluids. Overall, it is shown that the characteristic features of real molecular fluids are captured both qualitatively and quantitatively. For example, the average pore density deviates ∼2% from simulation data for attractive pentadecane in a 2-nm slit pore. Another example is the surface tension of ethane/heptane mixture, which deviates ∼1% from simulation data while the theory reproduces
Density Fluctuations of Hard-Sphere Fluids in Narrow Confinement
Directory of Open Access Journals (Sweden)
Kim Nygård
2016-02-01
Full Text Available Spatial confinement induces microscopic ordering of fluids, which in turn alters many of their dynamic and thermodynamic properties. However, the isothermal compressibility has hitherto been largely overlooked in the literature, despite its obvious connection to the underlying microscopic structure and density fluctuations in confined geometries. Here, we address this issue by probing density profiles and structure factors of hard-sphere fluids in various narrow slits, using x-ray scattering from colloid-filled nanofluidic containers and integral-equation-based statistical mechanics at the level of pair distributions for inhomogeneous fluids. Most importantly, we demonstrate that density fluctuations and isothermal compressibilities in confined fluids can be obtained experimentally from the long-wavelength limit of the structure factor, providing a formally exact and experimentally accessible connection between microscopic structure and macroscopic, thermodynamic properties. Our approach will thus, for example, allow direct experimental verification of theoretically predicted enhanced density fluctuations in liquids near solvophobic interfaces.
Atomistic Modeling of the Fluid-Solid Interface in Simple Fluids
Hadjiconstantinou, Nicolas; Wang, Gerald
2017-11-01
Fluids can exhibit pronounced structuring effects near a solid boundary, typically manifested in a layered structure that has been extensively shown to directly affect transport across the interface. We present and discuss several results from molecular-mechanical modeling and molecular-dynamics (MD) simulations aimed at characterizing the structure of the first fluid layer directly adjacent to the solid. We identify a new dimensionless group - termed the Wall number - which characterizes the degree of fluid layering, by comparing the competing effects of wall-fluid interaction and thermal energy. We find that in the layering regime, several key features of the first layer layer - including its distance from the solid, its width, and its areal density - can be described using mean-field-energy arguments, as well as asymptotic analysis of the Nernst-Planck equation. For dense fluids, the areal density and the width of the first layer can be related to the bulk fluid density using a simple scaling relation. MD simulations show that these results are broadly applicable and robust to the presence of a second confining solid boundary, different choices of wall structure and thermalization, strengths of fluid-solid interaction, and wall geometries.
Ghobadi, Ahmadreza F.; Elliott, J. Richard
2014-07-01
In this work, a new classical density functional theory is developed for group-contribution equations of state (EOS). Details of implementation are demonstrated for the recently-developed SAFT-γ WCA EOS and selective applications are studied for confined fluids and vapor-liquid interfaces. The acronym WCA (Weeks-Chandler-Andersen) refers to the characterization of the reference part of the third-order thermodynamic perturbation theory applied in formulating the EOS. SAFT-γ refers to the particular form of "statistical associating fluid theory" that is applied to the fused-sphere, heteronuclear, united-atom molecular models of interest. For the monomer term, the modified fundamental measure theory is extended to WCA-spheres. A new chain functional is also introduced for fused and soft heteronuclear chains. The attractive interactions are taken into account by considering the structure of the fluid, thus elevating the theory beyond the mean field approximation. The fluctuations of energy are also included via a non-local third-order perturbation theory. The theory includes resolution of the density profiles of individual groups such as CH2 and CH3 and satisfies stoichiometric constraints for the density profiles. New molecular simulations are conducted to demonstrate the accuracy of each Helmholtz free energy contribution in reproducing the microstructure of inhomogeneous systems at the united-atom level of coarse graining. At each stage, comparisons are made to assess where the present theory stands relative to the current state of the art for studying inhomogeneous fluids. Overall, it is shown that the characteristic features of real molecular fluids are captured both qualitatively and quantitatively. For example, the average pore density deviates ˜2% from simulation data for attractive pentadecane in a 2-nm slit pore. Another example is the surface tension of ethane/heptane mixture, which deviates ˜1% from simulation data while the theory reproduces the excess
Volume and density changes of biological fluids with temperature
Hinghofer-Szalkay, H.
1985-01-01
The thermal expansion of human blood, plasma, ultrafiltrate, and erythrocycte concentration at temperatures in the range of 4-48 C is studied. The mechanical oscillator technique which has an accuracy of 1 x 10 to the -5 th g/ml is utilized to measure fluid density. The relationship between thermal expansion, density, and temperature is analyzed. The study reveals that: (1) thermal expansion increases with increasing temperature; (2) the magnitude of the increase declines with increasing temperature; (3) thermal expansion increases with density at temperatures below 40 C; and (4) the thermal expansion of intracellular fluid is greater than that of extracellular fluid in the temperature range of 4-10 C, but it is equal at temperatures greater than or equal to 40 C.
Fluid Density and Impact Cavity Formation
Directory of Open Access Journals (Sweden)
Ga-Chun Lin
2018-01-01
Full Text Available Characteristics of the impact cavity formed when a steel ball is dropped into aqueous solutions of densities ranging from 0.98 g·cm-3 to 1.63 g·cm-3 were investigated. A high-speed camera was used to record the formation and collapse of the cavity. The results showed cavity diameter, volume, and pinch-off time are independent of fluid density, on average. There was an unexplained reduction in cavity formation for densities of 1.34 g·cm-3 and 1.45 g·cm-3.
Effects of nanoscale density inhomogeneities on shearing fluids
DEFF Research Database (Denmark)
Ben, Dalton,; Peter, Daivis,; Hansen, Jesper Schmidt
2013-01-01
It is well known that density inhomogeneities at the solid-liquid interface can have a strong effect on the velocity profile of a nanoconfined fluid in planar Poiseuille flow. However, it is difficult to control the density inhomogeneities induced by solid walls, making this type of system...... systems. Using the sinusoidal transverse force method to produce shearing velocity profiles and the sinusoidal longitudinal force method to produce inhomogeneous density profiles, we are able to observe the interactions between the two property inhomogeneities at the level of individual Fourier components....... This gives us a method for direct measurement of the coupling between the density and velocity fields and allows us to introduce various feedback control mechanisms which customize fluid behavior in individual Fourier components. We briefly discuss the role of temperature inhomogeneity and consider whether...
International Nuclear Information System (INIS)
Frink, L.J.D.; Salinger, A.G.
2000-01-01
Fluids adsorbed near surfaces, near macromolecules, and in porous materials are inhomogeneous, exhibiting spatially varying density distributions. This inhomogeneity in the fluid plays an important role in controlling a wide variety of complex physical phenomena including wetting, self-assembly, corrosion, and molecular recognition. One of the key methods for studying the properties of inhomogeneous fluids in simple geometries has been density functional theory (DFT). However, there has been a conspicuous lack of calculations in complex two- and three-dimensional geometries. The computational difficulty arises from the need to perform nested integrals that are due to nonlocal terms in the free energy functional. These integral equations are expensive both in evaluation time and in memory requirements; however, the expense can be mitigated by intelligent algorithms and the use of parallel computers. This paper details the efforts to develop efficient numerical algorithms so that nonlocal DFT calculations in complex geometries that require two or three dimensions can be performed. The success of this implementation will enable the study of solvation effects at heterogeneous surfaces, in zeolites, in solvated (bio)polymers, and in colloidal suspensions
Bridge density functional approximation for non-uniform hard core repulsive Yukawa fluid
International Nuclear Information System (INIS)
Zhou Shiqi
2008-01-01
In this work, a bridge density functional approximation (BDFA) (J. Chem. Phys. 112, 8079 (2000)) for a non-uniform hard-sphere fluid is extended to a non-uniform hard-core repulsive Yukawa (HCRY) fluid. It is found that the choice of a bulk bridge functional approximation is crucial for both a uniform HCRY fluid and a non-uniform HCRY fluid. A new bridge functional approximation is proposed, which can accurately predict the radial distribution function of the bulk HCRY fluid. With the new bridge functional approximation and its associated bulk second order direct correlation function as input, the BDFA can be used to well calculate the density profile of the HCRY fluid subjected to the influence of varying external fields, and the theoretical predictions are in good agreement with the corresponding simulation data. The calculated results indicate that the present BDFA captures quantitatively the phenomena such as the coexistence of solid-like high density phase and low density gas phase, and the adsorption properties of the HCRY fluid, which qualitatively differ from those of the fluids combining both hard-core repulsion and an attractive tail. (condensed matter: structure, thermal and mechanical properties)
A glimpse of fluid turbulence from the molecular scale
Komatsu, Teruhisa S.
2014-08-01
Large-scale molecular dynamics (MD) simulations of freely decaying turbulence in three-dimensional space are reported. Fluid components are defined from the microscopic states by eliminating thermal components from the coarse-grained fields. The energy spectrum of the fluid components is observed to scale reasonably well according to Kolmogorov scaling determined from the energy dissipation rate and the viscosity of the fluid, even though the Kolmogorov length is of the order of the molecular scale. © 2014 The Authors.
Optimized theory for simple and molecular fluids.
Marucho, M; Montgomery Pettitt, B
2007-03-28
An optimized closure approximation for both simple and molecular fluids is presented. A smooth interpolation between Perkus-Yevick and hypernetted chain closures is optimized by minimizing the free energy self-consistently with respect to the interpolation parameter(s). The molecular version is derived from a refinement of the method for simple fluids. In doing so, a method is proposed which appropriately couples an optimized closure with the variant of the diagrammatically proper integral equation recently introduced by this laboratory [K. M. Dyer et al., J. Chem. Phys. 123, 204512 (2005)]. The simplicity of the expressions involved in this proposed theory has allowed the authors to obtain an analytic expression for the approximate excess chemical potential. This is shown to be an efficient tool to estimate, from first principles, the numerical value of the interpolation parameters defining the aforementioned closure. As a preliminary test, representative models for simple fluids and homonuclear diatomic Lennard-Jones fluids were analyzed, obtaining site-site correlation functions in excellent agreement with simulation data.
Chen, Carl P C; Hsu, Chih Chin; Pei, Yu-Cheng; Chen, Ruo Li; Zhou, Shaobo; Shen, Hsuan-Chen; Lin, Shih-Cherng; Tsai, Wen Chung
2014-04-01
Knee pain is commonly seen in orthopedic and rehabilitation outpatient clinical settings, and in the aging population. Bursitis of the knee joint, especially when the volume of the synovial fluid is large enough, can compress and distend the nearby soft tissues, causing pain in the knee joint. Out of all the bursae surrounding the knee joint, supra-patellar bursitis is most often associated with knee pain. Treatment strategies in managing supra-patellar bursitis include the aspiration of joint synovial fluid and then followed by steroid injection into the bursa. When supra-patellar bursitis is caused by degenerative disorders, the concept of viscosupplementation treatment may be effective by injecting hyaluronic acid into the bursa. However, the rheology or the changes in the concentrations of proteins (biomarkers) that are related to the development of bursitis in the synovial fluid is virtually unexplored. Therefore, this study aimed to identify the concentration changes in the synovial fluid total protein amount and individual proteins associated with supra-patellar bursitis using the Bradford protein assay and western immunoglobulin methods. A total of 20 patients were divided into two groups with 10 patients in each group. One group received the high molecular weight hyaluronic acid product of Synvisc Hylan G-F 20 and the other group received the low molecular weight hyaluronic acid product of Hya-Joint Synovial Fluid Supplement once per week injection into the bursa for a total of 3 weeks. Significant decreases in the synovial fluid total protein concentrations were observed after the second dosage of high molecular weight hyaluronic acid injections. Apolipoprotein A-I, interleukin 1 beta, alpha 1 antitrypsin, and matrix metalloproteinase 1 proteins revealed a trend of decreasing western immunoblotting band densities after hyaluronic acid injections. The decreases in apolipoprotein A-I and interleukin 1 beta protein band densities were significant in the high
Husowitz, B; Talanquer, V
2007-02-07
Density functional theory is used to explore the solvation properties of a spherical solute immersed in a supercritical diatomic fluid. The solute is modeled as a hard core Yukawa particle surrounded by a diatomic Lennard-Jones fluid represented by two fused tangent spheres using an interaction site approximation. The authors' approach is particularly suitable for thoroughly exploring the effect of different interaction parameters, such as solute-solvent interaction strength and range, solvent-solvent long-range interactions, and particle size, on the local solvent structure and the solvation free energy under supercritical conditions. Their results indicate that the behavior of the local coordination number in homonuclear diatomic fluids follows trends similar to those reported in previous studies for monatomic fluids. The local density augmentation is particularly sensitive to changes in solute size and is affected to a lesser degree by variations in the solute-solvent interaction strength and range. The associated solvation free energies exhibit a nonmonotonous behavior as a function of density for systems with weak solute-solvent interactions. The authors' results suggest that solute-solvent interaction anisotropies have a major influence on the nature and extent of local solvent density inhomogeneities and on the value of the solvation free energies in supercritical solutions of heteronuclear molecules.
Chronic subdural hematoma fluid and its computerized tomographic density
International Nuclear Information System (INIS)
Masuzawa, Hideaki; Sato, Jinichi; Kamitani, Hiroshi; Yamashita, Midori
1983-01-01
Laboratory and in vivo CT analysis were performed on 19 chronic subdural hematomas and five subdural hygromas. In these 25 hematoma samples, red blood cells (RBC), hematocrit, and hemoglobin (Hgb) varied greatly, though, these values correlated well with the CT densities. Plasma protein content was fairly constant with an average of 7.1+-0.8g/dl. There were four hematoma samples with RBC of less than 20x10 4 μl or Hgb of less than 2.0g/dl. Their CT values ranged between 18 and 23 H.U., which were considered close to the in vivo serum level CT density. Five hygroma fluid showed no RBC and very little protein content of less than 0.4g/dl. CT density ranged between -2 and 13 H.U. The edge effect of the skull was experimentally studied using a phantom skull filled with water. This revealed a remarkable overshoot of the CT values within ten pixels from the inner wall of the skull. Visual observation of the original CT pictures revealed four low density hematomas and seven mixed density ones. When compared to the density of the ventricular cavity, all of the low density hematomas and the supernatant part of the mixed density ones were clearly higher in density. All five hygromas appeared CSF dense or lower. In conclusion, because of the edge effect by the skull, thin subdural fluids could not be diagnosed by CT alone. Thick subdural fluids could be differentiated as either hematoma or hygroma by their CT densities. Subdural hematomas had in vivo CT densities of at least serum level or approximately 20 H.U., while subdural hygromas had densities close to CSF. These characteristics were best appreciated by visual observation of the CT scan films. (J.P.N.)
Density functional study of the pressure tensor for inhomogeneous Lennard—Jones fluids
International Nuclear Information System (INIS)
Sun Zong-Li; Liu Zhi-Cheng; Kang Yan-Shuang; Ma Heng-Xin; Kang Yan-Mei
2012-01-01
Based on classical density functional theory, an expression of the pressure tensor for inhomogeneous fluids is presented. This takes into account greater correlation between particles, especially for systems that are geometrically confined or involve an interface. The density and pressure components of Lennard-Jones fluids confined in hard and softened nano-cavities are calculated. A comparison between the results of this work and IK expression suggests that the agreement depends on temperature. The interfacial tension for hard sphere fluids agrees well with the Monte Carlo result when the bulk density is not too large. The results of the solid-fluid interfacial tension for Lennard—Jones fluids demonstrate that different types of external potentials modulate the interfacial tension in different manners. (condensed matter: structural, mechanical, and thermal properties)
Molecular Entropy, Thermal Efficiency, and Designing of Working Fluids for Organic Rankine Cycles
Wang, Jingtao; Zhang, Jin; Chen, Zhiyou
2012-06-01
A shortage of fossil energy sources boosts the utilization of renewable energy. Among numerous novel techniques, recovering energy from low-grade heat sources through power generation via organic Rankine cycles (ORCs) is one of the focuses. Properties of working fluids are crucial for the ORC's performance. Many studies have been done to select proper working fluids or to design new working fluids. However, no researcher has systematically investigated the relationship between molecular structures and thermal efficiencies of various working fluids for an ideal ORC. This paper has investigated the interrelations of molecular structures, molecular entropies, and thermal efficiencies of various working fluids for an ideal ORC. By calculating thermal efficiencies and molecular entropies, we find that the molecular entropy is the most appropriate thermophysical property of a working fluid to determine how much energy can be converted into work and how much cannot in a system. Generally speaking, working fluids with low entropies will generally have high thermal efficiency for an ideal ORC. Based on this understanding, the direct interrelations of molecular structures and entropies provide an explicit interrelation between molecular structures and thermal efficiencies, and thus provide an insightful direction for molecular design of novel working fluids for ORCs.
International Nuclear Information System (INIS)
Cowie, L.L.
1981-01-01
In this, the second paper of a series on the galactodynamics of the cloudy interstellar medium, we consider the response of such a gas to a forcing potential in the tight-winding density wave theory. The cloud fluid is treated in the hydrodynamic limit with an equation of state which softens at high densities. It is shown that in the inner regions of the galaxy, cooling of the cloud fluid in the arms can result in gravitational instability and the formation of large bound complexes of clouds which we identify with the giant molecular clouds (GMCs). Masses dimensions, distributions, and scale heights of the GMCs are predicted by the theory. It is suggested that the interstellar gas density in the disk is regulated by the gravitational instability mechanism in the arms which siphons material into star formation. Implications for the evolution of individual GMCs and for galactic morphology are discussed
Role of Echogenic Amniotic Fluid Particles and Optical Density in ...
African Journals Online (AJOL)
This study was aimed to correlate echogenic amniotic fluid particle size (AFPS) in late third trimester to fetal lung maturity and amniotic fluid optical density (AFOD) at labor. AFPS were measured with specified criteria by real time transabdominal USG (3.5MHz) while Amniotic Fluid Index (AFI) was measured during routine ...
International Nuclear Information System (INIS)
Kim, Soon-Chul; Lee, Song Hi
2004-01-01
A density functional perturbation approximation (DFPT), which is based both on the fundamental-measure theory (FMT) to the hard-sphere repulsion and on the weighted-density approximations (WDAs) to the attractive contribution, has been proposed for studying the structural properties of model fluids with an attractive part of the potential. The advantage of the present theory is the simplicity of the calculation of the weight function due to the attractive contribution. It has been applied to predict the equilibrium particle density distributions and adsorption isotherms of Lennard-Jones fluids at interfaces. The theoretical results show that the present theory describes quite well the adsorption isotherms of a Lennard-Jones ethane in a graphite slit pore as well as the equilibrium particle density distributions of a Lennard-Jones fluid near a planar slit pore
Energy Technology Data Exchange (ETDEWEB)
Bowers, Geoffrey [Alfred Univ., NY (United States)
2017-04-05
United States Department of Energy grant DE-FG02-10ER16128, “Computational and Spectroscopic Investigations of the Molecular Scale Structure and Dynamics of Geologically Important Fluids and Mineral-Fluid Interfaces” (Geoffrey M. Bowers, P.I.) focused on developing a molecular-scale understanding of processes that occur in fluids and at solid-fluid interfaces using the combination of spectroscopic, microscopic, and diffraction studies with molecular dynamics computer modeling. The work is intimately tied to the twin proposal at Michigan State University (DOE DE-FG02-08ER15929; same title: R. James Kirkpatrick, P.I. and A. Ozgur Yazaydin, co-P.I.).
International Nuclear Information System (INIS)
Sun Zong-Li; Kang Yan-Shuang
2011-01-01
Classical density functional theory is used to study the associating Lennard—Jones fluids in contact with spherical hard wall of different curvature radii. The interfacial properties including contact density and fluid-solid interfacial tension are investigated. The influences of associating energy, curvature of hard wall and the bulk density of fluids on these properties are analyzed in detail. The results may provide helpful clues to understand the interfacial properties of other complex fluids. (condensed matter: structure, mechanical and thermal properties)
Correlated density matrix theory of spatially inhomogeneous Bose fluids
International Nuclear Information System (INIS)
Gernoth, K.A.; Clark, J.W.; Ristig, M.L.
1994-06-01
In this paper, the variational Hartree-Jastrow theory of the ground state of spatially inhomogeneous Bose systems is extended to finite temperatures. The theory presented here is a generalization also in the sense that it extends the correlated density matrix approach, formulated previously for uniform Bose fluids, to systems with nonuniform density profiles. The method provides a framework in which the effects of thermal excitations on the spatial structure of a Bose fluid, as represented by the density profile and the two-body distribution functions, may be discussed on the basis on an ab initio microscopic description of the system. Thermal excitations make their appearance through self-consistently determined one-body and two-body potentials which enter the nonlinear, coupled Euler-Lagrange equations for the one-body density and for the pair distribution function. Since back-flow correlations are neglected, the excitations are described by a Feynman eigenvalue equation, suitably generalized to nonzero temperatures. The only external quantities entering the correlated density matrix theory elaborated here are the bare two-body interaction potential and, in actual applications, the boundary conditions to be imposed on the one-body density. 30 refs
Particle-bearing currents in uniform density and two-layer fluids
Sutherland, Bruce R.; Gingras, Murray K.; Knudson, Calla; Steverango, Luke; Surma, Christopher
2018-02-01
Lock-release gravity current experiments are performed to examine the evolution of a particle bearing flow that propagates either in a uniform-density fluid or in a two-layer fluid. In all cases, the current is composed of fresh water plus micrometer-scale particles, the ambient fluid is saline, and the current advances initially either over the surface as a hypopycnal current or at the interface of the two-layer fluid as a mesopycnal current. In most cases the tank is tilted so that the ambient fluid becomes deeper with distance from the lock. For hypopycnal currents advancing in a uniform density fluid, the current typically slows as particles rain out of the current. While the loss of particles alone from the current should increase the current's buoyancy and speed, in practice the current's speed decreases because the particles carry with them interstitial fluid from the current. Meanwhile, rather than settling on the sloping bottom of the tank, the particles form a hyperpycnal (turbidity) current that advances until enough particles rain out that the relatively less dense interstitial fluid returns to the surface, carrying some particles back upward. When a hypopycnal current runs over the surface of a two-layer fluid, the particles that rain out temporarily halt their descent as they reach the interface, eventually passing through it and again forming a hyperpycnal current. Dramatically, a mesopycnal current in a two-layer fluid first advances along the interface and then reverses direction as particles rain out below and fresh interstitial fluid rises above.
Internal wave patterns in enclosed density-stratified and rotating fluids
Manders, A.M.A.
2003-01-01
Stratified fluids support internal waves, which propagate obliquely through the fluid. The angle with respectto the stratification direction is contrained: it is purely determined by the wave frequency and the strength of the density stratification (internal gravity waves) or the rotation rate
Application of the RISM theory to Lennard-Jones interaction site molecular fluids
International Nuclear Information System (INIS)
Johnson, E.; Hazoume, R.P.
1979-01-01
It seems that reference interaction site model (RISM) theory atom--atom distribution functions have been obtained directly from the RISM equations only for fused hard sphere molecular fluids. RISM distribution functions for Lennard-Jones interaction site fluids are presented. Results presented suggest that these distribution functions are as accurate as RISM distribution functions for fused hard sphere molecular fluids
A glimpse of fluid turbulence from the molecular scale
Komatsu, Teruhisa S.; Matsumoto, Shigenori; Shimada, Takashi; Ito, Nobuyasu
2014-01-01
. The energy spectrum of the fluid components is observed to scale reasonably well according to Kolmogorov scaling determined from the energy dissipation rate and the viscosity of the fluid, even though the Kolmogorov length is of the order of the molecular
Crystallisation of a Lennard-Jones fluid by large scale molecular dynamics simulation
International Nuclear Information System (INIS)
Snook, I.
1998-01-01
Full text: The evolution of the structure of a large system of atoms interacting via a Lennard-Jones pair potential was simulated by the use of the Molecular Dynamics computer simulation technique. The system was initially equilibrated in the one phase region of the phase diagram at a temperature above critical then a temperature quench was performed which placed the system in a region were the single fluid phase was unstable. Quenches to below the triple point temperature gave rise to crystallisation The mechanism and final morphology is shown to depend strongly on the starting conditions e.g. the starting density
Density functional theory of polydisperse fluid interfaces
International Nuclear Information System (INIS)
Baus, M.; Bellier-Castella, L.; Xu, H.
2002-01-01
Most colloids usually exhibit one or several polydispersities. A natural framework for the theoretical description of polydisperse systems is provided by the extension of density functional theory to 'continuous' mixtures. This will be illustrated here by the study of both the bulk and interfacial properties of a simple van der Waals model for a polydisperse colloidal fluid. (author)
Analytic solution of integral equations for molecular fluids
International Nuclear Information System (INIS)
Cummings, P.T.
1984-01-01
We review some recent progress in the analytic solution of integral equations for molecular fluids. The site-site Ornstein-Zernike (SSOZ) equation with approximate closures appropriate to homonuclear diatomic fluids both with and without attractive dispersion-like interactions has recently been solved in closed form analytically. In this paper, the close relationship between the SSOZ equation for homonuclear dumbells and the usual Ornstein-Zernike (OZ) equation for atomic fluids is carefully elucidated. This relationship is a key motivation for the analytic solutions of the SSOZ equation that have been obtained to date. (author)
Local elastic properties of nano-confined fluids: A density functional study
Energy Technology Data Exchange (ETDEWEB)
Sun, Zongli, E-mail: zongli_sun@163.com [Science and Technology College, North China Electric Power University, Baoding 071051 (China); Kang, Yanshuang [College of Science, Agriculture University of Hebei, Baoding 071001 (China)
2014-05-01
The understanding of mechanical properties of confined fluids is essential for modeling and manipulating of nano-scaled systems. Unlike the uniform phase, the confined fluids usually display different features in structure and related properties. Due to the presence of the confining geometry, the density profile and many physical and chemical properties may be position-dependent. The aim of our research is to derive an expression for the local elastic property by using the classical elastic theory. Both the bulk and shear moduli are expressed as functional of density of particle. The theoretical result derived is applied to the Lennard-Jones fluids confined in nano-cavity. Comparison of our numerical result and the simulation result is made and qualitative agreement is observed. Further, influence of bulk density, temperature and external potential on moduli is calculated and the physical mechanism is analyzed. Relationship between contact modulus and the interfacial tension is also calculated. Their opposite trend with temperature is observed.
Local elastic properties of nano-confined fluids: A density functional study
International Nuclear Information System (INIS)
Sun, Zongli; Kang, Yanshuang
2014-01-01
The understanding of mechanical properties of confined fluids is essential for modeling and manipulating of nano-scaled systems. Unlike the uniform phase, the confined fluids usually display different features in structure and related properties. Due to the presence of the confining geometry, the density profile and many physical and chemical properties may be position-dependent. The aim of our research is to derive an expression for the local elastic property by using the classical elastic theory. Both the bulk and shear moduli are expressed as functional of density of particle. The theoretical result derived is applied to the Lennard-Jones fluids confined in nano-cavity. Comparison of our numerical result and the simulation result is made and qualitative agreement is observed. Further, influence of bulk density, temperature and external potential on moduli is calculated and the physical mechanism is analyzed. Relationship between contact modulus and the interfacial tension is also calculated. Their opposite trend with temperature is observed.
Insulator-metal transition of fluid molecular hydrogen
International Nuclear Information System (INIS)
Ross, M.
1996-01-01
Dynamically compressed fluid hydrogen shows evidence for metallization at the relatively low pressure of 140 GPa (1.4 Mbar) while experiments on solid hydrogen made in a diamond-anvil cell have failed to detect any evidence for gap closure up to a pressure of 230 GPa (2.3 Mbar). Two possible mechanisms for metal- liclike resistivity are put forward. The first is that as a consequence of the large thermal disorder in the fluid (kT∼0.2 endash 0.3 eV) short-range molecular interactions lead to band tailing that extends the band edge into the gap, resulting in closure at a lower pressure than in the solid. The second mechanism argues that molecular dissociation creates H atoms that behave similar to n-type donors in a heavily doped semiconductor and undergo a nonmetal-metal Mott-type transition. copyright 1996 The American Physical Society
International Nuclear Information System (INIS)
Adebayo, G.A.; Anusionwu, B.C.; Njah, A.N.; Adeniran, O.J.; Mathew, B.; Sunmonu, R.S.
2009-01-01
Arising from the inability of theoretical calculations to give accurate descriptions of (shear) viscosity in rare gases at high densities, we investigated the likely cause of discrepancy between theory and experiments. Molecular Dynamics simulations were performed to calculate transport coefficients and collision frequency of rare gases at high densities and different temperatures using a Lennard-Jones modelled pair potential. The results, when compared with experiments show an underestimation of the viscosity calculated through the Green-Kubo formalism, but in agreement with some other calculations performed by other groups. In the present work the origin of the underestimation is considered. Analyses of the transport coefficients show a very high collision frequency which suggests an atom may spend much less time in the neighbourhood of the fields of force of another atom and that the distribution in the systems studied adjusts itself to a nearly Maxwellian type which resulted in a locally and temporarily slowly varying temperature. We show that the time spent in the fields of force is so small compared with relaxation time thereby leading to a possible reduction in local velocity auto-correlation between atoms. (author)
Krekelberg, William P; Siderius, Daniel W; Shen, Vincent K; Truskett, Thomas M; Errington, Jeffrey R
2017-08-03
Using molecular simulations, we investigate how the range of fluid-fluid (adsorbate-adsorbate) interactions and the strength of fluid-solid (adsorbate-adsorbent) interactions impact the strong connection between distinct adsorptive regimes and distinct self-diffusivity regimes reported in [Krekelberg, W. P.; Siderius, D. W.; Shen, V. K.; Truskett, T. M.; Errington, J. R. Langmuir 2013 , 29 , 14527-14535]. Although increasing the fluid-fluid interaction range changes both the thermodynamics and the dynamic properties of adsorbed fluids, the previously reported connection between adsorptive filling regimes and self-diffusivity regimes remains. Increasing the fluid-fluid interaction range leads to enhanced layering and decreased self-diffusivity in the multilayer-formation regime but has little effect on the properties within film-formation and pore-filling regimes. We also find that weakly attractive adsorbents, which do not display distinct multilayer formation, are hard-sphere-like at super- and subcritical temperatures. In this case, the self-diffusivity of the confined and bulk fluid has a nearly identical scaling-relationship with effective density.
International Nuclear Information System (INIS)
Neimark, Alexander V; Ravikovitch, Peter I; Vishnyakov, Aleksey
2003-01-01
With the example of the capillary condensation of Lennard-Jones fluid in nanopores ranging from 1 to 10 nm, we show that the non-local density functional theory (NLDFT) with properly chosen parameters of intermolecular interactions bridges the scale gap from molecular simulations to macroscopic thermodynamics. On the one hand, NLDFT correctly approximates the results of Monte Carlo simulations (shift of vapour-liquid equilibrium, spinodals, density profiles, adsorption isotherms) for pores wider than about 2 nm. On the other hand, NLDFT smoothly merges (above 7-10 nm) with the Derjaguin-Broekhoff-de Boer equations which represent augmented Laplace-Kelvin equations of capillary condensation and desorption
High Density Thermal Energy Storage with Supercritical Fluids
Ganapathi, Gani B.; Wirz, Richard
2012-01-01
A novel approach to storing thermal energy with supercritical fluids is being investigated, which if successful, promises to transform the way thermal energy is captured and utilized. The use of supercritical fluids allows cost-affordable high-density storage with a combination of latent heat and sensible heat in the two-phase as well as the supercritical state. This technology will enhance penetration of several thermal power generation applications and high temperature water for commercial use if the overall cost of the technology can be demonstrated to be lower than the current state-of-the-art molten salt using sodium nitrate and potassium nitrate eutectic mixtures.
A New Calculation Method of Dynamic Kill Fluid Density Variation during Deep Water Drilling
Directory of Open Access Journals (Sweden)
Honghai Fan
2017-01-01
Full Text Available There are plenty of uncertainties and enormous challenges in deep water drilling due to complicated shallow flow and deep strata of high temperature and pressure. This paper investigates density of dynamic kill fluid and optimum density during the kill operation process in which dynamic kill process can be divided into two stages, that is, dynamic stable stage and static stable stage. The dynamic kill fluid consists of a single liquid phase and different solid phases. In addition, liquid phase is a mixture of water and oil. Therefore, a new method in calculating the temperature and pressure field of deep water wellbore is proposed. The paper calculates the changing trend of kill fluid density under different temperature and pressure by means of superposition method, nonlinear regression, and segment processing technique. By employing the improved model of kill fluid density, deep water kill operation in a well is investigated. By comparison, the calculated density results are in line with the field data. The model proposed in this paper proves to be satisfactory in optimizing dynamic kill operations to ensure the safety in deep water.
International Nuclear Information System (INIS)
Eggert, Jon H.; Weck, Gunnar; Loubeyre, Paul; Mezouar, Mohamed
2002-01-01
We report quantitatively accurate high-pressure, structure-factor measurements of fluids in diamond anvil cells (DAC's) using x-ray diffraction. In the analysis of our diffraction data, we found it possible (and necessary) to determine the density directly. Thus, we also present a diffraction-based determination of the equation of state for fluid water. The analysis of these measurements is difficult since the diamond anvils are many times as thick as the sample and excessive care must be taken in the background subtraction. Due to the novel nature of the experiment and the complexity of the analysis, this paper is concerned primarily with a careful exposition of our analytical methods. Our analysis is applicable to both atomic and molecular fluids and glasses, and we present results for the structure factor and density of two relatively low-Z liquids: argon and water. In order to validate our methods we present an extensive comparison of our measurements on water at P≅0 in a DAC to recent state-of-the-art x-ray and neutron diffraction experiments and to first-principles simulations at ambient conditions
Kalani, Mahshid; Yunus, Robiah
2012-01-01
The reported work demonstrates and discusses the effect of supercritical fluid density (pressure and temperature of supercritical fluid carbon dioxide) on particle size and distribution using the supercritical antisolvent (SAS) method in the purpose of drug encapsulation. In this study, paracetamol was encapsulated inside L-polylactic acid, a semicrystalline polymer, with different process parameters, including pressure and temperature, using the SAS process. The morphology and particle size of the prepared nanoparticles were determined by scanning electron microscopy and transmission electron microscopy. The results revealed that increasing temperature enhanced mean particle size due to the plasticizing effect. Furthermore, increasing pressure enhanced molecular interaction and solubility; thus, particle size was reduced. Transmission electron microscopy images defined the internal structure of nanoparticles. Thermal characteristics of nanoparticles were also investigated via differential scanning calorimetry. Furthermore, X-ray diffraction pattern revealed the changes in crystallinity structure during the SAS process. In vitro drug release analysis determined the sustained release of paracetamol in over 4 weeks.
International Nuclear Information System (INIS)
Hamel, W.R.
1984-01-01
This invention relates to a new method and new apparatus for determining fluid mass flow rate and density. In one aspect of the invention, the fluid is passed through a straight cantilevered tube in which transient oscillation has been induced, thus generating Coriolis damping forces on the tube. The decay rate and frequency of the resulting damped oscillation are measured, and the fluid mass flow rate and density are determined therefrom. In another aspect of the invention, the fluid is passed through the cantilevered tube while an electrically powered device imparts steady-state harmonic excitation to the tube. This generates Coriolis tube-damping forces which are dependent on the mass flow rate of the fluid. Means are provided to respond to incipient flow-induced changes in the amplitude of vibration by changing the power input to the excitation device as required to sustain the original amplitude of vibration. The fluid mass flow rate and density are determined from the required change in power input. The invention provides stable, rapid, and accurate measurements. It does not require bending of the fluid flow
Lee, B H; Lee, C H; Seong Baek Seok
2000-01-01
A density functional perturbative approximation, which is based on the density functional expansion of the one-particle direct correlation function of model fluids with respect to the bulk density, has been employed to investigate the influence of the potential well and the potential barrier on the density behavior of confined-model fluids. The mean spherical approximation has been used to calculate the two-particle direct correlation function of the model fluids. At lower densities, the density distributions are strongly affected by the barrier height and the well depth of the model potential, the contribution from the short-range repulsive part being especially important. However, the effects of the barrier height and the well depth of the model potential decrease with increasing bulk density. The calculated results also show that in the region where the effect of the wall-fluid interaction is relatively weak, the square-barrier part of the model potential leads to a nonuniformity in the density distributio...
Experimental study on the fluid stratification mechanism in the density lock
International Nuclear Information System (INIS)
Gu Haifeng; Yan Changqi; Sun Licheng
2009-01-01
Visualized experiments were conducted on the forming process of stratification between hot and cold fluids in three tubes with different diameters. The results show that the working fluids were divided into three layers from top to bottom: convective, interfacial, and constant temperature layers. The working fluid in the convective layer always retains the property of a high rate of temperature increase. The rate of temperature increase in the interfacial layer gradually decreased from top to bottom and was less than that in the convective layer. The working fluid temperature in the constant-temperature layer remained stable. Based on the experimental study, we built a simplified theoretical model and analyzed the stratification mechanism. The results indicate the following stratification mechanism: because of the existence of the transition points in the heat transfer modes, the differences in the rates of temperature increase appear. These differences result in the appearance of fluid stratification. In addition, research on the process of stratification under different conditions tells us that the structure of the density lock influences the position of the transition point. The density lock with a structure of variable cross-sectional grids can effectively control the position of the transition points of the heat transfer modes. (author)
Displacement of one Newtonian fluid by another: density effects in axial annular flow
DEFF Research Database (Denmark)
Szabo, Peter; Hassager, Ole
1997-01-01
The arbitrary Lagrange-Euler (ALE) finite elementtechnique is used to simulate 3D displacement oftwo immiscible Newtonian fluids in vertical annular wells. For equally viscous fluids the effect of distinct fluid densities is investigated in the region of low to intermediate Reynolds numbers......, the efficiency of the displacement is analysed for various flow situations....
Time-dependent quantum fluid density functional theory of hydrogen ...
Indian Academy of Sciences (India)
A time-dependent generalized non-linear Schrödinger equation (GNLSE) of motion was earlier derived in our laboratory by combining density functional theory and quantum fluid dynamics in threedimensional space. In continuation of the work reported previously, the GNLSE is applied to provide additional knowledge on ...
Local linear viscoelasticity of confined fluids.
Hansen, J S; Daivis, P J; Todd, B D
2007-04-14
In this paper the authors propose a novel method to study the local linear viscoelasticity of fluids confined between two walls. The method is based on the linear constitutive equation and provides details about the real and imaginary parts of the local complex viscosity. They apply the method to a simple atomic fluid undergoing zero mean oscillatory flow using nonequilibrium molecular dynamics simulations. The method shows that the viscoelastic properties of the fluid exhibit dramatic spatial changes near the wall-fluid boundary due to the high density in this region. It is also shown that the real part of the viscosity converges to the frequency dependent local shear viscosity sufficiently far away from the wall. This also provides valuable information about the transport properties in the fluid, in general. The viscosity is compared with predictions from the local average density model. The two methods disagree in that the local average density model predicts larger viscosity variations near the wall-fluid boundary than what is observed through the method presented here.
International Nuclear Information System (INIS)
Bakosi, Jozsef; Ristorcelli, Raymond J.
2010-01-01
Probability density function (PDF) methods are extended to variable-density pressure-gradient-driven turbulence. We apply the new method to compute the joint PDF of density and velocity in a non-premixed binary mixture of different-density molecularly mixing fluids under gravity. The full time-evolution of the joint PDF is captured in the highly non-equilibrium flow: starting from a quiescent state, transitioning to fully developed turbulence and finally dissipated by molecular diffusion. High-Atwood-number effects (as distinguished from the Boussinesq case) are accounted for: both hydrodynamic turbulence and material mixing are treated at arbitrary density ratios, with the specific volume, mass flux and all their correlations in closed form. An extension of the generalized Langevin model, originally developed for the Lagrangian fluid particle velocity in constant-density shear-driven turbulence, is constructed for variable-density pressure-gradient-driven flows. The persistent small-scale anisotropy, a fundamentally 'non-Kolmogorovian' feature of flows under external acceleration forces, is captured by a tensorial diffusion term based on the external body force. The material mixing model for the fluid density, an active scalar, is developed based on the beta distribution. The beta-PDF is shown to be capable of capturing the mixing asymmetry and that it can accurately represent the density through transition, in fully developed turbulence and in the decay process. The joint model for hydrodynamics and active material mixing yields a time-accurate evolution of the turbulent kinetic energy and Reynolds stress anisotropy without resorting to gradient diffusion hypotheses, and represents the mixing state by the density PDF itself, eliminating the need for dubious mixing measures. Direct numerical simulations of the homogeneous Rayleigh-Taylor instability are used for model validation.
Molecular surface mesh generation by filtering electron density map.
Giard, Joachim; Macq, Benoît
2010-01-01
Bioinformatics applied to macromolecules are now widely spread and in continuous expansion. In this context, representing external molecular surface such as the Van der Waals Surface or the Solvent Excluded Surface can be useful for several applications. We propose a fast and parameterizable algorithm giving good visual quality meshes representing molecular surfaces. It is obtained by isosurfacing a filtered electron density map. The density map is the result of the maximum of Gaussian functions placed around atom centers. This map is filtered by an ideal low-pass filter applied on the Fourier Transform of the density map. Applying the marching cubes algorithm on the inverse transform provides a mesh representation of the molecular surface.
Molecular Surface Mesh Generation by Filtering Electron Density Map
Directory of Open Access Journals (Sweden)
Joachim Giard
2010-01-01
Full Text Available Bioinformatics applied to macromolecules are now widely spread and in continuous expansion. In this context, representing external molecular surface such as the Van der Waals Surface or the Solvent Excluded Surface can be useful for several applications. We propose a fast and parameterizable algorithm giving good visual quality meshes representing molecular surfaces. It is obtained by isosurfacing a filtered electron density map. The density map is the result of the maximum of Gaussian functions placed around atom centers. This map is filtered by an ideal low-pass filter applied on the Fourier Transform of the density map. Applying the marching cubes algorithm on the inverse transform provides a mesh representation of the molecular surface.
Hansen, J S; Daivis, Peter J; Dyre, Jeppe C; Todd, B D; Bruus, Henrik
2013-01-21
The extended Navier-Stokes theory accounts for the coupling between the translational and rotational molecular degrees of freedom. In this paper, we generalize this theory to non-zero frequencies and wavevectors, which enables a new study of spatio-temporal correlation phenomena present in molecular fluids. To discuss these phenomena in detail, molecular dynamics simulations of molecular chlorine are performed for three different state points. In general, the theory captures the behavior for small wavevector and frequencies as expected. For example, in the hydrodynamic regime and for molecular fluids with small moment of inertia like chlorine, the theory predicts that the longitudinal and transverse intrinsic angular velocity correlation functions are almost identical, which is also seen in the molecular dynamics simulations. However, the theory fails at large wavevector and frequencies. To account for the correlations at these scales, we derive a phenomenological expression for the frequency dependent rotational viscosity and wavevector and frequency dependent longitudinal spin viscosity. From this we observe a significant coupling enhancement between the molecular angular velocity and translational velocity for large frequencies in the gas phase; this is not observed for the supercritical fluid and liquid state points.
Measurement of average density and relative volumes in a dispersed two-phase fluid
Sreepada, Sastry R.; Rippel, Robert R.
1992-01-01
An apparatus and a method are disclosed for measuring the average density and relative volumes in an essentially transparent, dispersed two-phase fluid. A laser beam with a diameter no greater than 1% of the diameter of the bubbles, droplets, or particles of the dispersed phase is directed onto a diffraction grating. A single-order component of the diffracted beam is directed through the two-phase fluid and its refraction is measured. Preferably, the refracted beam exiting the fluid is incident upon a optical filter with linearly varing optical density and the intensity of the filtered beam is measured. The invention can be combined with other laser-based measurement systems, e.g., laser doppler anemometry.
Study of the hard-disk system at high densities: the fluid-hexatic phase transition.
Mier-Y-Terán, Luis; Machorro-Martínez, Brian Ignacio; Chapela, Gustavo A; Del Río, Fernando
2018-06-21
Integral equations of uniform fluids have been considered unable to predict any characteristic feature of the fluid-solid phase transition, including the shoulder that arises in the second peak of the fluid-phase radial distribution function, RDF, of hard-core systems obtained by computer simulations, at fluid densities very close to the structural two-step phase transition. This reasoning is based on the results of traditional integral approximations, like Percus-Yevick, PY, which does not show such a shoulder in hard-core systems, neither in two nor three dimensions. In this work, we present results of three Ansätze, based on the PY theory, that were proposed to remedy the lack of PY analytical solutions in two dimensions. This comparative study shows that one of those Ansätze does develop a shoulder in the second peak of the RDF at densities very close to the phase transition, qualitatively describing this feature. Since the shoulder grows into a peak at still higher densities, this integral equation approach predicts the appearance of an orientational order characteristic of the hexatic phase in a continuous fluid-hexatic phase transition.
Simulating the phosphorus fluid-liquid phase transition up to the critical point
International Nuclear Information System (INIS)
Ghiringhelli, Luca M; Meijer, Evert Jan
2007-01-01
We report a Car-Parrinello molecular dynamics study of the temperature dependence of the fluid-liquid phase transition in phosphorous, involving the transformation of a molecular fluid phase into a network-like phase. We employed density-functional theory (DFT) with a gradient-corrected functional (B-LYP) to describe the electronic structure and interatomic interactions and performed simulations in a constant pressure ensemble. We spanned a temperature interval ranging from 2500 to 3500 K. With increasing temperature, we found that the structural conversion from the molecular P 4 fluid into the network liquid occurs at decreasing pressures, consistent with experimental observations. At lower temperatures the transition is characterized by a sudden increase of density in the sample. The magnitude of the density change decreases with increasing temperature and vanishes at 3500 K. In the temperature range 3100-3500 K we found signals of near- and super-criticality. We identified local structural changes that serve as seeds triggering the overall structural transition
Directory of Open Access Journals (Sweden)
Libo Zhao
2016-06-01
Full Text Available Methods to calculate fluid density and viscosity using a micro-cantilever and based on the resonance principle were put forward. Their measuring mechanisms were analyzed and the theoretical equations to calculate the density and viscosity were deduced. The fluid-solid coupling simulations were completed for the micro-cantilevers with different shapes. The sensing chips with micro-cantilevers were designed based on the simulation results and fabricated using the micro electromechanical systems (MEMS technology. Finally, the MEMS resonant sensor was packaged with the sensing chip to measure the densities and viscosities of eight different fluids under the flexural and torsional vibrating modes separately. The relative errors of the measured densities from 600 kg/m3 to 900 kg/m3 and viscosities from 200 μPa·s to 1000 μPa·s were calculated and analyzed with different microcantilevers under various vibrating modes. The experimental results showed that the effects of the shape and vibrating mode of micro-cantilever on the measurement accuracies of fluid density and viscosity were analyzed in detail.
Density fluctuations and the structure of a nonuniform hard sphere fluid
Katsov, Kirill; Weeks, John D.
2000-01-01
We derive an exact equation for density changes induced by a general external field that corrects the hydrostatic approximation where the local value of the field is adsorbed into a modified chemical potential. Using linear response theory to relate density changes self-consistently in different regions of space, we arrive at an integral equation for a hard sphere fluid that is exact in the limit of a slowly varying field or at low density and reduces to the accurate Percus-Yevick equation fo...
Bulk viscosity of molecular fluids
Jaeger, Frederike; Matar, Omar K.; Müller, Erich A.
2018-05-01
The bulk viscosity of molecular models of gases and liquids is determined by molecular simulations as a combination of a dilute gas contribution, arising due to the relaxation of internal degrees of freedom, and a configurational contribution, due to the presence of intermolecular interactions. The dilute gas contribution is evaluated using experimental data for the relaxation times of vibrational and rotational degrees of freedom. The configurational part is calculated using Green-Kubo relations for the fluctuations of the pressure tensor obtained from equilibrium microcanonical molecular dynamics simulations. As a benchmark, the Lennard-Jones fluid is studied. Both atomistic and coarse-grained force fields for water, CO2, and n-decane are considered and tested for their accuracy, and where possible, compared to experimental data. The dilute gas contribution to the bulk viscosity is seen to be significant only in the cases when intramolecular relaxation times are in the μs range, and for low vibrational wave numbers (<1000 cm-1); This explains the abnormally high values of bulk viscosity reported for CO2. In all other cases studied, the dilute gas contribution is negligible and the configurational contribution dominates the overall behavior. In particular, the configurational term is responsible for the enhancement of the bulk viscosity near the critical point.
Molecular Electron Density Theory: A Modern View of Reactivity in Organic Chemistry
Luis R. Domingo
2016-01-01
A new theory for the study of the reactivity in Organic Chemistry, named Molecular Electron Density Theory (MEDT), is proposed herein. MEDT is based on the idea that while the electron density distribution at the ground state is responsible for physical and chemical molecular properties, as proposed by the Density Functional Theory (DFT), the capability for changes in electron density is responsible for molecular reactivity. Within MEDT, the reactivity in Organic Chemistry is studied through ...
Density, distribution, and orientation of water molecules inside and outside carbon nanotubes.
Thomas, J A; McGaughey, A J H
2008-02-28
The behavior of water molecules inside and outside 1.1, 2.8, 6.9, and 10.4 nm diameter armchair carbon nanotubes (CNTs) is predicted using molecular dynamics simulations. The effects of CNT diameter on mass density, molecular distribution, and molecular orientation are identified for both the confined and unconfined fluids. Within 1 nm of the CNT surface, unconfined water molecules assume a spatially varying density profile. The molecules distribute nonuniformly around the carbon surface and have preferred orientations. The behavior of the unconfined water molecules is invariant with CNT diameter. The behavior of the confined water, however, can be correlated to tube diameter. Inside the 10.4 nm CNT, the molecular behavior is indistinguishable from that of the unconfined fluid. Within the smaller CNTs, surface curvature effects reduce the equilibrium water density and force water molecules away from the surface. This effect changes both the molecular distribution and preferred molecular orientations.
Directory of Open Access Journals (Sweden)
Deokman Kim
2017-10-01
Full Text Available The determination of fluid density and viscosity using most cantilever-based sensors is based on changes in resonant frequency and peak width. Here, we present a wave propagation analysis using piezoelectrically excited micro-cantilevers under distributed fluid loading. The standing wave shapes of microscale-thickness cantilevers partially immersed in liquids (water, 25% glycerol, and acetone, and nanoscale-thickness microfabricated cantilevers fully immersed in gases (air at three different pressures, carbon dioxide, and nitrogen were investigated to identify the effects of fluid-structure interactions to thus determine the fluid properties. This measurement method was validated by comparing with the known fluid properties, which agreed well with the measurements. The relative differences for the liquids were less than 4.8% for the densities and 3.1% for the viscosities, and those for the gases were less than 6.7% for the densities and 7.3% for the viscosities, showing better agreements in liquids than in gases.
Sergiievskyi, Volodymyr P; Jeanmairet, Guillaume; Levesque, Maximilien; Borgis, Daniel
2014-06-05
Molecular density functional theory (MDFT) offers an efficient implicit-solvent method to estimate molecule solvation free-energies, whereas conserving a fully molecular representation of the solvent. Even within a second-order approximation for the free-energy functional, the so-called homogeneous reference fluid approximation, we show that the hydration free-energies computed for a data set of 500 organic compounds are of similar quality as those obtained from molecular dynamics free-energy perturbation simulations, with a computer cost reduced by 2-3 orders of magnitude. This requires to introduce the proper partial volume correction to transform the results from the grand canonical to the isobaric-isotherm ensemble that is pertinent to experiments. We show that this correction can be extended to 3D-RISM calculations, giving a sound theoretical justification to empirical partial molar volume corrections that have been proposed recently.
Efficient molecular density functional theory using generalized spherical harmonics expansions.
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.
Mesoscopic model for binary fluids
Echeverria, C.; Tucci, K.; Alvarez-Llamoza, O.; Orozco-Guillén, E. E.; Morales, M.; Cosenza, M. G.
2017-10-01
We propose a model for studying binary fluids based on the mesoscopic molecular simulation technique known as multiparticle collision, where the space and state variables are continuous, and time is discrete. We include a repulsion rule to simulate segregation processes that does not require calculation of the interaction forces between particles, so binary fluids can be described on a mesoscopic scale. The model is conceptually simple and computationally efficient; it maintains Galilean invariance and conserves the mass and energy in the system at the micro- and macro-scale, whereas momentum is conserved globally. For a wide range of temperatures and densities, the model yields results in good agreement with the known properties of binary fluids, such as the density profile, interface width, phase separation, and phase growth. We also apply the model to the study of binary fluids in crowded environments with consistent results.
Molecular Electron Density Theory: A Modern View of Reactivity in Organic Chemistry.
Domingo, Luis R
2016-09-30
A new theory for the study of the reactivity in Organic Chemistry, named Molecular Electron Density Theory (MEDT), is proposed herein. MEDT is based on the idea that while the electron density distribution at the ground state is responsible for physical and chemical molecular properties, as proposed by the Density Functional Theory (DFT), the capability for changes in electron density is responsible for molecular reactivity. Within MEDT, the reactivity in Organic Chemistry is studied through a rigorous quantum chemical analysis of the changes of the electron density as well as the energies associated with these changes along the reaction path in order to understand experimental outcomes. Studies performed using MEDT allow establishing a modern rationalisation and to gain insight into molecular mechanisms and reactivity in Organic Chemistry.
Density Relaxation of Liquid-Vapor Critical Fluids Examined in Earth's Gravity
Wilkinson, R. Allen
2000-01-01
This work shows quantitatively the pronounced differences between the density equilibration of very compressible dense fluids in Earth's gravity and those in microgravity. The work was performed onsite at the NASA Glenn Research Center at Lewis Field and is complete. Full details are given in references 1 and 2. Liquid-vapor critical fluids (e.g., water) at their critical temperature and pressure, are very compressible. They collapse under their own weight in Earth's gravity, allowing only a thin meniscus-like layer with the critical pressure to survive. This critical layer, however, greatly slows down the equilibration process of the entire sample. A complicating feature is the buoyancy-driven slow flows of layers of heavier and lighter fluid. This work highlights the incomplete understanding of the hydrodynamics involved in these fluids.
International Nuclear Information System (INIS)
Longelin, St.
2004-04-01
Super-critical fluids are largely used in industrial sectors. However the knowledge of the physical phenomena in which they are involved stays insufficient because of their particular properties. A new model of adjusting molecular structures is proposed, this model has been validated through neutron scattering experiments with high momentum transfer on C 2 D 6 . The experimental representation of the critical universal function for C 2 D 6 and CO 2 has been obtained through the neutron echo spin and by relying on structure measurements made through neutron elastic scattering at small angles. Raman spectroscopy and molecular dynamics simulation have been used to feature structure and dynamics. Scattering as well as microscopic molecular density fluctuations have been analysed
Annihilation Radiation Gauge for Relative Density and Multiphase Fluid Monitoring
Directory of Open Access Journals (Sweden)
Vidal A.
2014-03-01
Full Text Available The knowledge of the multi-phase flow parameters are important for the petroleum industry, specifically during the transport in pipelines and network related to exploitation’s wells. Crude oil flow is studied by Monte Carlo simulation and experimentally to determine transient liquid phase in a laboratory system. Relative density and fluid phase time variation is monitored employing a fast nuclear data acquisition setup that includes two large volume BaF2 scintillator detectors coupled to an electronic chain and data display in a LabView® environment. Fluid parameters are determined by the difference in count rate of coincidence pulses. The operational characteristics of the equipment indicate that 2 % deviation in the CCR corresponds to a variation, on average, of 20 % in the fraction of liquid of the multiphase fluid.
Low density molecular cloud in the vicinity of the Pleiades
International Nuclear Information System (INIS)
Federman, S.R.; Wilson, R.F.
1984-01-01
The central region of a small, low density molecular cloud, which lies to the south of the Pleiades cluster, has been studied through the use of molecular line observations. Column densities for CH, OH, 12 CO, and 13 CO are derived from the radio data. The CH and OH data yield a visual extinction through the center of the cloud of about 3 mag. The ratio of the antenna temperatures for the OH main lines is consistent with optically thin emission; therefore, the OH results are a good indication of the total extinction through the optically thin emission; therefore, the OH results are a good indication of the total extinction through the cloud. The analysis of the carbon monoxide data produces a relatively high kinetic temperature of at least 20 K, a low total gas density of approx.300-500 cm -3 , and a column density of approx.4 x 10 17 cm -2 for 12 CO. Thus this small molecular cloud is not typical of the molecular material generally studied in Taurus
Molecular Electron Density Theory: A Modern View of Reactivity in Organic Chemistry
Directory of Open Access Journals (Sweden)
Luis R. Domingo
2016-09-01
Full Text Available A new theory for the study of the reactivity in Organic Chemistry, named Molecular Electron Density Theory (MEDT, is proposed herein. MEDT is based on the idea that while the electron density distribution at the ground state is responsible for physical and chemical molecular properties, as proposed by the Density Functional Theory (DFT, the capability for changes in electron density is responsible for molecular reactivity. Within MEDT, the reactivity in Organic Chemistry is studied through a rigorous quantum chemical analysis of the changes of the electron density as well as the energies associated with these changes along the reaction path in order to understand experimental outcomes. Studies performed using MEDT allow establishing a modern rationalisation and to gain insight into molecular mechanisms and reactivity in Organic Chemistry.
Fluid and gyrokinetic modelling of particle transport in plasmas with hollow density profiles
International Nuclear Information System (INIS)
Tegnered, D; Oberparleiter, M; Nordman, H; Strand, P
2016-01-01
Hollow density profiles occur in connection with pellet fuelling and L to H transitions. A positive density gradient could potentially stabilize the turbulence or change the relation between convective and diffusive fluxes, thereby reducing the turbulent transport of particles towards the center, making the fuelling scheme inefficient. In the present work, the particle transport driven by ITG/TE mode turbulence in regions of hollow density profiles is studied by fluid as well as gyrokinetic simulations. The fluid model used, an extended version of the Weiland transport model, Extended Drift Wave Model (EDWM), incorporates an arbitrary number of ion species in a multi-fluid description, and an extended wavelength spectrum. The fluid model, which is fast and hence suitable for use in predictive simulations, is compared to gyrokinetic simulations using the code GENE. Typical tokamak parameters are used based on the Cyclone Base Case. Parameter scans in key plasma parameters like plasma β, R/L T , and magnetic shear are investigated. It is found that β in particular has a stabilizing effect in the negative R/L n region, both nonlinear GENE and EDWM show a decrease in inward flux for negative R/L n and a change of direction from inward to outward for positive R/L n . This might have serious consequences for pellet fuelling of high β plasmas. (paper)
Development and application of ZM-2 drilling fluid density adjustment mixing device
Directory of Open Access Journals (Sweden)
Zongming Lei
2015-01-01
Full Text Available High-pressure shallow (gas/water flow is often hidden in the deepwater seabed, so penetrating shallow flow in drilling without BOP will be highly risky. In this case, the conventional well killing method to balance the formation pressure with back pressure generated by well head equipment is no longer suitable. Based on the analysis of structural characteristics of domestic and foreign multi-phase mixing systems, a ZM-2 drilling fluid density adjustment mixing device with independent intellectual property right was developed according to the principles of dynamic well killing. The device is mainly composed of a throttle valve, a high-precision electromagnetic flowmeter, a mixer, dumbbell-shaped nozzles, connecting pipes and other components. Fixed on the mixer are three inlets to fill heavy mud, seawater and additives. Opposed jetting is adopted to realize rapid and uniform mixing of fluids with different densities. A laboratory test was conducted to work out the relationship between throttle opening and injection flow rate and establish a linear relationship between killing fluid density and heavy mud flow. The results of field test conducted in the Nanhai No.8 drill ship showed that the mixing device was stable in operation and excellent in mixing performance. The density difference of ingredient mixture could be controlled within 0.05 g/cm3 after the mixture flowed out of the mixing chamber of the mixer of about 0.3 m long, so such high precision can meet the requirement of dynamic well killing.
Thermostating highly confined fluids.
Bernardi, Stefano; Todd, B D; Searles, Debra J
2010-06-28
In this work we show how different use of thermostating devices and modeling of walls influence the mechanical and dynamical properties of confined nanofluids. We consider a two dimensional fluid undergoing Couette flow using nonequilibrium molecular dynamics simulations. Because the system is highly inhomogeneous, the density shows strong fluctuations across the channel. We compare the dynamics produced by applying a thermostating device directly to the fluid with that obtained when the wall is thermostated, considering also the effects of using rigid walls. This comparison involves an analysis of the chaoticity of the fluid and evaluation of mechanical properties across the channel. We look at two thermostating devices with either rigid or vibrating atomic walls and compare them with a system only thermostated by conduction through vibrating atomic walls. Sensitive changes are observed in the xy component of the pressure tensor, streaming velocity, and density across the pore and the Lyapunov localization of the fluid. We also find that the fluid slip can be significantly reduced by rigid walls. Our results suggest caution in interpreting the results of systems in which fluid atoms are thermostated and/or wall atoms are constrained to be rigid, such as, for example, water inside carbon nanotubes.
Crystal nucleation in simple and complex fluids.
Oxtoby, David W
2003-03-15
The application of density-functional methods from statistical mechanics to the nucleation of crystals from the melt is described. Simple fluids such as metals, with sizes comparable with the range of their attractive forces, are compared with complex fluids such as colloidal suspensions and proteins dissolved in solution. A different mechanism for crystal nucleation is proposed in the latter case, in which density (concentration) changes before periodic crystalline order appears. This leads to a theoretical foundation for empirical observations on the 'crystallization window' in protein crystallization. Comparisons are made with the results of computer simulation via molecular dynamics.
Density-ratio effects on buoyancy-driven variable-density turbulent mixing
Aslangil, Denis; Livescu, Daniel; Banerjee, Arindam
2017-11-01
Density-ratio effects on the turbulent mixing of two incompressible, miscible fluids with different densities subject to constant acceleration are studied by means of high-resolution Direct Numerical Simulations. In a triply periodic domain, turbulence is generated by stirring in response to the differential buoyancy forces within the flow. Later, as the fluids become molecularly mixed, dissipation starts to overcome turbulence generation by bouyancy. Thus, the flow evolution includes both turbulence growth and decay, and it displays features present in the core region of the mixing layer of the Rayleigh-Taylor as well as Richtmyer-Meshkov instabilities. We extend the previous studies by investigating a broad range of density-ratio, from 1-14.4:1, corresponding to Atwood numbers of 0.05-0.87. Here, we focus on the Atwood number dependence of mixing-efficiency, that is defined based on the energy-conversion ratios from potential energy to total and turbulent kinetic energies, the decay characteristics of buoyancy-assisted variable-density homogeneous turbulence, and the effects of high density-ratios on the turbulence structure and mixing process. Authors acknowledge financial support from DOE-SSAA (DE-NA0003195) and NSF CAREER (#1453056) awards.
Extended Lagrangian Density Functional Tight-Binding Molecular Dynamics for Molecules and Solids
International Nuclear Information System (INIS)
Aradi, Balint; Frauenheim, Thomas
2015-01-01
A computationally fast quantum mechanical molecular dynamics scheme using an extended Lagrangian density functional tight-binding formulation has been developed and implemented in the DFTB+ electronic structure program package for simulations of solids and molecular systems. The scheme combines the computational speed of self-consistent density functional tight-binding theory with the efficiency and long-term accuracy of extended Lagrangian Born-Oppenheimer molecular dynamics. Furthermore, for systems without self-consistent charge instabilities, only a single diagonalization or construction of the single-particle density matrix is required in each time step. The molecular dynamics simulation scheme can also be applied to a broad range of problems in materials science, chemistry, and biology
Extended Lagrangian Density Functional Tight-Binding Molecular Dynamics for Molecules and Solids.
Aradi, Bálint; Niklasson, Anders M N; Frauenheim, Thomas
2015-07-14
A computationally fast quantum mechanical molecular dynamics scheme using an extended Lagrangian density functional tight-binding formulation has been developed and implemented in the DFTB+ electronic structure program package for simulations of solids and molecular systems. The scheme combines the computational speed of self-consistent density functional tight-binding theory with the efficiency and long-term accuracy of extended Lagrangian Born-Oppenheimer molecular dynamics. For systems without self-consistent charge instabilities, only a single diagonalization or construction of the single-particle density matrix is required in each time step. The molecular dynamics simulation scheme can be applied to a broad range of problems in materials science, chemistry, and biology.
Changes in permittivity and density of molecular liquids under high pressure.
Kiselev, Vladimir D; Kornilov, Dmitry A; Konovalov, Alexander I
2014-04-03
We collected and analyzed the density and permittivity of 57 nonpolar and dipolar molecular liquids at different temperatures (143 sets) and pressures (555 sets). No equation was found that could accurately predict the change to polar liquid permittivity by the change of its density in the range of the pressures and temperatures tested. Consequently, the influence of high hydrostatic pressure and temperature on liquid permittivity may be a more complicated process compared to density changes. The pressure and temperature coefficients of permittivity can be drastically larger than the pressure and temperature coefficients of density, indicating that pressure and particularly temperature significantly affect the structure of molecular liquids. These changes have less influence on the density change but can strongly affect the permittivity change. The clear relationship between the tangent and secant moduli of the permittivity curvatures under pressure for various molecular liquids at different temperatures was obtained, from which one can calculate the Tait equation coefficients from the experimental values of the pressure influence on the permittivity at ambient pressure.
The reliability of Raman micro-spectroscopy in measuring the density of CO2 mantle fluids
Remigi, S.; Frezzotti, M. L.; Ferrando, S.; Villa, I. M.; Maffeis, A.
2017-12-01
Recent evaluations of carbon fluxes into and out the Earth's interior recognize that a significant part of the total outgassing of deep Earth carbon occurs in tectonically active areas (Kelemen and Manning, 2015). Potential tracers of carbon fluxes at mantle depths include CO2 fluid inclusions in peridotites. Raman micro-spectroscopy allows calculating the density of CO2 fluids based on the distance of the CO2 Fermi doublet, Δ, in cm-1 (Rosso and Bodnar, 1995). The aim of this work is to check the reliability of Raman densimeter equations (cf. Lamadrid et al., 2016) for high-density CO2 fluids originating at mantle depths. Forty pure CO2 inclusions in peridotites (El Hierro, Canary Islands) of known density (microthermometry) have been analyzed by Raman micro-spectroscopy. In order to evaluate the influence of contaminants on the reliability of equations, 22 CO2-rich inclusions containing subordinate amounts of N2, CO, SO2 have also been studied. Raman spectrometer analytical conditions are: 532 nm laser, 80 mW emission power, T 18°C, 1800 and 600 grating, 1 accumulation x 80 sec. Daily calibration included diamond and atmosphere N2. Results suggest that the "Raman densimeter" represents an accurate method to calculate the density of CO2 mantle fluids. Equations, however, must be applied only to pure CO2 fluids, since contaminants, even in trace amounts (0.39 mol%), affect the Δ resulting in density overestimation. Present study further highlights how analytical conditions and data processing, such as spectral resolution (i.e., grating), calibration linearity, and statistical treatment of spectra, influence the accuracy and the precision of Δ measurements. As a consequence, specific analytical protocols for single Raman spectrometers should be set up in order to get reliable CO2 density data. Kelemen, Peter B., & Craig E. Manning. PNAS, 112.30 (2015): E3997-E4006.Lamadrid, H. M., Moore, L. R., Moncada, D., Rimstidt, J. D., Burruss, R. C., & Bodnar, R. J. Chem
Molecularly Imprinted Polymers for 5-Fluorouracil Release in Biological Fluids
Directory of Open Access Journals (Sweden)
Franco Alhaique
2007-04-01
Full Text Available The aim of this work was to investigate the possibility of employing Molecularly Imprinted Polymers (MIPs as a controlled release device for 5-fluorouracil (5-FU in biological fluids, especially gastrointestinal ones, compared to Non Imprinted Polymers (NIPs. MIPs were synthesized using methacrylic acid (MAA as functional monomer and ethylene glycol dimethacrylate (EGDMA as crosslinking agent. The capacity of the polymer to recognize and to bind the template selectively in both organic and aqueous media was evaluated. An in vitro release study was performed both in gastrointestinal and in plasma simulating fluids. The imprinted polymers bound much more 5-Fu than the corresponding non-imprinted ones and showed a controlled/sustained drug release, with MIPs release rate being indeed much more sustained than that obtained from NIPs. These polymers represent a potential valid system for drug delivery and this study indicates that the selective binding characteristic of molecularly imprinted polymers is promising for the preparation of novel controlled release drug dosage form.
Density nonlinearities and a field theory for the dynamics of simple fluids
Mazenko, Gene F.; Yeo, Joonhyun
1994-01-01
We study the role of the Jacobian arising from a constraint enforcing the nonlinear relation: ${\\bf g}=\\rho{\\bf V}$, where $\\rho,\\: {\\bf g}$ and ${\\bf V}$ are the mass density, the momentum density and the local velocity field, respectively, in the field theoretic formulation of the nonlinear fluctuating hydrodynamics of simple fluids. By investigating the Jacobian directly and by developing a field theoretic formulation without the constraint, we find that no changes in dynamics result as co...
Molecular simulation studies on thermophysical properties with application to working fluids
Raabe, Gabriele
2017-01-01
This book discusses the fundamentals of molecular simulation, starting with the basics of statistical mechanics and providing introductions to Monte Carlo and molecular dynamics simulation techniques. It also offers an overview of force-field models for molecular simulations and their parameterization, with a discussion of specific aspects. The book then summarizes the available know-how for analyzing molecular simulation outputs to derive information on thermophysical and structural properties. Both the force-field modeling and the analysis of simulation outputs are illustrated by various examples. Simulation studies on recently introduced HFO compounds as working fluids for different technical applications demonstrate the value of molecular simulations in providing predictions for poorly understood compounds and gaining a molecular-level understanding of their properties. This book will prove a valuable resource to researchers and students alike.
Three-particle equilibrium correlations in dense hard-sphere fluids
Haffmans, A.F.E.M.; Schepper, I.M. de; Michels, J.P.J.; Beijeren, H. van
1988-01-01
We performed molecular-dynamics simulation experiments for a hard-sphere fluid at four high densities and determined the spatial Fourier transform of the three-particle equilibrium correlation function with two of the three particles at contact.
Fluid mechanics in fluids at rest.
Brenner, Howard
2012-07-01
Using readily available experimental thermophoretic particle-velocity data it is shown, contrary to current teachings, that for the case of compressible flows independent dye- and particle-tracer velocity measurements of the local fluid velocity at a point in a flowing fluid do not generally result in the same fluid velocity measure. Rather, tracer-velocity equality holds only for incompressible flows. For compressible fluids, each type of tracer is shown to monitor a fundamentally different fluid velocity, with (i) a dye (or any other such molecular-tagging scheme) measuring the fluid's mass velocity v appearing in the continuity equation and (ii) a small, physicochemically and thermally inert, macroscopic (i.e., non-Brownian), solid particle measuring the fluid's volume velocity v(v). The term "compressibility" as used here includes not only pressure effects on density, but also temperature effects thereon. (For example, owing to a liquid's generally nonzero isobaric coefficient of thermal expansion, nonisothermal liquid flows are to be regarded as compressible despite the general perception of liquids as being incompressible.) Recognition of the fact that two independent fluid velocities, mass- and volume-based, are formally required to model continuum fluid behavior impacts on the foundations of contemporary (monovelocity) fluid mechanics. Included therein are the Navier-Stokes-Fourier equations, which are now seen to apply only to incompressible fluids (a fact well-known, empirically, to experimental gas kineticists). The findings of a difference in tracer velocities heralds the introduction into fluid mechanics of a general bipartite theory of fluid mechanics, bivelocity hydrodynamics [Brenner, Int. J. Eng. Sci. 54, 67 (2012)], differing from conventional hydrodynamics in situations entailing compressible flows and reducing to conventional hydrodynamics when the flow is incompressible, while being applicable to both liquids and gases.
Characterization of Phase Transition in Heisenberg Fluids from Density Functional Theory
International Nuclear Information System (INIS)
Li Liangsheng; Li Li; Chen Xiaosong
2009-01-01
The phase transition of Heisenberg fluid has been investigated with the density functional theory in mean-field approximation (MF). The matrix of the second derivatives of the grand canonical potential Ω with respect to the particle density fluctuations and the magnetization fluctuations has been investigated and diagonalized. The smallest eigenvalue being 0 signalizes the phase instability and the related eigenvector characterizes this phase transition. We find a Curie line where the order parameter is pure magnetization and a spinodal where the order parameter is a mixture of particle density and magnetization. Along the spinodal, the character of phase instability changes continuously from predominant condensation to predominant ferromagnetic phase transition with the decrease of total density. The spinodal meets the Curie line at the critical endpoint with the reduced density ρ* = ρσ 3 = 0.224 and the reduced temperature T* = kT/ element of = 1.87 (σ is the diameter of Heisenberg hard sphere and element of is the coupling constant).
Addendum to ''Density fluctuations in liquid rubidium''
International Nuclear Information System (INIS)
Haan, S.W.; Mountain, R.D.; Hsu, C.S.; Rahman, A.
1980-01-01
We performed molecular-dynamics simulations of liquid rubidium and the Lennard-Jones fluid at several densities and temperatures, and of a system whose pair potential is the repulsive core of the rubidium potential. In all cases, propagating density fluctuations occurred in the rubidiumlike systems at much shorter wavelengths than in the Lennard-Jones system. This indicates that the repulsive part of the pair potential is the dominant factor in determining the relaxation of short-wavelength density fluctuations
Dynamics of the Gay-Berne fluid
International Nuclear Information System (INIS)
de Miguel, E.; Rull, L.F.; Gubbins, K.E.
1992-01-01
Using molecular-dynamics computer simulation, we study the dynamical behavior of the isotropic and nematic phases of highly anisotropic molecular fluids. The interactions are modeled by means of the Gay-Berne potential with anisotropy parameters κ=3 and κ'=5. The linear-velocity autocorrelation function shows no evidence of a negative region in the isotropic phase, even at the higher densities considered. The self-diffusion coefficient parallel to the molecular axis shows an anomalous increase with density as the system enters the nematic region. This enhancement in parallel diffusion is also observed in the isotropic side of the transition as a precursor effect. The molecular reorientation is discussed in the light of different theoretical models. The Debye diffusion model appears to explain the reorientational mechanism in the nematic phase. None of the models gives a satisfactory account of the reorientation process in the isotropic phase
Stauss, Sven
2014-10-01
Plasma-based fabrication of novel nanomaterials and nanostructures is paramount for the development of next-generation electronic devices and for green energy applications. In particular, controlling the interactions between plasmas and materials interfaces, and the plasma fluctuations are crucial for further development of plasma-based processes and bottom-up growth of nanomaterials. Discharge microplasmas generated in supercritical fluids represent a special class of high-pressure plasmas, where fluctuations on the molecular scale influence the discharge properties and the possible bottom-up growth of nanomaterials. In the first part of the talk, we will discuss an anomaly observed for microplasmas generated near the critical point, a local decrease in the breakdown voltage, which has been observed for both molecular and monoatomic gases. This anomalous behavior is suggested to be caused by the concomitant decrease of the ionization potential due to the formation of clusters near the critical point, and the formation of extended electron mean free paths induced by the high-density fluctuation near the critical point. We will also show that when generating microplasma discharges close to the critical point, that the high-density fluctuation of the supercritical fluid persists. In the second part of the presentation, we will first introduce the basic properties of diamondoids and their potential for application in many different fields - biotechnology, medicine, opto- and nanoelectronics - before discussing their synthesis by microplasmas generated inside both conventional batch-type and continuous flow reactors, using the smallest diamondoid, adamantane, as a precursor and seed. Finally we show that one possible growth mechanism of larger diamondoids from smaller ones consists in the repeated abstraction of hydrogen terminations and the addition of methyl radicals. Supported financially in part by Grant No. 23760688 and Grant No. 21110002 from the Ministry of
An accurate expression for radial distribution function of the Lennard-Jones fluid
International Nuclear Information System (INIS)
Morsali, Ali; Goharshadi, Elaheh K.; Ali Mansoori, G.; Abbaspour, Mohsen
2005-01-01
A simple and accurate expression for radial distribution function (RDF) of the Lennard-Jones fluid is presented. The expression explicitly states the RDF as a continuous function of reduced interparticle distance, temperature, and density. It satisfies the limiting conditions of zero density and infinite distance imposed by statistical thermodynamics. The distance dependence of this expression is expressed by an equation which contains 11 adjustable parameters. These parameters are fitted to 353 RDF data, obtained by molecular dynamics calculations, and then expressed as functions of reduced distance, temperature and density. This expression, having a total of 65 constants, reproduces the RDF data with an average root-mean-squared deviation of 0.0152 for the range of state variables of 0.5= * = * = * =ρσ 3 are reduced temperature and density, respectively). The expression predicts the pressure and the internal energy of the Lennard-Jones fluid with an uncertainty that is comparable to that obtained directly from the molecular dynamics simulations
Optical Absorption in Molecular Crystals from Time-Dependent Density Functional Theory
2017-04-23
Our approach represents a full solid-state calculation, allowing for polarization ef- fects while still capable of capturing inter-molecular dis...AFRL-AFOSR-UK-TR-2017-0030 Optical absorption in molecular crystals from time-dependent density functional theory Leeor Kronik WEIZMANN INSTITUTE OF...from time-dependent density functional theory 5a. CONTRACT NUMBER 5b. GRANT NUMBER FA9550-15-1-0290 5c. PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S
Generalized extended Navier-Stokes theory: multiscale spin relaxation in molecular fluids.
Hansen, J S
2013-09-01
This paper studies the relaxation of the molecular spin angular velocity in the framework of generalized extended Navier-Stokes theory. Using molecular dynamics simulations, it is shown that for uncharged diatomic molecules the relaxation time decreases with increasing molecular moment of inertia per unit mass. In the regime of large moment of inertia the fast relaxation is wave-vector independent and dominated by the coupling between spin and the fluid streaming velocity, whereas for small inertia the relaxation is slow and spin diffusion plays a significant role. The fast wave-vector-independent relaxation is also observed for highly packed systems. The transverse and longitudinal spin modes have, to a good approximation, identical relaxation, indicating that the longitudinal and transverse spin viscosities have same value. The relaxation is also shown to be isomorphic invariant. Finally, the effect of the coupling in the zero frequency and wave-vector limit is quantified by a characteristic length scale; if the system dimension is comparable to this length the coupling must be included into the fluid dynamical description. It is found that the length scale is independent of moment of inertia but dependent on the state point.
Relation between boundary slip mechanisms and waterlike fluid behavior
Ternes, Patricia; Salcedo, Evy; Barbosa, Marcia C.
2018-03-01
The slip of a fluid layer in contact with a solid confining surface is investigated for different temperatures and densities using molecular dynamic simulations. We show that for an anomalous waterlike fluid the slip goes as follows: for low levels of shear, defect slip appears and is related to the particle exchange between the fluid layers; at high levels of shear, global slip occurs and is related to the homogeneous distribution of the fluid in the confining surfaces. The oscillations in the transition velocity from defect to global slip are shown to be associated with changes in the layering distribution in the anomalous fluid.
Collision frequency of Lennard–Jones fluids at high densities by ...
Indian Academy of Sciences (India)
Detailed classical molecular dynamics simulation of transport coefficients and collision frequencies at high densities in rare gases are presented in this paper with a view to investigate the likely cause of discrepancy between theory and experiments. The results, when compared with experiments, showed an ...
International Nuclear Information System (INIS)
Kirkpatrick, R. James; Kalinichev, Andrey G.
2008-01-01
Research supported by this grant focuses on molecular scale understanding of central issues related to the structure and dynamics of geochemically important fluids, fluid-mineral interfaces, and confined fluids using computational modeling and experimental methods. Molecular scale knowledge about fluid structure and dynamics, how these are affected by mineral surfaces and molecular-scale (nano-) confinement, and how water molecules and dissolved species interact with surfaces is essential to understanding the fundamental chemistry of a wide range of low-temperature geochemical processes, including sorption and geochemical transport. Our principal efforts are devoted to continued development of relevant computational approaches, application of these approaches to important geochemical questions, relevant NMR and other experimental studies, and application of computational modeling methods to understanding the experimental results. The combination of computational modeling and experimental approaches is proving highly effective in addressing otherwise intractable problems. In 2006-2007 we have significantly advanced in new, highly promising research directions along with completion of on-going projects and final publication of work completed in previous years. New computational directions are focusing on modeling proton exchange reactions in aqueous solutions using ab initio molecular dynamics (AIMD), metadynamics (MTD), and empirical valence bond (EVB) approaches. Proton exchange is critical to understanding the structure, dynamics, and reactivity at mineral-water interfaces and for oxy-ions in solution, but has traditionally been difficult to model with molecular dynamics (MD). Our ultimate objective is to develop this capability, because MD is much less computationally demanding than quantum-chemical approaches. We have also extended our previous MD simulations of metal binding to natural organic matter (NOM) to a much longer time scale (up to 10 ns) for
Energy Technology Data Exchange (ETDEWEB)
Asiaee, Alireza; Benjamin, Kenneth M., E-mail: kenneth.benjamin@sdsmt.edu [Department of Chemical and Biological Engineering, South Dakota School of Mines and Technology, 501 E. Saint Joseph St., Rapid City, South Dakota 57701 (United States)
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 (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.
A fluid density sensor based on a resonant tube
International Nuclear Information System (INIS)
Zhu, Yong; Dao, Dzung Viet; Woodfield, Peter
2014-01-01
A fluid density sensor based on resonance frequency change of a metallic tube is presented. The sensor has been developed without using a complex micro-fabrication process. The sensor is able to identify fluid types/contaminations and improve the performance by reducing testing time, decreasing complexity of testing equipment and reducing sample sizes. The sensor can measure the resonance frequency of its own structure and determine the change in resonance frequency due to the subsequent sample inside the tube. Numerical modelling, analytical modelling and physical testing of a prototype sensor showed comparable results for both the magnitude and resonance frequency shift. The modelling results yielded a resonance frequency shift of 200 Hz from 9.87 kHz to 9.67 kHz after the water was filled into the tube. The actual testing illustrated a resonance frequency change of 280 Hz from 9.11 kHz to 8.83 kHz. The ultimate aim of the work is to determine resonance frequencies of desired samples at a level that could detect genetic disease on a cellular level. (paper)
International Nuclear Information System (INIS)
Winstanley, D.; Carrasco, R.; Zurkoff, J.
1986-01-01
A field effort is presently being conducted at the Waste Isolation Pilot Plant (WIPP) to collect accurate pressure and density information from the Culebra and Magenta dolomite members of the Rustler formation. The spatial variation of fluid density that occurs in these water-bearing units requires the use of numerical models to accurately solve for flow direction and velocity. The groundwater regime is a vital element in possible release scenarios of radionuclide-bearing fluid from the repository. Field tests were conducted on four wells utilizing a testing apparatus composed of two pressure and temperature monitoring systems and a point water sampler. Pressure versus depth plots are linear with a correlation coefficient of 0.999 or greater. Comparison of the calculated density and measured density of water obtained at depth agree within 2 percent of density measurements obtained after continuous pumping of the formation for several days before sampling. The temperature gradients ranged from 0.4 0 to 0.6 0 C per 100 feet. The data presented here are preliminary and serve as developmental information for the detailed operating plan currently under preparation
Coexistence of monatomic and diatomic molecular fluid character in liquid gallium
Energy Technology Data Exchange (ETDEWEB)
Gong, X.G. (International Centre for Theoretical Physics (ICTP), Trieste (Italy)); Chiarotti, G.L. (International School for Advanced Studies (SISSA), Trieste (Italy) Lab. Tecnologie Avanzate Superfici e Catalisi (TASC), Consorzio Interuniv. Nazionale per la Fisica della Materia (INFM), Trieste (Italy)); Parrinello, M. (IBM Research Div., Zurich Forschungslab., Rueschlikon (Switzerland) International School for Advanced Studies (SISSA), Trieste (Italy)); Tosatti, E. (International School for Advanced Studies (SISSA), Trieste (Italy) International Centre for Theoretical Physics (ICTP), Trieste (Italy) IBM Research Div., Zurich Forschungslab., Rueschlikon (Switzerland))
1993-02-01
We have performed an ab initio molecular-dynamics simulation of liquid Ga at high temperature (1000 K). Our results are in good agreement with scattering data and with Knight-shift experiments. A remarkable feature of our findings is the coexistence in the liquid state of metallic and covalent characters. Covalency manifests itself in the appearance of very short-lived Ga-Ga bonds, which represent remnants in the liquid of the crystalline form [alpha]-Ga. We set up a two-fluid scheme which can be used for the analysis of fluids where metallic and covalent characters coexist. (orig.).
Coexistence of monatomic and diatomic molecular fluid character in liquid gallium
International Nuclear Information System (INIS)
Gong, X.G.; Chiarotti, G.L.; Parrinello, M.; Tosatti, E.
1993-01-01
We have performed an ab initio molecular-dynamics simulation of liquid Ga at high temperature (1000 K). Our results are in good agreement with scattering data and with Knight-shift experiments. A remarkable feature of our findings is the coexistence in the liquid state of metallic and covalent characters. Covalency manifests itself in the appearance of very short-lived Ga-Ga bonds, which represent remnants in the liquid of the crystalline form α-Ga. We set up a two-fluid scheme which can be used for the analysis of fluids where metallic and covalent characters coexist. (orig.)
Directory of Open Access Journals (Sweden)
S. Dastgeer
2005-01-01
Full Text Available Interstellar scintillation and angular radio wave broadening measurements show that interstellar and solar wind (electron density fluctuations exhibit a Kolmogorov-like k-5/3 power spectrum extending over many decades in wavenumber space. The ubiquity of the Kolmogorov-like interstellar medium (ISM density spectrum led to an explanation based on coupling incompressible magnetohydrodynamic (MHD fluctuations to density fluctuations through a 'pseudosound' relation within the context of 'nearly incompressible' (NI hydrodynamics (HD and MHD models. The NI theory provides a fundamentally different explanation for the observed ISM density spectrum in that the density fluctuations can be a consequence of passive scalar convection due to background incompressible fluctuations. The theory further predicts generation of long-scale structures and various correlations between the density, temperature and the (magneto acoustic as well as convective pressure fluctuations in the compressible ISM fluids in different thermal regimes that are determined purely by the thermal fluctuation level. In this paper, we present the results of our two dimensional nonlinear fluid simulations, exploring various nonlinear aspects that lead to inertial range ISM turbulence within the context of a NI hydrodymanics model. In qualitative agreement with the NI predictions and the in-situ observations, we find that i the density fluctuations exhibit a Kolmogorov-like spectrum via a passive convection in the field of the background incompressible fluctuations, ii the compressible ISM fluctuations form long scale flows and structures, and iii the density and the temperature fluctuations are anti-correlated.
Experimental observation for the heat transfer in fluids
International Nuclear Information System (INIS)
Salinas R, G.A.
1996-01-01
The heat transfer that occurs into a cavity with a relation 2/1 with constant heat supply in a vertical wall and on the opposed wall at constant temperature is studied. The energy transfer process causes the heat convection that occurs mainly due to energy transport that is present by means of the motion of the fluid itself. Also the heat conduction process by molecular exchange is obtained. During the fluid particle displacements, the high energy regions take contact with the low energy regions resulting by this way the free convection by density differences. The flow can be followed by means of tracers and the changes of density can be registered by optical techniques like interferometry. (Author)
Theory and computer simulation of structure, transport, and flow of fluid in micropores
International Nuclear Information System (INIS)
Davis, H.T.; Bitsanis, I.; Vanderlick, T.K.; Tirrell, M.V.
1987-01-01
An overview is given of recent progress made in our laboratory on this topic. The density profiles of fluid in micropores are found by solving numerically an approximate Yvon-Born-Green equation. A related local average density model (LADM) allows prediction of transport and flow in inhomogeneous fluids from density profiles. A rigorous extension of the Enskog theory of transport is also outlined. Simple results of this general approach for the tracer diffusion and Couette flow between planar micropore walls are presented. Equilibrium and flow (molecular dynamics) simulations are compared with the theoretical predictions. Simulated density profiles of the micropore fluid exhibit substantial fluid layering. The number and sharpness of fluid layers depend sensitively on the pore width. The solvation force and the pore average density and diffusivity are oscillating functions of the pore width. The theoretical predictions for these quantities agree qualitatively with the simulation results. The flow simulations indicate that the flow does not affect the fluid structure and diffusivity even at extremely high shear rates (10/sup 10/s/sup -1/). The fluid structure induces large deviations of the shear stress and the effective viscosity from the bulk fluid values. The flow velocity profiles are correlated with the density profiles and differ from those of a bulk fluid. The LADM and extended Enskog theory predictions for the velocity profiles and the pore average diffusivity agree very well with each other and with the simulation results. The LADM predictions for the shear stress and the effective viscosity agrees fairly well with the simulation results
Surface tension and contact angles: Molecular origins and associated microstructure
Davis, H. T.
1982-01-01
Gradient theory converts the molecular theory of inhomogeneous fluid into nonlinear boundary value problems for density and stress distributions in fluid interfaces, contact line regions, nuclei and microdroplets, and other fluid microstructures. The relationship between the basic patterns of fluid phase behavior and the occurrence and stability of fluid microstructures was clearly established by the theory. All the inputs of the theory have molecular expressions which are computable from simple models. On another level, the theory becomes a phenomenological framework in which the equation of state of homogeneous fluid and sets of influence parameters of inhomogeneous fluids are the inputs and the structures, stress tensions and contact angles of menisci are the outputs. These outputs, which find applications in the science and technology of drops and bubbles, are discussed.
International Nuclear Information System (INIS)
Helmi, Abbas; Keshavarzi, Ezat
2014-01-01
Highlights: • The effect of concavo-convex walls of nanopores on the density profile was studied. • For HS fluids the contact density at concave wall is greater than for convex wall. • For Yukawa fluid the contact density at concave wall can be less than convex wall. • Capillary condensation was observed for Yukawa fluids in the homocentric pores. - Abstract: We investigate the effects of concavo-convex walls of a nanopore on the structure and certain thermodynamic properties of confined fluids. Adsorption, solvation force, and capillary condensation in a nanopore formed between two homocentric spheres will be determined using the MFMT. For hard sphere fluids, contact density is greater at the concave wall than it is at the convex wall. In Yukawa fluids, for the thermodynamic state in which the energy effect is the dominant factor, contact density at a concave wall is less than that at a convex wall; this will be reversed for the thermodynamic state in which the entropy effect is the dominant factor. It is possible to find thermodynamic states in which contact densities at concave and convex walls become identical. The adsorption and solvation force of hard sphere fluid show an oscillatory behavior versus H. Capillary condensation is in certain cases observed for Yukawa fluids
Sun, Shuyu
2013-06-01
This paper introduces an efficient technique to generate new molecular simulation Markov chains for different temperature and density conditions, which allow for rapid extrapolation of canonical ensemble averages at a range of temperatures and densities different from the original conditions where a single simulation is conducted. Obtained information from the original simulation are reweighted and even reconstructed in order to extrapolate our knowledge to the new conditions. Our technique allows not only the extrapolation to a new temperature or density, but also the double extrapolation to both new temperature and density. The method was implemented for Lennard-Jones fluid with structureless particles in single-gas phase region. Extrapolation behaviors as functions of extrapolation ranges were studied. Limits of extrapolation ranges showed a remarkable capability especially along isochors where only reweighting is required. Various factors that could affect the limits of extrapolation ranges were investigated and compared. In particular, these limits were shown to be sensitive to the number of particles used and starting point where the simulation was originally conducted.
Sun, Shuyu; Kadoura, Ahmad Salim; Salama, Amgad
2013-01-01
This paper introduces an efficient technique to generate new molecular simulation Markov chains for different temperature and density conditions, which allow for rapid extrapolation of canonical ensemble averages at a range of temperatures and densities different from the original conditions where a single simulation is conducted. Obtained information from the original simulation are reweighted and even reconstructed in order to extrapolate our knowledge to the new conditions. Our technique allows not only the extrapolation to a new temperature or density, but also the double extrapolation to both new temperature and density. The method was implemented for Lennard-Jones fluid with structureless particles in single-gas phase region. Extrapolation behaviors as functions of extrapolation ranges were studied. Limits of extrapolation ranges showed a remarkable capability especially along isochors where only reweighting is required. Various factors that could affect the limits of extrapolation ranges were investigated and compared. In particular, these limits were shown to be sensitive to the number of particles used and starting point where the simulation was originally conducted.
Dissecting molecular descriptors into atomic contributions in density functional reactivity theory
International Nuclear Information System (INIS)
Rong, Chunying; Lu, Tian; Liu, Shubin
2014-01-01
Density functional reactivity theory (DFRT) employs the electron density of a molecule and its related quantities such as gradient and Laplacian to describe its structure and reactivity properties. Proper descriptions at both molecular (global) and atomic (local) levels are equally important and illuminating. In this work, we make use of Bader's zero-flux partition scheme and consider atomic contributions for a few global reactivity descriptors in DFRT, including the density-based quantification of steric effect and related indices. Earlier, we proved that these quantities are intrinsically correlated for atomic and molecular systems [S. B. Liu, J. Chem. Phys. 126, 191107 (2007); ibid. 126, 244103 (2007)]. In this work, a new basin-based integration algorithm has been implemented, whose reliability and effectiveness have been extensively examined. We also investigated a list of simple hydrocarbon systems and different scenarios of bonding processes, including stretching, bending, and rotating. Interesting changing patterns for the atomic and molecular values of these quantities have been revealed for different systems. This work not only confirms the strong correlation between these global reactivity descriptors for molecular systems, as theoretically proven earlier by us, it also provides new and unexpected changing patterns for their atomic values, which can be employed to understand the origin and nature of chemical phenomena
Dissecting molecular descriptors into atomic contributions in density functional reactivity theory
Energy Technology Data Exchange (ETDEWEB)
Rong, Chunying [Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China) and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081 (China); Lu, Tian [School of Chemical and Biological Engineering, University of Science and Technology Beijing, Beijing (China); Liu, Shubin, E-mail: shubin@email.unc.edu [Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China) and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081 (China); Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420 (United States)
2014-01-14
Density functional reactivity theory (DFRT) employs the electron density of a molecule and its related quantities such as gradient and Laplacian to describe its structure and reactivity properties. Proper descriptions at both molecular (global) and atomic (local) levels are equally important and illuminating. In this work, we make use of Bader's zero-flux partition scheme and consider atomic contributions for a few global reactivity descriptors in DFRT, including the density-based quantification of steric effect and related indices. Earlier, we proved that these quantities are intrinsically correlated for atomic and molecular systems [S. B. Liu, J. Chem. Phys. 126, 191107 (2007); ibid. 126, 244103 (2007)]. In this work, a new basin-based integration algorithm has been implemented, whose reliability and effectiveness have been extensively examined. We also investigated a list of simple hydrocarbon systems and different scenarios of bonding processes, including stretching, bending, and rotating. Interesting changing patterns for the atomic and molecular values of these quantities have been revealed for different systems. This work not only confirms the strong correlation between these global reactivity descriptors for molecular systems, as theoretically proven earlier by us, it also provides new and unexpected changing patterns for their atomic values, which can be employed to understand the origin and nature of chemical phenomena.
International Nuclear Information System (INIS)
Goel, Gaurav; Krekelberg, William P; Pond, Mark J; Truskett, Thomas M; Mittal, Jeetain; Shen, Vincent K; Errington, Jeffrey R
2009-01-01
Although classical density functional theory provides reliable predictions for the static properties of simple equilibrium fluids under confinement, a theory of comparative accuracy for the transport coefficients has yet to emerge. Nonetheless, there is evidence that knowledge of how confinement modifies static behavior can aid in forecasting dynamics. Specifically, recent molecular simulation studies have shown that the relationship between excess entropy and self-diffusivity of a bulk equilibrium fluid changes only modestly when the fluid is isothermally confined, indicating that knowledge of the former might allow semi-quantitative predictions of the latter. Do other static measures, such as those that characterize free or available volume, also strongly correlate with single-particle dynamics of confined fluids? Here, we investigate this question for both the single-component hard-sphere fluid and hard-sphere mixtures. Specifically, we use molecular simulations and fundamental measure theory to study these systems at approximately 10 3 equilibrium state points. We examine three different confining geometries (slit pore, square channel, and cylindrical pore) and the effects of particle packing fraction and particle–boundary interactions. Although average density fails to predict some key qualitative trends for the self-diffusivity of confined fluids, we provide strong empirical evidence that a new generalized measure of available volume for inhomogeneous fluids correlates excellently with self-diffusivity across a wide parameter space in these systems, approximately independently of the degree of confinement. An important consequence, which we demonstrate here, is that density functional theory predictions of this static property can be used together with knowledge of bulk fluid behavior to semi-quantitatively estimate the self-diffusion coefficient of confined fluids under equilibrium conditions
Towards the design of new and improved drilling fluid additives using molecular dynamics simulations
International Nuclear Information System (INIS)
Anderson, Richard L.; Greenwel, H. Christopher; Suter, James L.; Coveney, Peter V.; Jarvis, Rebecca M.
2010-01-01
During exploration for oil and gas, a technical drilling fluid is used to lubricate the drill bit, maintain hydrostatic pressure, transmit sensor readings, remove rock cuttings and inhibit swelling of unstable clay based reactive shale formations. Increasing environmental awareness and resulting legislation has led to the search for new, improved biodegradable drilling fluid components. In the case of additives for clay swelling inhibition, an understanding of how existing effective additives interact with clays must be gained to allow the design of improved molecules. Owing to the disordered nature and nano scope dimension of the interlayer pores of clay minerals, computer simulations have become an increasingly useful tool for studying clay-swelling inhibitor interactions. In this work we briefly review the history of the development of technical drilling fluids, the environmental impact of drilling fluids and the use of computer simulations to study the interactions between clay minerals and swelling inhibitors. We report on results from some recent large-scale molecular dynamics simulation studies on low molecular weight water-soluble macromolecular inhibitor molecules. The structure and interactions of poly(propylene oxide)-diamine, poly(ethylene glycol) and poly(ethylene oxide)-diacrylate inhibitor molecules with montmorillonite clay are studied. (author)
A new analysing approach for the structure of density fluctuation of supercritical fluid
International Nuclear Information System (INIS)
Sato, T; Sugiyama, M; Itoh, K; Mori, K; Fukunaga, T; Misawa, M; Otomo, T; Takata, S
2008-01-01
Large scale structural evolution of supercritical carbon dioxide along the isotherm at 32 deg. C was investigated with small-angle neutron scattering. The maximum of the density fluctuation, the so-called 'ridge', was confirmed with Ornstein-Zernike analysis. To investigate the structural change in more detail, the molecular distribution over a large domain was determined with a newly developed reverse Monte Carlo method. From the molecular distribution obtained, the pair distribution function and cluster-size distribution can be calculated. With increasing density of carbon dioxide, the cluster size increases monotonically, whereas the pair distribution function for the range of sizes shorter than 10 A shows a monotonic decrease. From this result, it is suggested that the structural change along the isotherm is caused by the change of balance between growth of clusters and increase of the average density
Keshavarzi, Ezat; Kamalvand, Mohammad
2009-04-23
The structure and properties of fluids confined in nanopores may show a dramatic departure from macroscopic bulk fluids. The main reason for this difference lies in the influence of system walls. In addition to the entropic wall effect, system walls can significantly change the energy of the confined fluid compared to macroscopic bulk fluids. The energy effect of the walls on a nanoconfined fluid appears in two forms. The first effect is the cutting off of the intermolecular interactions by the walls, which appears for example in the integrals for calculation of the thermodynamic properties. The second wall effect involves the wall-molecule interactions. In such confined fluids, the introduction of wall forces and the competition between fluid-wall and fluid-fluid forces could lead to interesting thermodynamic properties, including new kinds of phase transitions not observed in the macroscopic fluid systems. In this article, we use the perturbative fundamental measure density functional theory to study energy effects on the structure and properties of a hard core two-Yukawa fluid confined in a nanoslit. Our results show the changes undergone by the structure and phase transition of the nanoconfined fluids as a result of energy effects.
Equations of state of nonspherical fluids by spherical intermolecular potentials
International Nuclear Information System (INIS)
Bastea, S; Ree, F H
1999-01-01
The equilibrium properties of anisotropic molecular fluids can be in principle calculated in a statistical mechanics framework, but the theory is generally too cumbersome for many practical applications. Fortunately, at high densities and temperatures the anisotropy can be averaged-out by means of a density and temperature independent potential (the median) that produces reliable thermodynamics[1,2]. The proposal of Shaw and Johnson[1], which turns out to be the so-called median potential[2], is very successful in predicting the thermodynamics of simple fluids such as N(sub 2) and CO(sub 2) at reasonable high pressures and temperatures[3]. Lebowitz and Percus[2] pointed out some time ago that the success of this approximation could perhaps be understood in terms of a simple theory that treats the asphericity as a perturbation. The median appears to be the best choice for hard nonspherical potential[4], which may explain its success for fluids at high densities, where the hard core contribution is known to be dominant
Rajalakshmi, K.; Gunasekaran, S.; Kumaresan, S.
2015-06-01
The Fourier transform infrared spectra and Fourier transform Raman spectra of Linezolid have been recorded in the regions 4,000-400 and 4,000-100 cm-1, respectively. Utilizing the observed Fourier transform infrared spectra and Fourier transform Raman spectra data, a complete vibrational assignment and analysis of the fundamental modes of the compound have been carried out. The optimum molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, have been calculated by density functional theory with 6-31G(d,p), 6-311G(d,p) and M06-2X/6-31G(d,p) levels. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. A detailed interpretation of the infrared and Raman spectra of Linezolid is reported. Mulliken's net charges have also been calculated. Ultraviolet-visible spectrum of the title molecule has also been calculated using time-dependent density functional method. Besides, molecular electrostatic potential, highest occupied molecular orbital and lowest unoccupied molecular orbital analysis and several thermodynamic properties have been performed by the density functional theoretical method.
Molecular density modulation type ultrahigh vacuum gauge
International Nuclear Information System (INIS)
Horikoshi, Gen-ichi; Komada, Kazutaka; Mizuno, Hajime
1978-01-01
When pressure is measured in ultrahigh vacuum region, with an ionization gauge one of the causes producing the measuring limit is its dark current due to so-called soft X-ray effect and ion desorption. A kind of the modulation gauge provided with a modulation electrode is described in this paper. If a plate is vibrating perpendicularly to its surface in the sufficiently low pressure gas to satisfy molecular conditions (molecular density n), the molecular density in the space in front of the plate is expected to vary with time, affected by the vibration of the plate. When the vacuum gauge is placed in this space, the modulated current is proportional to pressure P, which is not related to the current due to soft X-ray effect and ion desorption. The other cause of determining the pressure-measuring limit is noises, among which only the noise coherent with the vibration of the plate affects the measurement. To avoid the induced current by this type of noise, it is considered to use the pulse-counting technique using an electron multiplier. It is anticipated that the induced currents generated from electrical noises and mechanical vibrations can be avoided almost completely by this method. As a result, the theoretical measuring limit may be estimated at approximately 5 x 10 -13 Torr, if the mean residence time in the collision of molecules with the plate is assumed to be 1 sec, the sensitivity of the vacuum gauge S is 20 Torr -1 , electron current Ie is 2 x 10 -3 A and modulation coefficient m is 3 x 10 -3 . (Wakatsuki, Y.)
International Nuclear Information System (INIS)
Pshenichnikov, A.F.
2012-01-01
A new algorithm for calculating magnetic fields in a concentrated magnetic fluid with inhomogeneous density is proposed. Inhomogeneity of the fluid is caused by magnetophoresis. In this case, the diffusion and magnetostatic parts of the problem are tightly linked together and are solved jointly. The dynamic diffusion equation is solved by the finite volume method and, to calculate the magnetic field inside the fluid, an iterative process is performed in parallel. The solution to the problem is sought in Cartesian coordinates, and the computational domain is decomposed into rectangular elements. This technique eliminates the need to solve the related boundary-value problem for magnetic fields, accelerates computations and eliminates the error caused by the finite sizes of the outer region. Formulas describing the contribution of the rectangular element to the field intensity in the case of a plane problem are given. Magnetic and concentration fields inside the magnetic fluid filling a rectangular cavity generated under the action of the uniform external filed are calculated. - Highlights: ▶ New algorithm for calculating magnetic field intense magnetic fluid with account of magnetophoresis and diffusion of particles. ▶ We do not need to solve boundary-value problem, but we accelerate computations and eliminate some errors. ▶ We solve nonlinear flow equation by the finite volume method and calculate magnetic and focus fields in the fluid for plane case.
Polydispersity effect on solid-fluid transition in hard sphere systems
Nogawa, T.
2010-02-01
The solid-fluid transition of the hard elastic particle system with size polydispersity is studied by molecular dynamics simulations. Using nonequilibrium relaxation from the mixed initial condition we determines the melting point where the first order transition between the solid, fcc crystal, and fluid states occurs. It is found that the density gap between the bistable states decreases with increasing the strength of the polydispersity and continuously approaches to zero at the critical point. © 2010.
International Nuclear Information System (INIS)
Zhang Yujuan; Wang Cong; Zhang Ping
2012-01-01
First-principles molecular-dynamics simulations based on density-functional theory have been used to study the electronic and optical properties of fluid nitrous oxide under extreme conditions. Systematic descriptions of pair-correlation function, atomic structure, and the charge density distribution are used to investigate the dissociation of fluid nitrous oxide. The electrical and optical properties are derived from the Kubo-Greenwood formula. It is found that the nonmetal-metal transition for fluid nitrous oxide can be directly associated to the dissociation and has significant influence on the optical properties of the fluid.
Danel, J.-F.; Kazandjian, L.
2018-06-01
It is shown that the equation of state (EOS) and the radial distribution functions obtained by density-functional theory molecular dynamics (DFT-MD) obey a simple scaling law. At given temperature, the thermodynamic properties and the radial distribution functions given by a DFT-MD simulation remain unchanged if the mole fractions of nuclei of given charge and the average volume per atom remain unchanged. A practical interest of this scaling law is to obtain an EOS table for a fluid from that already obtained for another fluid if it has the right characteristics. Another practical interest of this result is that an asymmetric mixture made up of light and heavy atoms requiring very different time steps can be replaced by a mixture of atoms of equal mass, which facilitates the exploration of the configuration space in a DFT-MD simulation. The scaling law is illustrated by numerical results.
Molecular dynamics simulations of oscillatory flows in microfluidic channels
DEFF Research Database (Denmark)
Hansen, J.S.; Ottesen, Johnny T.
2006-01-01
In this paper we apply the direct non-equilibrium molecular dynamics technique to oscillatory flows of fluids in microscopic channels. Initially, we show that the microscopic simulations resemble the macroscopic predictions based on the Navier–Stokes equation very well for large channel width, high...... density and low temperature. Further simulations for high temperature and low density show that the non-slip boundary condition traditionally used in the macroscopic equation is greatly compromised when the fluid–wall interactions are the same as the fluid–fluid interactions. Simulations of a system...
Energy Technology Data Exchange (ETDEWEB)
Barbante, Paolo [Dipartimento di Matematica, Politecnico di Milano - Piazza Leonardo da Vinci 32 - 20133 Milano (Italy); Frezzotti, Aldo; Gibelli, Livio [Dipartimento di Scienze e Tecnologie Aerospaziali, Politecnico di Milano - Via La Masa 34 - 20156 Milano (Italy)
2014-12-09
The unsteady evaporation of a thin planar liquid film is studied by molecular dynamics simulations of Lennard-Jones fluid. The obtained results are compared with the predictions of a diffuse interface model in which capillary Korteweg contributions are added to hydrodynamic equations, in order to obtain a unified description of the liquid bulk, liquid-vapor interface and vapor region. Particular care has been taken in constructing a diffuse interface model matching the thermodynamic and transport properties of the Lennard-Jones fluid. The comparison of diffuse interface model and molecular dynamics results shows that, although good agreement is obtained in equilibrium conditions, remarkable deviations of diffuse interface model predictions from the reference molecular dynamics results are observed in the simulation of liquid film evaporation. It is also observed that molecular dynamics results are in good agreement with preliminary results obtained from a composite model which describes the liquid film by a standard hydrodynamic model and the vapor by the Boltzmann equation. The two mathematical model models are connected by kinetic boundary conditions assuming unit evaporation coefficient.
Maximizing performance in supercritical fluid chromatography using low-density mobile phases.
Gritti, Fabrice; Fogwill, Michael; Gilar, Martin; Jarrell, Joseph A
2016-10-14
The performance of a 3.0mm×150mm column packed with 1.8μm fully porous HSS-SB-C 18 particles was investigated in supercritical fluid chromatography (SFC) with low-density, highly expansible carbon dioxide. These conditions are selected for the analysis of semi-volatile compounds. Elevated temperatures (>100°C) were then combined with low column back pressures (<100bar). In this work, the inlet temperature of pure carbon dioxide was set at 107°C, the active back pressure regulator (ABPR) pressure was fixed at 100bar, and the flow rate was set at 2.1mL/min at 12°C (liquefied carbon dioxide) and at an inlet column pressure close to 300bar. Nine n-alkylbenzenes (from benzene to octadecylbenzene) were injected under linear (no sample overload) conditions. The severe steepness of the temperature gradients across the column diameter were predicted from a simplified heat transfer model. Such conditions dramatically lower the column performance by affecting the symmetry of the peak shape. In order to cope with this problem, three different approaches were experimentally tested. They include (1) the decoupling and the proper selection of the inlet eluent temperature with respect to the oven temperature, (2) the partial thermal insulation of the column using polyethylene aerogel, and (3) the application of a high vacuum (10 -5 Torr provided by a turbo-molecular pump) in a housing chamber surrounding the whole column body. The results reveal that (1) the column efficiency can be maximized by properly selecting the difference between the eluent and the oven temperatures, (2) the mere wrapping of the column with an excellent insulating material is insufficient to fully eliminate heat exchanges by conduction and the undesirable radial density gradients across the column i.d., and (3) the complete thermal insulation of the SFC column under high vacuum allows to maximize the column efficiency by maintaining the integrity of the peak shape. Copyright © 2016 Elsevier B.V. All
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.
Measurement of the density profile of pure and seeded molecular beams by femtosecond ion imaging
Energy Technology Data Exchange (ETDEWEB)
Meng, Congsen [LaserLaB Amsterdam, VU University Amsterdam, de Boelelaan 1083, 1081 HV Amsterdam (Netherlands); Department of Physics, National University of Defense Technology, Changsha 410073 (China); Janssen, Maurice H. M. [LaserLaB Amsterdam, VU University Amsterdam, de Boelelaan 1083, 1081 HV Amsterdam (Netherlands)
2015-02-15
Here, we report on femtosecond ion imaging experiments to measure the density profile of a pulsed supersonic molecular beam. Ion images are measured for both a molecular beam and bulk gas under identical experimental conditions via femtosecond multiphoton ionization of Xe atoms. We report the density profile of the molecular beam, and the measured absolute density is compared with theoretical calculations of the centre line beam density. Subsequently, we discuss reasons accounting for the differences between measurements and calculations and propose that strong skimmer interference is the most probable cause for the differences. Furthermore, we report on experiments measuring the centre line density of seeded supersonic beams. The femtosecond ion images show that seeding the heavy Xe atom at low relative seed fractions (1%-10%) in a light carrier gas like Ne results in strong relative enhancements of up to two orders of magnitude.
DEFF Research Database (Denmark)
Johansen, Per; Roemer, Daniel Beck; Andersen, Torben O.
2015-01-01
-stroke displacement simulations are used as basis for the parametric analysis. From the parametric analysis a change, in the minimum film thickness as function of piston and cylinder density, is shown for certain operating modes of the digital fluid power displacement motor. This indicate a need for careful....... In this paper the influence of the inertia term on the lubrication gaps of a radial piston motor are studied by a parametric analysis of the piston and cylinder density in a multibody tribodynamic simulation model. The motor is modeled as a digital fluid power displacement machine and a series of full...... assessment of the applicability, of the force balance condition, if it is used in multibody tribodynamic simulations of radial piston digital fluid power displacement motors....
Single-particle density matrix and superfluidity in the two-dimensional Bose Coulomb fluid
International Nuclear Information System (INIS)
Minguzzi, A.; Tosi, M.P.; Davoudi, B.
2002-01-01
A study by Magro and Ceperley [Phys. Rev. Lett. 73, 826 (1994)] has shown that the ground state of the two-dimensional fluid of charged bosons with logarithmic interactions is not Bose condensed, but exhibits algebraic off-diagonal order in the single-particle density matrix ρ(r). We use a hydrodynamic Hamiltonian expressed in terms of density and phase operators, in combination with an f-sum rule on the superfluid fraction, to reproduce these results and to extend the evaluation of the density matrix to finite temperature T. This approach allows us to treat the liquid as a superfluid in the absence of a condensate. The algebraic decay of the one-body density matrix is due to correlations between phase fluctuations, and we find that the exponent in the power law is determined by the superfluid density n s (T). We also find that the plasmon gap in the single-particle energy spectrum at long wavelengths decreases with increasing T and closes at the critical temperature for the onset of superfluidity
Thermodynamic properties of fluids from Fluctuation Solution Theory
International Nuclear Information System (INIS)
O'Connell, J.P.
1990-01-01
Fluctuation Theory develops exact relations between integrals of molecular correlation functions and concentration derivatives of pressure and chemical potential. These quantities can be usefully correlated, particularly for mechanical and thermal properties of pure and mixed dense fluids and for activities of strongly nonideal liquid solutions. The expressions yield unique formulae for the desirable thermodynamic properties of activity and density. The molecular theory origins of the flucuation properties, their behavior for systems of technical interest and some of their successful correlations will be described. Suggestions for fruitful directions will be suggested
THE 'TRUE' COLUMN DENSITY DISTRIBUTION IN STAR-FORMING MOLECULAR CLOUDS
International Nuclear Information System (INIS)
Goodman, Alyssa A.; Pineda, Jaime E.; Schnee, Scott L.
2009-01-01
We use the COMPLETE Survey's observations of the Perseus star-forming region to assess and intercompare the three methods used for measuring column density in molecular clouds: near-infrared (NIR) extinction mapping; thermal emission mapping in the far-IR; and mapping the intensity of CO isotopologues. Overall, the structures shown by all three tracers are morphologically similar, but important differences exist among the tracers. We find that the dust-based measures (NIR extinction and thermal emission) give similar, log-normal, distributions for the full (∼20 pc scale) Perseus region, once careful calibration corrections are made. We also compare dust- and gas-based column density distributions for physically meaningful subregions of Perseus, and we find significant variations in the distributions for those (smaller, ∼few pc scale) regions. Even though we have used 12 CO data to estimate excitation temperatures, and we have corrected for opacity, the 13 CO maps seem unable to give column distributions that consistently resemble those from dust measures. We have edited out the effects of the shell around the B-star HD 278942 from the column density distribution comparisons. In that shell's interior and in the parts where it overlaps the molecular cloud, there appears to be a dearth of 13 CO, which is likely due either to 13 CO not yet having had time to form in this young structure and/or destruction of 13 CO in the molecular cloud by the HD 278942's wind and/or radiation. We conclude that the use of either dust or gas measures of column density without extreme attention to calibration (e.g., of thermal emission zero-levels) and artifacts (e.g., the shell) is more perilous than even experts might normally admit. And, the use of 13 CO data to trace total column density in detail, even after proper calibration, is unavoidably limited in utility due to threshold, depletion, and opacity effects. If one's main aim is to map column density (rather than temperature
Adsorption of short-chain fluids at solid substrates from density functional theory
International Nuclear Information System (INIS)
Bryk, P.; Bucior, K.; Sokolowski, S.; Zukocinski, G.
2005-01-01
We use microscopic density functional theory to investigate the adsorption of short-chains at solid surfaces. The fluid is modeled as freely-jointed tangent spheres that interact via a short-ranged attractive potential. Within the framework of fundamental measure theory we study how the structure and surface phase behaviour of adsorbed fluid changes when the chain length is increased. We observe that the wetting temperature rescaled by the bulk critical temperature decreases with an increase of the chain length. For longer chains this temperature reaches a plateau. For the surface critical temperature an inverse effect is observed, i.e. the surface critical temperature increases with the chain length and then attains a plateau. Furthermore, we analyze how the layering transitions change with the change of the chain length and with relative strength of the fluid-solid interaction. The critical temperature of the first layering transition, rescaled by the bulk critical temperature increases slightly with an increase of the chain length. We have found that for longer chains the layering transitions within consecutive layers are shifted towards very low temperatures and that their sequence is finally replaced by a single transition. Finally we investigate capillary condensation of chain fluid in slit-like pores. We find that for a fluid of chains consisting of a larger number of segments we observe an inversion effect. Namely, the critical temperature of capillary condensation decreases with increasing pore width for a certain interval of values of the pore width. This anomalous behavior is also influenced by the interaction between molecules and pore walls. (author)
Predicting diffusivities in dense fluid mixtures
Directory of Open Access Journals (Sweden)
C. DARIVA
1999-09-01
Full Text Available In this work the Enskog solution of the Boltzmann equation, as corrected by Speedy, together with the Weeks-Chandler-Andersen (WCA perturbation theory of liquids is employed in correlating and predicting self-diffusivities of dense fluids. Afterwards this theory is used to estimate mutual diffusion coefficients of solutes at infinite dilution in sub and supercritical solvents. We have also investigated the behavior of Fick diffusion coefficients in the proximity of a binary vapor-liquid critical point since this subject is of great interest for extraction purposes. The approach presented here, which makes use of a density and temperature dependent hard-sphere diameter, is shown to be excellent for predicting diffusivities in dense pure fluids and fluid mixtures. The calculations involved highly nonideal mixtures as well as systems with high molecular asymmetry. The predicted diffusivities are in good agreement with the experimental data for the pure and binary systems. The methodology proposed here makes only use of pure component information and density of mixtures. The simple algebraic relations are proposed without any binary adjustable parameters and can be readily used for estimating diffusivities in multicomponent mixtures.
Lecoutre, C.; Marre, S.; Garrabos, Y.; Beysens, D.; Hahn, I.
2018-05-01
Analyses of ground-based experiments on near-critical fluids to precisely determine their density can be hampered by several effects, especially the density stratification of the sample, the liquid wetting behavior at the cell walls, and a possible singular curvature of the "rectilinear" diameter of the density coexisting curve. For the latter effect, theoretical efforts have been made to understand the amplitude and shape of the critical hook of the density diameter, which depart from predictions from the so-called ideal lattice-gas model of the uniaxial 3D-Ising universality class. In order to optimize the observation of these subtle effects on the position and shape of the liquid-vapor meniscus in the particular case of SF6, we have designed and filled a cell that is highly symmetrized with respect to any median plane of the total fluid volume. In such a viewed quasi-perfect symmetrical fluid volume, the precise detection of the meniscus position and shape for different orientations of the cell with respect to the Earth's gravity acceleration field becomes a sensitive probe to estimate the cell mean density filling and to test the singular diameter effects. After integration of this cell in the ALI-R insert, we take benefit of the high optical and thermal performances of the DECLIC Engineering Model. Here we present the sensitive imaging method providing the precise ground-based SF6 benchmark data. From these data analysis it is found that the temperature dependence of the meniscus position does not reflect the expected critical hook in the rectilinear density diameter. Therefore the off-density criticality of the cell is accurately estimated, before near future experiments using the same ALI-R insert in the DECLIC facility already on-board the International Space Station.
Bulk properties and near-critical behaviour of SiO2 fluid
Green, Eleanor C. R.; Artacho, Emilio; Connolly, James A. D.
2018-06-01
Rocky planets and satellites form through impact and accretion processes that often involve silicate fluids at extreme temperatures. First-principles molecular dynamics (FPMD) simulations have been used to investigate the bulk thermodynamic properties of SiO2 fluid at high temperatures (4000-6000 K) and low densities (500-2240 kg m-3), conditions which are relevant to protoplanetary disc condensation. Liquid SiO2 is highly networked at the upper end of this density range, but depolymerises with increasing temperature and volume, in a process characterised by the formation of oxygen-oxygen (Odbnd O) pairs. The onset of vaporisation is closely associated with the depolymerisation process, and is likely to be non-stoichiometric at high temperature, initiated via the exsolution of O2 molecules to leave a Si-enriched fluid. By 6000 K the simulated fluid is supercritical. A large anomaly in the constant-volume heat capacity occurs near the critical temperature. We present tabulated thermodynamic properties for silica fluid that reconcile observations from FPMD simulations with current knowledge of the SiO2 melting curve and experimental Hugoniot curves.
Available states and available space: Static properties that predict dynamics of confined fluids
Goel, Gaurav; Krekelberg, William P.; Pond, Mark J.; Mittal, Jeetain; Shen, Vincent K.; Errington, Jeffrey R.; Truskett, Thomas M.
2009-01-01
Although density functional theory provides reliable predictions for the static properties of simple fluids under confinement, a theory of comparative accuracy for the transport coefficients has yet to emerge. Nonetheless, there is evidence that knowledge of how confinement modifies static behavior can aid in forecasting dynamics. Specifically, molecular simulation studies have shown that the relationship between excess entropy and self diffusivity of a bulk equilibrium fluid changes only mod...
Collective dynamics in dense fluid mixtures
International Nuclear Information System (INIS)
Sinha, S.
1992-01-01
This thesis deals with the short wavelength collective dynamics of dense binary fluid mixtures. The analysis shows that at the level of linearized generalized hydrodynamics, the longitudinal modes of the system separates essentially into two parts - one involves the coupling of partial density fluctuations of the two species and the other involves coupling of longitudinal momentum and temperature fluctuations. The authors have shown that the coupling of longitudinal momentum and temperature fluctuations leads to an adequate description of sound propagation in such systems. In particular, they show that structural disorder controls the trapping of sound waves in dense mixtures. The coupling of the partial density fluctuations of the two species leads to a simple description of the partial dynamic structure factors. The results are in agreement with the molecular dynamics simulations of soft sphere mixtures. The partial density fluctuations are the slowest decaying fluctuations on molecular length scales and it turns out that nonlinear coupling of these slow modes leads to important corrections to the long time behavior of the time correlation functions determining the shear viscosity in dense mixtures
The heat current density correlation function: sum rules and thermal conductivity
International Nuclear Information System (INIS)
Singh, Shaminder; Tankeshwar, K; Pathak, K N; Ranganathan, S
2006-01-01
Expressions for the second and fourth sum rules of the heat current density correlation function have been derived in an appropriate ensemble. The thermal conductivity of Lennard-Jones fluids has been calculated using these sum rules for the heat current density correlation function and the Gaussian form of the memory function. It is found that the results obtained for the thermal conductivity are in good agreement with the molecular dynamics simulation results over a wide range of densities and temperatures. Earlier results obtained using the energy current density correlation function are also discussed
The heat current density correlation function: sum rules and thermal conductivity
Energy Technology Data Exchange (ETDEWEB)
Singh, Shaminder [Department of Physics, Panjab University, Chandigarh-160 014 (India); Tankeshwar, K [Department of Physics, Panjab University, Chandigarh-160 014 (India); Pathak, K N [Department of Physics, Panjab University, Chandigarh-160 014 (India); Ranganathan, S [Department of Physics, Royal Military College, Kingston, ON, K7K 7B4 (Canada)
2006-02-01
Expressions for the second and fourth sum rules of the heat current density correlation function have been derived in an appropriate ensemble. The thermal conductivity of Lennard-Jones fluids has been calculated using these sum rules for the heat current density correlation function and the Gaussian form of the memory function. It is found that the results obtained for the thermal conductivity are in good agreement with the molecular dynamics simulation results over a wide range of densities and temperatures. Earlier results obtained using the energy current density correlation function are also discussed.
Investigation of the silicon ion density during molecular beam epitaxy growth
Eifler, G.; Kasper, E.; Ashurov, Kh.; Morozov, S.
2002-05-01
Ions impinging on a surface during molecular beam epitaxy influence the growth and the properties of the growing layer, for example, suppression of dopant segregation and the generation of crystal defects. The silicon electron gun in the molecular beam epitaxy (MBE) equipment is used as a source for silicon ions. To use the effect of ion bombardment the mechanism of generation and distribution of ions was investigated. A monitoring system was developed and attached at the substrate position in the MBE growth chamber to measure the ion and electron densities towards the substrate. A negative voltage was applied to the substrate to modify the ion energy and density. Furthermore the current caused by charge carriers impinging on the substrate was measured and compared with the results of the monitoring system. The electron and ion densities were measured by varying the emission current of the e-gun achieving silicon growth rates between 0.07 and 0.45 nm/s and by changing the voltage applied to the substrate between 0 to -1000 V. The dependencies of ion and electron densities were shown and discussed within the framework of a simple model. The charged carrier densities measured with the monitoring system enable to separate the ion part of the substrate current and show its correlation to the generation rate. Comparing the ion density on the whole substrate and in the center gives a hint to the ion beam focusing effect. The maximum ion and electron current densities obtained were 0.40 and 0.61 μA/cm2, respectively.
Accurate Kirkwood-Buff Integrals from Molecular Dynamics Simulations
DEFF Research Database (Denmark)
Wedberg, Nils Hejle Rasmus Ingemar; O'Connell, John P.; Peters, Günther H.J.
2010-01-01
A method is proposed for obtaining thermodynamic properties via Kirkwood–Buff (KB) integrals from molecular simulations. In order to ensure that the KB integration converges, the pair distribution function is extrapolated to large distances using the extension method of Verlet, which enforces...... of state fitted to simulation results. Good agreement is achieved for both fluids at densities larger than 1.5 times the critical density....
The dynamics of variable-density turbulence
International Nuclear Information System (INIS)
Sandoval, D.L.
1995-11-01
The dynamics of variable-density turbulent fluids are studied by direct numerical simulation. The flow is incompressible so that acoustic waves are decoupled from the problem, and implying that density is not a thermodynamic variable. Changes in density occur due to molecular mixing. The velocity field, is in general, divergent. A pseudo-spectral numerical technique is used to solve the equations of motion. Three-dimensional simulations are performed using a grid size of 128 3 grid points. Two types of problems are studied: (1) the decay of isotropic, variable-density turbulence, and (2) buoyancy-generated turbulence in a fluid with large density fluctuations. In the case of isotropic, variable-density turbulence, the overall statistical decay behavior, for the cases studied, is relatively unaffected by the presence of density variations when the initial density and velocity fields are statistically independent. The results for this case are in quantitative agreement with previous numerical and laboratory results. In this case, the initial density field has a bimodal probability density function (pdf) which evolves in time towards a Gaussian distribution. The pdf of the density field is symmetric about its mean value throughout its evolution. If the initial velocity and density fields are statistically dependent, however, the decay process is significantly affected by the density fluctuations. For the case of buoyancy-generated turbulence, variable-density departures from the Boussinesq approximation are studied. The results of the buoyancy-generated turbulence are compared with variable-density model predictions. Both a one-point (engineering) model and a two-point (spectral) model are tested against the numerical data. Some deficiencies in these variable-density models are discussed and modifications are suggested
Directory of Open Access Journals (Sweden)
Mostapha Marzban
2017-10-01
Full Text Available Measuring of fluid properties such as dynamic viscosity and density has tremendous potential for various applications from physical to biological to chemical sensing. However, it is almost impossible to affect only one of these properties, as dynamic viscosity and density are coupled. Hence, this paper proposes kinematic viscosity as a comprehensive parameter which can be used to study the effect of fluid properties applicable to various fluids from Newtonian fluids, such as water, to non-Newtonian fluids, such as blood. This paper also proposes an ideal microplatform, namely polymeric suspended microfluidics (SPMF3, with flow plane orthogonal to the bending plane of the structure, along with tested results of various fluids covering a wide range of engineering applications. Kinematic viscosity, also called momentum diffusivity, considers changes in both fluid intermolecular forces and molecular inertia that define dynamic viscosity and fluid density, respectively. In this study a 3D suspended polymeric microfluidic system (SPMF3 was employed to detect changes in fluid parameters such as dynamic viscosity and density during fluid processes. Using this innovative design along with theoretical and experimental results, it is shown that, in fluids, the variations of fluid density and dynamic viscosity are not easily comprehensible due to their interconnectivity. Since any change in a fluid will affect both density and dynamic viscosity, measuring both of them is necessary to identify the fluid or process status. Finally, changes in fluid properties were analyzed using simulation and experiments. The experimental results with salt-DI water solution and milk with different fat concentrations as a colloidal fluid show that kinematic viscosity is a comprehensive parameter that can identify the fluids in a unique way using the proposed microplatform.
Directory of Open Access Journals (Sweden)
Redzic Zoran
2011-01-01
Full Text Available Abstract Efficient processing of information by the central nervous system (CNS represents an important evolutionary advantage. Thus, homeostatic mechanisms have developed that provide appropriate circumstances for neuronal signaling, including a highly controlled and stable microenvironment. To provide such a milieu for neurons, extracellular fluids of the CNS are separated from the changeable environment of blood at three major interfaces: at the brain capillaries by the blood-brain barrier (BBB, which is localized at the level of the endothelial cells and separates brain interstitial fluid (ISF from blood; at the epithelial layer of four choroid plexuses, the blood-cerebrospinal fluid (CSF barrier (BCSFB, which separates CSF from the CP ISF, and at the arachnoid barrier. The two barriers that represent the largest interface between blood and brain extracellular fluids, the BBB and the BCSFB, prevent the free paracellular diffusion of polar molecules by complex morphological features, including tight junctions (TJs that interconnect the endothelial and epithelial cells, respectively. The first part of this review focuses on the molecular biology of TJs and adherens junctions in the brain capillary endothelial cells and in the CP epithelial cells. However, normal function of the CNS depends on a constant supply of essential molecules, like glucose and amino acids from the blood, exchange of electrolytes between brain extracellular fluids and blood, as well as on efficient removal of metabolic waste products and excess neurotransmitters from the brain ISF. Therefore, a number of specific transport proteins are expressed in brain capillary endothelial cells and CP epithelial cells that provide transport of nutrients and ions into the CNS and removal of waste products and ions from the CSF. The second part of this review concentrates on the molecular biology of various solute carrier (SLC transport proteins at those two barriers and underlines
The influence of hapten density on the assay of penicilloylated proteins in fluids
International Nuclear Information System (INIS)
Lee, D.; Dewdney, J.M.; Edwards, R.G.
1985-01-01
The use of inhibition radioimmunoassays for the measurement of penicilloylated proteins in biological fluids is compromised by the dominant influence of hapten density. Precise quantitation, and therefore assessment of antigenicity and immunogenicity, cannot be achieved in the absence of knowledge of the number and distribution of haptenic groups on the protein carrier. These assays may not, therefore, be appropriate for the measurement of potential allergenic residues in food products. (Auth.)
Molecular Simulation Of Phase Equilibria For Complex Fluids
International Nuclear Information System (INIS)
Panagiotopoulos, Athanassios Z.
2009-01-01
The general area of this project was the development and application of novel molecular simulation methods for prediction of thermodynamic and structural properties of complex polymeric, surfactant and ionic fluids. Over this project period, we have made considerable progress in developing novel algorithms to meet the computational challenges presented by the strong or long-range interactions in these systems and have generated data for well-defined mod-els that can be used to test theories and compare to experimental data. Overall, 42 archival papers and many invited and contributed presentations and lectures have been based on work supported by this project. 6 PhD, 1 M.S. and 2 postdoctoral students have been associated with this work, as listed in the body of the report.
MOLECULAR SIMULATION OF PHASE EQUILIBRIA FOR COMPLEX FLUIDS
Energy Technology Data Exchange (ETDEWEB)
Athanassios Z. Panagiotopoulos
2009-09-09
The general area of this project was the development and application of novel molecular simulation methods for prediction of thermodynamic and structural properties of complex polymeric, surfactant and ionic fluids. Over this project period, we have made considerable progress in developing novel algorithms to meet the computational challenges presented by the strong or long-range interactions in these systems and have generated data for well-defined mod-els that can be used to test theories and compare to experimental data. Overall, 42 archival papers and many invited and contributed presentations and lectures have been based on work supported by this project. 6 PhD, 1 M.S. and 2 postdoctoral students have been associated with this work, as listed in the body of the report.
Investigation of the silicon ion density during molecular beam epitaxy growth
Eifler, G; Ashurov, K; Morozov, S
2002-01-01
Ions impinging on a surface during molecular beam epitaxy influence the growth and the properties of the growing layer, for example, suppression of dopant segregation and the generation of crystal defects. The silicon electron gun in the molecular beam epitaxy (MBE) equipment is used as a source for silicon ions. To use the effect of ion bombardment the mechanism of generation and distribution of ions was investigated. A monitoring system was developed and attached at the substrate position in the MBE growth chamber to measure the ion and electron densities towards the substrate. A negative voltage was applied to the substrate to modify the ion energy and density. Furthermore the current caused by charge carriers impinging on the substrate was measured and compared with the results of the monitoring system. The electron and ion densities were measured by varying the emission current of the e-gun achieving silicon growth rates between 0.07 and 0.45 nm/s and by changing the voltage applied to the substrate betw...
Transport tensors in perfectly aligned low-density fluids: Self-diffusion and thermal conductivity
International Nuclear Information System (INIS)
Singh, G. S.; Kumar, B.
2001-01-01
The modified Taxman equation for the kinetic theory of low-density fluids composed of rigid aspherical molecules possessing internal degrees of freedom is generalized to obtain the transport tensors in a fluid of aligned molecules. The theory takes care of the shape of the particles exactly but the solution has been obtained only for the case of perfectly aligned hard spheroids within the framework of the first Sonine polynomial approximation. The expressions for the thermal-conductivity components have been obtained for the first time whereas the self-diffusion components obtained here turn out to be exactly the same as those derived by Kumar and Masters [Mol. Phys. >81, 491 (1994)] through the solution of the Lorentz-Boltzmann equation. All our expressions yield correct results in the hard-sphere limit
International Nuclear Information System (INIS)
Primas, H.; Schleicher, M.
1975-01-01
A comprehensive review of the attempts to rephrase molecular quantum mechanics in terms of the particle density operator and the current density or phase density operator is given. All pertinent investigations which have come to attention suffer from severe mathematical inconsistencies and are not adequate to the few-body problem of quantum chemistry. The origin of the failure of these attempts is investigated, and it is shown that a realization of a local quantum field theory of molecular matter in terms of observables would presuppose the solution of many highly nontrivial mathematical problems
Stokes-Einstein relation for pure simple fluids
Cappelezzo, M.; Capellari, C. A.; Pezzin, S. H.; Coelho, L. A. F.
2007-06-01
The authors employed the equilibrium molecular dynamics technique to calculate the self-diffusion coefficient and the shear viscosity for simple fluids that obey the Lennard-Jones 6-12 potential in order to investigate the validity of the Stokes-Einstein (SE) relation for pure simple fluids. They performed calculations in a broad range of density and temperature in order to test the SE relation. The main goal of this work is to exactly calculate the constant, here denominated by α, present in the SE relation. Also, a modified SE relation where a fluid density is raised to a power in the usual expression is compared to the classical expression. According to the authors' simulations slip boundary conditions (α=4) can be satisfied in some state points. An intermediate value of α =5 was found in some regions of the phase diagram confirming the mode coupling theory. In addition depending on the phase diagram point and the definition of hydrodynamics radius, stick boundary condition (α=6) can be reproduced. The authors investigated the role of the hydrodynamic radius in the SE relation using three different definitions. The authors also present calculations for α in a hard-sphere system showing that the slip boundary conditions hold at very high density. They discuss possible explanations for their results and the role of the hydrodynamic radius for different definitions in the SE relation.
International Nuclear Information System (INIS)
Tang, Qian; Li, Zai-yong; Wei, Yu-bo; Yang, Xia; Liu, Lan-tao; Gong, Cheng-bin; Ma, Xue-bing; Lam, Michael Hon-wah; Chow, Cheuk-fai
2016-01-01
A photoresponsive surface molecularly imprinted polymer for uric acid in physiological fluids was fabricated through a facile and effective method using bio-safe and biocompatible ZnO nanorods as a support. The strategy was carried out by introducing double bonds on the surface of the ZnO nanorods with 3-methacryloxypropyltrimethoxysilane. The surface molecularly imprinted polymer on ZnO nanorods was then prepared by surface polymerization using uric acid as template, water-soluble 5-[(4-(methacryloyloxy)phenyl)diazenyl]isophthalic acid as functional monomer, and triethanolamine trimethacryl ester as cross-linker. The surface molecularly imprinted polymer on ZnO nanorods showed good photoresponsive properties, high recognition ability, and fast binding kinetics toward uric acid, with a dissociation constant of 3.22 × 10"−"5 M in aqueous NaH_2PO_4 buffer at pH = 7.0 and a maximal adsorption capacity of 1.45 μmol g"−"1. Upon alternate irradiation at 365 and 440 nm, the surface molecularly imprinted polymer on ZnO nanorods can quantitatively uptake and release uric acid. - Highlights: • Novel surface molecularly imprinted polymer on ZnO nanorods was synthesized. • ZnO-SMIP showed good selectivity toward uric acid in physiological fluids. • ZnO-SMIP displayed good photoresponsive properties.
Energy Technology Data Exchange (ETDEWEB)
Tang, Qian [The Key Laboratory of Applied Chemistry of Chongqing Municipality, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715 (China); Department of Science and Environmental Studies, The Hong Kong Institute of Education (Hong Kong); Li, Zai-yong; Wei, Yu-bo; Yang, Xia; Liu, Lan-tao [The Key Laboratory of Applied Chemistry of Chongqing Municipality, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715 (China); Gong, Cheng-bin, E-mail: gongcbtq@swu.edu.cn [The Key Laboratory of Applied Chemistry of Chongqing Municipality, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715 (China); Ma, Xue-bing [The Key Laboratory of Applied Chemistry of Chongqing Municipality, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715 (China); Lam, Michael Hon-wah [Department of Biology and Chemistry, City University of Hong Kong (Hong Kong); Chow, Cheuk-fai, E-mail: cfchow@ied.edu.hk [Department of Science and Environmental Studies, The Hong Kong Institute of Education (Hong Kong)
2016-09-01
A photoresponsive surface molecularly imprinted polymer for uric acid in physiological fluids was fabricated through a facile and effective method using bio-safe and biocompatible ZnO nanorods as a support. The strategy was carried out by introducing double bonds on the surface of the ZnO nanorods with 3-methacryloxypropyltrimethoxysilane. The surface molecularly imprinted polymer on ZnO nanorods was then prepared by surface polymerization using uric acid as template, water-soluble 5-[(4-(methacryloyloxy)phenyl)diazenyl]isophthalic acid as functional monomer, and triethanolamine trimethacryl ester as cross-linker. The surface molecularly imprinted polymer on ZnO nanorods showed good photoresponsive properties, high recognition ability, and fast binding kinetics toward uric acid, with a dissociation constant of 3.22 × 10{sup −5} M in aqueous NaH{sub 2}PO{sub 4} buffer at pH = 7.0 and a maximal adsorption capacity of 1.45 μmol g{sup −1}. Upon alternate irradiation at 365 and 440 nm, the surface molecularly imprinted polymer on ZnO nanorods can quantitatively uptake and release uric acid. - Highlights: • Novel surface molecularly imprinted polymer on ZnO nanorods was synthesized. • ZnO-SMIP showed good selectivity toward uric acid in physiological fluids. • ZnO-SMIP displayed good photoresponsive properties.
Blatchford, Marc A; Wallen, Scott L
2002-04-15
The further development of new processes utilizing liquid or supercritical CO2 as a solvent will benefit from the rational design of new CO2-philes. Understanding solvation structures and mechanisms of these molecules is an important part of this process. In such studies, determining the change in density as a function of the measured thermodynamic conditions (pressure and temperature) provides an excellent means of directly monitoring the solution conditions in the detection volume for a given technique. By integrating spectroscopic peaks, changes in area can be used to determine changes in analyte concentration in the detection volume, and thus, it should be possible to monitor the system density in situ. In the present study, we examine the utility of Raman and NMR spectroscopy as a means of following changes in solution density conditions and validate this approach in pure fluids and gases (N2 and CO2) and supercritical fluid mixtures (acetaldehyde vapor in N2). In addition, we present the design of a simple, inexpensive cell for conducting Raman and NMR measurements under moderate pressure conditions.
Ishizuka, M; Kato, R; Moriya, Y; Noguchi, E; Koide, Y; Inoue, S; Itabe, H; Yamamoto, M
2017-06-01
Periodontal disease is a chronic inflammatory disease caused by bacterial infection that can lead to tooth loss. Gingival crevicular fluid can be collected easily and noninvasively. We previously discovered the presence of apolipoprotein B (apoB), the main constituent of low-density lipoprotein, and oxidized low-density lipoprotein (oxLDL) in the gingival crevicular fluid of healthy subjects. In this study, we investigated whether periodontal conditions affect the levels of apoB and oxLDL in gingival crevicular fluid. The study population comprised 11 patients with chronic periodontitis. A pair of gingival crevicular fluid samples was collected from each patient at a healthy site and at a site with periodontitis (baseline samples). Thereafter, gingival crevicular fluid samples were collected from the same patients again at 4 and 8 wk after scaling and root planing (SRP). The levels of apoB, oxLDL, protein and cytokines in gingival crevicular fluid, in addition to gingival crevicular fluid volume, were measured. At baseline, the levels of apoB and oxLDL in gingival crevicular fluid were higher at the sites with periodontitis than at the healthy sites. The levels of apoB and oxLDL at periodontal sites decreased after SRP. The level of oxLDL in gingival crevicular fluid correlated well with the probing pocket depth. The oxLDL : apoB ratio in gingival crevicular fluid was significantly higher than that in plasma. The levels of apoB and oxLDL in gingival crevicular fluid change according to the periodontal tissue conditions. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.
Dense fluid self-diffusion coefficient calculations using perturbation theory and molecular dynamics
Directory of Open Access Journals (Sweden)
COELHO L. A. F.
1999-01-01
Full Text Available A procedure to correlate self-diffusion coefficients in dense fluids by using the perturbation theory (WCA coupled with the smooth-hard-sphere theory is presented and tested against molecular simulations and experimental data. This simple algebraic expression correlates well the self-diffusion coefficients of carbon dioxide, ethane, propane, ethylene, and sulfur hexafluoride. We have also performed canonical ensemble molecular dynamics simulations by using the Hoover-Nosé thermostat and the mean-square displacement formula to compute self-diffusion coefficients for the reference WCA intermolecular potential. The good agreement obtained from both methods, when compared with experimental data, suggests that the smooth-effective-sphere theory is a useful procedure to correlate diffusivity of pure substances.
Molecular Dynamics Simulation of High Density DNA Arrays
Directory of Open Access Journals (Sweden)
Rudolf Podgornik
2018-01-01
Full Text Available Densely packed DNA arrays exhibit hexagonal and orthorhombic local packings, as well as a weakly first order transition between them. While we have some understanding of the interactions between DNA molecules in aqueous ionic solutions, the structural details of its ordered phases and the mechanism governing the respective phase transitions between them remains less well understood. Since at high DNA densities, i.e., small interaxial spacings, one can neither neglect the atomic details of the interacting macromolecular surfaces nor the atomic details of the intervening ionic solution, the atomistic resolution is a sine qua non to properly describe and analyze the interactions between DNA molecules. In fact, in order to properly understand the details of the observed osmotic equation of state, one needs to implement multiple levels of organization, spanning the range from the molecular order of DNA itself, the possible ordering of counterions, and then all the way to the induced molecular ordering of the aqueous solvent, all coupled together by electrostatic, steric, thermal and direct hydrogen-bonding interactions. Multiscale simulations therefore appear as singularly suited to connect the microscopic details of this system with its macroscopic thermodynamic behavior. We review the details of the simulation of dense atomistically resolved DNA arrays with different packing symmetries and the ensuing osmotic equation of state obtained by enclosing a DNA array in a monovalent salt and multivalent (spermidine counterions within a solvent permeable membrane, mimicking the behavior of DNA arrays subjected to external osmotic stress. By varying the DNA density, the local packing symmetry, and the counterion type, we are able to analyze the osmotic equation of state together with the full structural characterization of the DNA subphase, the counterion distribution and the solvent structural order in terms of its different order parameters and
Molecular dynamics simulation for the baryon-quark phase transition at finite baryon density
International Nuclear Information System (INIS)
Akimura, Y.; Maruyama, T.; Chiba, S.; Yoshinaga, N.
2005-01-01
We study the baryon-quark phase transition in the molecular dynamics (MD) of the quark degrees of freedom at finite baryon density. The baryon state at low baryon density, and the deconfined quark state at high baryon density are reproduced. We investigate the equations of state of matters with different u-d-s compositions. It is found that the baryon-quark transition is sensitive to the quark width. (orig.)
DEFF Research Database (Denmark)
Frutiger, Jerome; Abildskov, Jens; Sin, Gürkan
. Multi-criteria database search and Computer Aided Molecular Design (CAMD) can be applied to generate, test and evaluate promising pure component/mixture candidate as process fluids to help optimize cycle design and performance [1]. The problem formulation for the development of novel working fluids...... a certain working fluid property parameter on the performance of the power cycle, i.e. the net power output, can facilitate the identification key properties for working fluids. In that sense a sensitivity analysis of the different parameters is suggested in this work as a systematic method to efficiently...... technology to convert such waste heat sources into usable energy. So far the low-temperature heat is not utilized efficiently for electricity generation. To optimize the heat transfer process and the power generation, the influence of the working fluid, the cycle designs and the operating conditions is vital...
An EQT-based cDFT approach for a confined Lennard-Jones fluid mixture
Energy Technology Data Exchange (ETDEWEB)
Motevaselian, M. H.; Mashayak, S. Y.; Aluru, N. R., E-mail: aluru@illinois.edu [Department of Mechanical Science and Engineering, Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States)
2015-09-28
Empirical potential-based quasi-continuum theory (EQT) provides a route to incorporate atomistic detail into continuum framework such as the Nernst-Planck equation. EQT can also be used to construct a grand potential functional for classical density functional theory (cDFT). The combination of EQT and cDFT provides a simple and fast approach to predict the inhomogeneous density, potential profiles, and thermodynamic properties of confined fluids. We extend the EQT-cDFT approach to confined fluid mixtures and demonstrate it by simulating a mixture of methane and hydrogen inside slit-like channels of graphene. We show that the EQT-cDFT predictions for the structure of the confined fluid mixture compare well with the molecular dynamics simulation results. In addition, our results show that graphene slit nanopores exhibit a selective adsorption of methane over hydrogen.
Fluid inclusion geothermometry
Cunningham, C.G.
1977-01-01
Fluid inclusions trapped within crystals either during growth or at a later time provide many clues to the histories of rocks and ores. Estimates of fluid-inclusion homogenization temperature and density can be obtained using a petrographic microscope with thin sections, and they can be refined using heating and freezing stages. Fluid inclusion studies, used in conjunction with paragenetic studies, can provide direct data on the time and space variations of parameters such as temperature, pressure, density, and composition of fluids in geologic environments. Changes in these parameters directly affect the fugacity, composition, and pH of fluids, thus directly influencing localization of ore metals. ?? 1977 Ferdinand Enke Verlag Stuttgart.
Kohn-Sham orbitals and potentials from quantum Monte Carlo molecular densities
International Nuclear Information System (INIS)
Varsano, Daniele; Barborini, Matteo; Guidoni, Leonardo
2014-01-01
In this work we show the possibility to extract Kohn-Sham orbitals, orbital energies, and exchange correlation potentials from accurate Quantum Monte Carlo (QMC) densities for atoms (He, Be, Ne) and molecules (H 2 , Be 2 , H 2 O, and C 2 H 4 ). The Variational Monte Carlo (VMC) densities based on accurate Jastrow Antisymmetrised Geminal Power wave functions are calculated through different estimators. Using these reference densities, we extract the Kohn-Sham quantities with the method developed by Zhao, Morrison, and Parr (ZMP) [Phys. Rev. A 50, 2138 (1994)]. We compare these extracted quantities with those obtained form CISD densities and with other data reported in the literature, finding a good agreement between VMC and other high-level quantum chemistry methods. Our results demonstrate the applicability of the ZMP procedure to QMC molecular densities, that can be used for the testing and development of improved functionals and for the implementation of embedding schemes based on QMC and Density Functional Theory
Synthesis of Polyimides in Molecular-Scale Confinement for Low-Density Hybrid Nanocomposites.
Isaacson, Scott G; Fostvedt, Jade I; Koerner, Hilmar; Baur, Jeffery W; Lionti, Krystelle; Volksen, Willi; Dubois, Geraud; Dauskardt, Reinhold H
2017-11-08
In this work, we exploit a confinement-induced molecular synthesis and a resulting bridging mechanism to create confined polyimide thermoset nanocomposites that couple molecular confinement-enhanced toughening with an unprecedented combination of high-temperature properties at low density. We describe a synthesis strategy that involves the infiltration of individual polymer chains through a nanoscale porous network while simultaneous imidization reactions increase the molecular backbone stiffness. In the extreme limit where the confinement length scale is much smaller than the polymer's molecular size, confinement-induced molecular mechanisms give rise to exceptional mechanical properties. We find that polyimide oligomers can undergo cross-linking reactions even in such molecular-scale confinement, increasing the molecular weight of the organic phase and toughening the nanocomposite through a confinement-induced energy dissipation mechanism. This work demonstrates that the confinement-induced molecular bridging mechanism can be extended to thermoset polymers with multifunctional properties, such as excellent thermo-oxidative stability and high service temperatures (>350 °C).
Directory of Open Access Journals (Sweden)
Chinthaka GOONERATNE
2008-04-01
Full Text Available Hyperthermia treatment has been gaining momentum in the past few years as a possible method to manage cancer. Cancer cells are different to normal cells in many ways including how they react to heat. Due to this difference it is possible for hyperthermia treatment to destroy cancer cells without harming the healthy normal cells surrounding the tumor. Magnetic particles injected into the body generate heat by hysteresis loss and temperature is increased when a time varying external magnetic field is applied. Successful treatment depends on how efficiently the heat is controlled. Thus, it is very important to estimate the magnetic fluid density in the body. Experimental apparatus designed for testing, numerical analysis, and results obtained by experimentation using a simple yet novel and minimally invasive needle type spin-valve giant magnetoresistance (SV-GMR sensor, to estimate low concentration magnetic fluid weight density and detection of magnetic fluid in a reference medium is reported.
Two-fluid mixing in a microchannel
International Nuclear Information System (INIS)
Liu Yingzheng; Kim, Byoung Jae; Sung, Hyung Jin
2004-01-01
A numerical study of the mixing of two fluids (pure water and a solution of glycerol in water) in a microchannel was carried out. By varying the glycerol content of the glycerol/water solution, the variation in mixing behavior with changes in the difference in the properties of the two fluids (e.g., viscosity, density and diffusivity) was investigated. The mixing phenomena were tested for three micromixers: a squarewave mixer, a three-dimensional serpentine mixer and a staggered herringbone mixer. The governing equations of continuity, momentum and solute mass fraction were solved numerically. To evaluate mixing performance, a criterion index of mixing uniformity was proposed. In the systems considered, the Reynolds number based on averaged properties was Re=1 and 10. For low Reynolds number (Re=1), the mixing performance varied inversely with mass fraction of glycerol due to the dominance of molecular diffusion. The mixing performance deteriorated due to a significant reduction in the residence time of the fluid inside the mixers
Mixing process of a binary gas in a density stratified layer
Energy Technology Data Exchange (ETDEWEB)
Takeda, Tetsuaki [Japan Atomic Energy Research Inst., Oarai, Ibaraki (Japan). Oarai Research Establishment
1997-09-01
This study is to investigate the effect of natural convection on the mixing process by molecular diffusion in a vertical stratified layer of a binary fluid. There are many experimental and analytical studies on natural convection in the vertical fluid layer. However, there are few studies on natural convection with molecular diffusion in the vertical stratified layer of a binary gas. Experimental study has been performed on the combined phenomena of molecular diffusion and natural convection in a binary gas system to investigate the mixing process of the binary gas in a vertical slot consisting of one side heated and the other side cooled. The range of Rayleigh number based on the slot width was about 0 < Ra{sub d} < 7.5 x 10{sup 4}. The density change of the gas mixture and the temperature distribution in the slot was obtained and the mixing process when the heavier gas ingress into the vertical slot filled with the lighter gas from the bottom side of the slot was discussed. The experimental results showed that the mixing process due to molecular diffusion was affected significantly by the natural convection induced by the slightly temperature difference between both vertical walls even if a density difference by the binary gas is larger than that by the temperature difference. (author). 81 refs.
Thermodynamic and transport properties of nitrogen fluid: Molecular theory and computer simulations
Eskandari Nasrabad, A.; Laghaei, R.
2018-04-01
Computer simulations and various theories are applied to compute the thermodynamic and transport properties of nitrogen fluid. To model the nitrogen interaction, an existing potential in the literature is modified to obtain a close agreement between the simulation results and experimental data for the orthobaric densities. We use the Generic van der Waals theory to calculate the mean free volume and apply the results within the modified Cohen-Turnbull relation to obtain the self-diffusion coefficient. Compared to experimental data, excellent results are obtained via computer simulations for the orthobaric densities, the vapor pressure, the equation of state, and the shear viscosity. We analyze the results of the theory and computer simulations for the various thermophysical properties.
Shin, Hyun Kyung; Choi, Bongsik; Talkner, Peter; Lee, Eok Kyun
2014-12-01
Based on the generalized Langevin equation for the momentum of a Brownian particle a generalized asymptotic Einstein relation is derived. It agrees with the well-known Einstein relation in the case of normal diffusion but continues to hold for sub- and super-diffusive spreading of the Brownian particle's mean square displacement. The generalized asymptotic Einstein relation is used to analyze data obtained from molecular dynamics simulations of a two-dimensional soft disk fluid. We mainly concentrated on medium densities for which we found super-diffusive behavior of a tagged fluid particle. At higher densities a range of normal diffusion can be identified. The motion presumably changes to sub-diffusion for even higher densities.
Measuring the Density of a Molecular Cluster Injector via Visible Emission from an Electron Beam
Energy Technology Data Exchange (ETDEWEB)
Lundberg, D. P.; Kaita, R.; Majeski, R. M.; Stotler, D. P.
2010-06-28
A method to measure the density distribution of a dense hydrogen gas jet is pre- sented. A Mach 5.5 nozzle is cooled to 80K to form a flow capable of molecular cluster formation. A 250V, 10mA electron beam collides with the jet and produces Hα emission that is viewed by a fast camera. The high density of the jet, several 10^{16}cm^{-3}, results in substantial electron depletion, which attenuates the H_{α} emission. The attenuated emission measurement, combined with a simplified electron-molecule collision model, allows us to determine the molecular density profile via a simple iterative calculation.
Dynamic analysis of electron density in the course of the internal motion of molecular system
International Nuclear Information System (INIS)
Tachibana, A.; Hori, K.; Asai, Y.; Yamabe, T.
1984-01-01
The general dynamic aspect of electron density of a molecular system is studied on the basis of the general equation of the electron orbital which is formulated for the dynamic study of electronic motion. The newly defined electron orbital incorporates the dynamics of molecular vibration into the electronic structures. In this scheme, the change of electron distribution caused by excitation of vibrational state is defined as the ''dynamic electron transfer.'' The dynamic electron density is found to have the remarkable ''additive'' property. The time-dependent aspect of the dynamic electron redistribution is also analyzed on the basis of the ''coherent state.'' The new method relates the classical vibrational amplitude to the quantum number of the vibrational state. As a preliminary application of the present treatment, the dynamic electron densities of H 2 , HD, HT, HF, and HCl molecules are calculated by use of ab initio molecular orbital method
Frontiers for Discovery in High Energy Density Physics
Energy Technology Data Exchange (ETDEWEB)
Davidson, R. C.; Katsouleas, T.; Arons, J.; Baring, M.; Deeney, C.; Di Mauro, L.; Ditmire, T.; Falcone, R.; Hammer, D.; Hill, W.; Jacak, B.; Joshi, C.; Lamb, F.; Lee, R.; Logan, B. G.; Melissinos, A.; Meyerhofer, D.; Mori, W.; Murnane, M.; Remington, B.; Rosner, R.; Schneider, D.; Silvera, I.; Stone, J.; Wilde, B.; Zajc. W.
2004-07-20
The report is intended to identify the compelling research opportunities of high intellectual value in high energy density physics. The opportunities for discovery include the broad scope of this highly interdisciplinary field that spans a wide range of physics areas including plasma physics, laser and particle beam physics, nuclear physics, astrophysics, atomic and molecular physics, materials science and condensed matter physics, intense radiation-matter interaction physics, fluid dynamics, and magnetohydrodynamics
Moritz, Katharina; Kleinrahm, Reiner; McLinden, Mark O.; Richter, Markus
2017-12-01
For the determination of dew-point densities and pressures of fluid mixtures, a new densimeter has been developed. The new apparatus is based on the well-established two-sinker density measurement principle with the additional capability of quantifying sorption effects. In the vicinity of the dew line, such effects cause a change in composition of the gas mixture under study, which can significantly distort accurate density measurements. The new experimental technique enables the accurate measurement of dew-point densities and pressures and the quantification of sorption effects at the same time.
Recent development of momentum density measurement of polyatomics by molecular (e,2e) spectroscopy
International Nuclear Information System (INIS)
Leung, K.T.
1996-01-01
The use of coincidence techniques to study molecular electron collisions has enabled detailed investigation of collision dynamics and development of electron scattering theories. This has in turn facilitated powerful applications in studying electron-impact ionization phenomena using the so-called (e,2e) technique. Of particular interest is the use of the triple differential cross section for modelling ionic-state-specific electronic wavefunction density in momentum space. To date, detailed electronic structural information of well over sixty atomic and molecular systems have been obtained by this method. In the past five years, there has also been intense development in the application of (e,2e) spectroscopy to study larger molecular systems and condensed matter. This paper will review the recent progress made in this field, with a special focus on the development of momentum density measurement of open-quotes largeclose quotes molecular aggregates, oligomers and bio-molecules examined in this laboratory and elsewhere
Departure of microscopic friction from macroscopic drag in molecular fluid dynamics
Energy Technology Data Exchange (ETDEWEB)
Hanasaki, Itsuo [Institute of Engineering, Tokyo University of Agriculture and Technology, Naka-cho 2-24-16, Koganei, Tokyo 184-8588 (Japan); Fujiwara, Daiki; Kawano, Satoyuki, E-mail: kawano@me.es.osaka-u.ac.jp [Graduate School of Engineering Science, Osaka University, Machikaneyama-cho 1-3, Toyonaka, Osaka 560-8531 (Japan)
2016-03-07
Friction coefficient of the Langevin equation and drag of spherical macroscopic objects in steady flow at low Reynolds numbers are usually regarded as equivalent. We show that the microscopic friction can be different from the macroscopic drag when the mass is taken into account for particles with comparable scale to the surrounding fluid molecules. We illustrate it numerically by molecular dynamics simulation of chloride ion in water. Friction variation by the atomistic mass effect beyond the Langevin regime can be of use in the drag reduction technology as well as the electro or thermophoresis.
Ludeña, E V; Echevarría, L; Lopez, X; Ugalde, J M
2012-02-28
We consider the calculation of non-Born-Oppenheimer, nBO, one-particle densities for both electrons and nuclei. We show that the nBO one-particle densities evaluated in terms of translationally invariant coordinates are independent of the wavefunction describing the motion of center of mass of the whole system. We show that they depend, however, on an arbitrary reference point from which the positions of the vectors labeling the particles are determined. We examine the effect that this arbitrary choice has on the topology of the one-particle density by selecting the Hooke-Calogero model of a three-body system for which expressions for the one-particle densities can be readily obtained in analytic form. We extend this analysis to the one-particle densities obtained from full Coulomb interaction wavefunctions for three-body systems. We conclude, in view of the fact that there is a close link between the choice of the reference point and the topology of one-particle densities that the molecular structure inferred from the topology of these densities is not unique. We analyze the behavior of one-particle densities for the Hooke-Calogero Born-Oppenheimer, BO, wavefunction and show that topological transitions are also present in this case for a particular mass value of the light particles even though in the BO regime the nuclear masses are infinite. In this vein, we argue that the change in topology caused by variation of the mass ratio between light and heavy particles does not constitute a true indication in the nBO regime of the emergence of molecular structure.
Microscopic aspects of wetting using classical density functional theory
Yatsyshin, P.; Durán-Olivencia, M.-A.; Kalliadasis, S.
2018-07-01
Wetting is a rather efficient mechanism for nucleation of a phase (typically liquid) on the interface between two other phases (typically solid and gas). In many experimentally accessible cases of wetting, the interplay between the substrate structure, and the fluid–fluid and fluid–substrate intermolecular interactions brings about an entire ‘zoo’ of possible fluid configurations, such as liquid films with a thickness of a few nanometers, liquid nanodrops and liquid bridges. These fluid configurations are often associated with phase transitions occurring at the solid–gas interface and at lengths of just several molecular diameters away from the substrate. In this special issue article, we demonstrate how a fully microscopic classical density-functional framework can be applied to the efficient, rational and systematic exploration of the rich phase space of wetting phenomena. We consider a number of model prototype systems such as wetting on a planar wall, a chemically patterned wall and a wedge. Through density-functional computations we demonstrate that for these simply structured substrates the behaviour of the solid–gas interface is already highly complex and non-trivial.
Transport Coefficients of Fluids
Eu, Byung Chan
2006-01-01
Until recently the formal statistical mechanical approach offered no practicable method for computing the transport coefficients of liquids, and so most practitioners had to resort to empirical fitting formulas. This has now changed, as demonstrated in this innovative monograph. The author presents and applies new methods based on statistical mechanics for calculating the transport coefficients of simple and complex liquids over wide ranges of density and temperature. These molecular theories enable the transport coefficients to be calculated in terms of equilibrium thermodynamic properties, and the results are shown to account satisfactorily for experimental observations, including even the non-Newtonian behavior of fluids far from equilibrium.
Energy Technology Data Exchange (ETDEWEB)
Kadoura, Ahmad; Sun, Shuyu, E-mail: shuyu.sun@kaust.edu.sa; Salama, Amgad
2014-08-01
Accurate determination of thermodynamic properties of petroleum reservoir fluids is of great interest to many applications, especially in petroleum engineering and chemical engineering. Molecular simulation has many appealing features, especially its requirement of fewer tuned parameters but yet better predicting capability; however it is well known that molecular simulation is very CPU expensive, as compared to equation of state approaches. We have recently introduced an efficient thermodynamically consistent technique to regenerate rapidly Monte Carlo Markov Chains (MCMCs) at different thermodynamic conditions from the existing data points that have been pre-computed with expensive classical simulation. This technique can speed up the simulation more than a million times, making the regenerated molecular simulation almost as fast as equation of state approaches. In this paper, this technique is first briefly reviewed and then numerically investigated in its capability of predicting ensemble averages of primary quantities at different neighboring thermodynamic conditions to the original simulated MCMCs. Moreover, this extrapolation technique is extended to predict second derivative properties (e.g. heat capacity and fluid compressibility). The method works by reweighting and reconstructing generated MCMCs in canonical ensemble for Lennard-Jones particles. In this paper, system's potential energy, pressure, isochoric heat capacity and isothermal compressibility along isochors, isotherms and paths of changing temperature and density from the original simulated points were extrapolated. Finally, an optimized set of Lennard-Jones parameters (ε, σ) for single site models were proposed for methane, nitrogen and carbon monoxide.
Kadoura, Ahmad Salim
2014-08-01
Accurate determination of thermodynamic properties of petroleum reservoir fluids is of great interest to many applications, especially in petroleum engineering and chemical engineering. Molecular simulation has many appealing features, especially its requirement of fewer tuned parameters but yet better predicting capability; however it is well known that molecular simulation is very CPU expensive, as compared to equation of state approaches. We have recently introduced an efficient thermodynamically consistent technique to regenerate rapidly Monte Carlo Markov Chains (MCMCs) at different thermodynamic conditions from the existing data points that have been pre-computed with expensive classical simulation. This technique can speed up the simulation more than a million times, making the regenerated molecular simulation almost as fast as equation of state approaches. In this paper, this technique is first briefly reviewed and then numerically investigated in its capability of predicting ensemble averages of primary quantities at different neighboring thermodynamic conditions to the original simulated MCMCs. Moreover, this extrapolation technique is extended to predict second derivative properties (e.g. heat capacity and fluid compressibility). The method works by reweighting and reconstructing generated MCMCs in canonical ensemble for Lennard-Jones particles. In this paper, system\\'s potential energy, pressure, isochoric heat capacity and isothermal compressibility along isochors, isotherms and paths of changing temperature and density from the original simulated points were extrapolated. Finally, an optimized set of Lennard-Jones parameters (ε, σ) for single site models were proposed for methane, nitrogen and carbon monoxide. © 2014 Elsevier Inc.
Gmitterová, K; Heinemann, U; Krasnianski, A; Gawinecka, J; Zerr, I
2016-06-01
Cerebrospinal fluid (CSF) analysis supports the clinical diagnosis of sporadic Creutzfeldt-Jakob disease (sCJD) when applied within an adequate clinical context. A diagnostic potential has been attributed to CSF proteins such as 14-3-3, but also tau protein, phosphorylated tau (181P) (p-tau) protein, amyloid β1-42 , S100B and neuron-specific enolase (NSE). There has been only limited information available about the contribution of CSF analysis in the differentiation of various molecular sCJD subtypes. The CSF levels of the aforementioned proteins from 73 sCJD patients with distinct molecular subtypes were determined. Differences in tau values were significant amongst the homozygous patients (MM and VV genotype) compared to the heterozygous group (P = 0.07 and P = 0.02 respectively). Significantly higher CSF tau levels (P = 0.003) and NSE (P = 0.02) but lower p-tau/tau ratio (P = 0.01) were observed in MM1 compared to MM2 patients. The p-tau/tau ratio enabled the differentiation of MV genotype with higher levels in PrP(sc) type 2 (P = 0.04). Elevation of S100B (P disease duration and clinical stage influenced the test sensitivity in all proteins. Cerebrospinal fluid protein levels might be useful in the pre-mortem differentiation of molecular sCJD subtypes when the codon 129 genotype is known. © 2016 EAN.
Density-functional theory for fluid-solid and solid-solid phase transitions.
Bharadwaj, Atul S; Singh, Yashwant
2017-03-01
We develop a theory to describe solid-solid phase transitions. The density functional formalism of classical statistical mechanics is used to find an exact expression for the difference in the grand thermodynamic potentials of the two coexisting phases. The expression involves both the symmetry conserving and the symmetry broken parts of the direct pair correlation function. The theory is used to calculate phase diagram of systems of soft spheres interacting via inverse power potentials u(r)=ε(σ/r)^{n}, where parameter n measures softness of the potential. We find that for 1/nfcc) structure while for 1/n≥0.154 the body-centred-cubic (bcc) structure is preferred. The bcc structure transforms into the fcc structure upon increasing the density. The calculated phase diagram is in good agreement with the one found from molecular simulations.
Zhao, Feihu; Vaughan, Ted J; Mc Garrigle, Myles J; McNamara, Laoise M
2017-10-01
Tissue formation within tissue engineering (TE) scaffolds is preceded by growth of the cells throughout the scaffold volume and attachment of cells to the scaffold substrate. It is known that mechanical stimulation, in the form of fluid perfusion or mechanical strain, enhances cell differentiation and overall tissue formation. However, due to the complex multi-physics environment of cells within TE scaffolds, cell transport under mechanical stimulation is not fully understood. Therefore, in this study, we have developed a coupled multiphysics model to predict cell density distribution in a TE scaffold. In this model, cell transport is modelled as a thermal conduction process, which is driven by the pore fluid pressure under applied loading. As a case study, the model is investigated to predict the cell density patterns of pre-osteoblasts MC3T3-e1 cells under a range of different loading regimes, to obtain an understanding of desirable mechanical stimulation that will enhance cell density distribution within TE scaffolds. The results of this study have demonstrated that fluid perfusion can result in a higher cell density in the scaffold region closed to the outlet, while cell density distribution under mechanical compression was similar with static condition. More importantly, the study provides a novel computational approach to predict cell distribution in TE scaffolds under mechanical loading. Copyright © 2017 Elsevier Ltd. All rights reserved.
Morris, J. F.
1981-01-01
Thermionic energy conversion (TEC) and metallic-fluid heat pipes (MFHPs), offering unique advantages in terrestrial and space energy processing by virtue of operating on working-fluid vaporization/condensation cycles that accept great thermal power densities at high temperatures, share complex materials problems. Simplified equations are presented that verify and solve such problems, suggesting the possibility of cost-effective applications in the near term for TEC and MFHP devices. Among the problems discussed are: the limitation of alkali-metal corrosion, protection against hot external gases, external and internal vaporization, interfacial reactions and diffusion, expansion coefficient matching, and creep deformation.
Friction mechanisms and interfacial slip at fluid-solid interfaces
Leger, L
2003-01-01
We present series of experiments based on near field laser velocimetry, developed to characterize the friction mechanisms at fluid-solid interfaces. For polymers, entangled polymer melts are sheared against smooth solid surfaces, covered by surface attached polymer chains of the same chemical species, having a controlled surface density. Direct measurements of the interfacial velocity and of the shear force allow identification of the molecular mechanisms of friction. Depending on the value of the inverse of the shear rate experienced by the polymer compared to the reptation time, the transition between a regime of high and a regime of low friction observed when increasing the shear rate can be related to disentanglement or to the extraction of the surface chains from the bulk polymer. Surfaces with adjusted friction properties can thus be designed by choosing chain anchored length and surface density. For simple fluids, the direct measurements of the interfacial velocity show that, contrary to the usual hypo...
Measurement of the density profile of pure and seeded molecular beams by femtosecond ion imaging
Meng, C.; Janssen, M.H.M.
2015-01-01
Here, we report on femtosecond ion imaging experiments to measure the density profile of a pulsed supersonic molecular beam. Ion images are measured for both a molecular beam and bulk gas under identical experimental conditions via femtosecond multiphoton ionization of Xe atoms. We report the
Simon, Sílvia; Duran, Miquel
1997-08-01
Quantum molecular similarity (QMS) techniques are used to assess the response of the electron density of various small molecules to application of a static, uniform electric field. Likewise, QMS is used to analyze the changes in electron density generated by the process of floating a basis set. The results obtained show an interrelation between the floating process, the optimum geometry, and the presence of an external field. Cases involving the Le Chatelier principle are discussed, and an insight on the changes of bond critical point properties, self-similarity values and density differences is performed.
The Effect of the Density Ratio on the Nonlinear Dynamics of the Unstable Fluid Interface
Abarzhi, S. I.
2003-01-01
Here we report multiple harmonic theoretical solutions for a complete system of conservation laws, which describe the large-scale coherent dynamics in RTI and RMI for fluids with a finite density ratio in the general three-dimensional case. The analysis yields new properties of the bubble front dynamics. In either RTI or RMI, the obtained dependencies of the bubble velocity and curvature on the density ratio differ qualitatively and quantitatively from those suggested by the models of Sharp (1984), Oron et al. (2001), and Goncharov (2002). We show explicitly that these models violate the conservation laws. For the first time, our theory reveals an important qualitative distinction between the dynamics of the RT and RM bubbles.
International Nuclear Information System (INIS)
Palmer, B.J.
1994-01-01
A method to calculate the thermal diffusivity D T from spontaneous fluctuations in the local heat energy density is presented. Calculations of the thermal diffusivity are performed for the Lennard-Jones fluid, carbon dioxide, and water. The results for the Lennard-Jones fluid are in agreement with calculations of the thermal conductivity using Green-Kubo relations and nonequilibrium molecular-dynamics techniques. The results for carbon dioxide and water give thermal diffusivities within a factor of 2 of the experimental values
Wang, X.; Chou, I-Ming; Hu, W.; Burruss, Robert; Sun, Q.; Song, Y.
2011-01-01
Raman spectroscopy is a powerful method for the determination of CO2 densities in fluid inclusions, especially for those with small size and/or low fluid density. The relationship between CO2 Fermi diad split (Δ, cm−1) and CO2 density (ρ, g/cm3) has been documented by several previous studies. However, significant discrepancies exist among these studies mainly because of inconsistent calibration procedures and lack of measurements for CO2fluids having densities between 0.21 and 0.75 g/cm3, where liquid and vapor phases coexist near room temperature.In this study, a high-pressure optical cell and fused silica capillary capsules were used to prepare pure CO2 samples with densities between 0.0472 and 1.0060 g/cm3. The measured CO2 Fermi diad splits were calibrated with two well established Raman bands of benzonitrile at 1192.6 and 1598.9 cm−1. The relationship between the CO2 Fermi diad split and density can be represented by: ρ = 47513.64243 − 1374.824414 × Δ + 13.25586152 × Δ2 − 0.04258891551 × Δ3(r2 = 0.99835, σ = 0.0253 g/cm3), and this relationship was tested by synthetic fluid inclusions and natural CO2-rich fluid inclusions. The effects of temperature and the presence of H2O and CH4 on this relationship were also examined.
Skarmoutsos, Ioannis
2018-05-15
Force field based-Molecular dynamics simulations were deployed to systematically explore the dynamics of confined molecules of different shapes and sizes, i.e. linear (CO2 and N2) and spherical (CH4) fluids, in a model small pore system, i.e. the Metal-Organic Framework SIFSIX-2-Cu-i. These computations unveil an unprecedented molecular symmetry dependence of the translational and rotational dynamics of fluids confined in channel-like nanoporous materials. In particular this peculiar behaviour is reflected by the extremely slow decay of the Legendre reorientational correlation functions of even-parity order for the linear fluids which is associated to jump-like orientation flips, while the spherical fluid shows a very fast decay taking place in a sub-picosecond time scale. Such a fundamental understanding is relevant to diverse disciplines such as in chemistry, physics, biology and materials science where diatomic or polyatomic molecules of different shapes/sizes diffuse through nanopores.
Karch, André; Hermann, Peter; Ponto, Claudia; Schmitz, Matthias; Arora, Amandeep; Zafar, Saima; Llorens, Franc; Müller-Heine, Annika; Zerr, Inga
2015-05-01
The molecular subtype of sporadic Creutzfeldt-Jakob disease (sCJD) is an important prognostic marker for patient survival. However, subtype determination is not possible during lifetime. Because the rate of disease progression is associated with the molecular subtype, this study aimed at investigating if total tau, a marker of neuronal death, allows premortem diagnosis of molecular subtype when codon 129 genotype is known. Two hundred ninety-six sCJD patients were tested for their cerebrospinal fluid total tau level at the time of diagnosis and were investigated for their sCJD subtype postmortem. There was a significant association between tau levels and the prion protein type in patients with codon 129 MM (p disease. Copyright © 2015 Elsevier Inc. All rights reserved.
Hybrid Fluid/Kinetic Modeling Of Magnetized High Energy Density Plasmas
Hansen, David; Held, Eric; King, Jacob; Stoltz, Peter; Masti, Robert; Srinivasan, Bhuvana
2017-10-01
MHD modeling with an equation of state (EOS) of the Rayleigh-Taylor (RT) instabily in Z indicates that it is seeded by the electro-thermal instability. Large thermodynamic drives associated with gradients at the interface between the liner and the coronal regions distort distribution functions and likely lead to non-local transport effects in a plasma which varies from weakly to strongly coupled. In this work, we discuss using effective potential theory along with a Chapman-Ensksog-like (CEL) formalism to develop hybrid fluid/kinetic modeling capabilities for these plasmas. Effective potential theory addresses the role of Coulomb collisions on transport across coupling regimes and the CEL approach bridges the gap between full-blow kinetic simulations and the EOS tables, which only depend locally on density and temperature. Quantitative results on the Spitzer problem across coupling coupling regimes will be presented as a first step. DOE Grant No. DE-SC0016525.
Muon radiolysis affected by density inhomogeneity in near-critical fluids.
Cormier, P J; Alcorn, C; Legate, G; Ghandi, K
2014-04-01
In this article we show the significant tunability of radiation chemistry in supercritical ethane and to a lesser extent in near critical CO2. The information was obtained by studies of muonium (Mu = μ(+)e(-)), which is formed by the thermalization of positive muons in different materials. The studies of the proportions of three fractions of muon polarization, PMu, diamagnetic PD and lost fraction, PL provided the information on radiolysis processes involved in muon thermalization. Our studies include three different supercritical fluids, water, ethane and carbon dioxide. A combination of mobile electrons and other radiolysis products such as (•)C2H5 contribute to interesting behavior at densities ∼40% above the critical point in ethane. In carbon dioxide, an increase in electron mobility contributes to the lost fraction. The hydrated electron in water is responsible for the lost fraction and decreases the muonium fraction.
Experimental observation of triple correlations in fluids
Directory of Open Access Journals (Sweden)
M.Ya. Sushko
2013-03-01
Full Text Available We present arguments for the hypothesis that under some conditions, triple correlations of density fluctuations in fluids can be detected experimentally by the method of molecular spectroscopy. These correlations manifest themselves in the form of so-called 1.5-(or sesquialteral scattering. The latter is of most significance in the pre-asymptotic vicinity of the critical point and can be registered along certain thermodynamic paths. Its presence in the overall scattering pattern is demonstrated by our processing available experimental data for the depolarization factor. Some consequences of these results are discussed.
Phase diagram and transport properties for hydrogen-helium fluid planets
International Nuclear Information System (INIS)
Stevenson, D.J.; Salpeter, E.E.
1977-01-01
Hydrogen and helium are the major constituents of Jupiter and Saturn, and phase transitions can have important effects on the planetary structure. In this paper, the relevant phase diagrams and microscopic transport properties are analyzed in detail. The following paper (Paper II) applies these results to the evolution and present dynamic structure of the Jovian planets.Pure hydrogen is first discussed, especially the nature of the molecular-metallic transition and the melting curves for the two phases. It is concluded that at the temperatures and pressures of interest (Tapprox. =10 4 K, Papprox. =1--10 Mbar), both phases are fluid, but the transition between them might nevertheless be first-order. The insulator-metal transition in helium occurs at a much higher pressure (approx.70 Mbars) and is not of interest.The phase diagrams for both molecular and metallic hydrogen-helium mixtures are discussed. In the metallic mixture, calculations indicate a miscibility gap for T9 or approx. =10 4 K. Immiscibility in the molecular mixture is more difficult to predict but almost certainly occurs at much lower temperatures. A fluid-state model is constructed which predicts the likely topology of the three-dimensional phase diagram. The greater solubility of helium in the molecular phase leads to the prediction that the He/H mass ratio is typically twice as large in the molecular phase as in the coexisting metallic phase. Under these circumstances a ''density inversion'' is possible in which the molecular phase becomes more dense than the metallic phase.The partitioning of minor constituents is also considered: The deuterium/hydrogen mass ratio is essentially the same for all coexisting hydrogen-helium phases, at least for T> or approx. =5000 K. The partitioning of H 2 O, CH 4 , and NH 3 probably favors the molecular (or helium-rich) phase. Substances with high conduction electron density (e.g., Al) may partition into the metallic phase
Density functional study of molecular interactions in secondary structures of proteins.
Takano, Yu; Kusaka, Ayumi; Nakamura, Haruki
2016-01-01
Proteins play diverse and vital roles in biology, which are dominated by their three-dimensional structures. The three-dimensional structure of a protein determines its functions and chemical properties. Protein secondary structures, including α-helices and β-sheets, are key components of the protein architecture. Molecular interactions, in particular hydrogen bonds, play significant roles in the formation of protein secondary structures. Precise and quantitative estimations of these interactions are required to understand the principles underlying the formation of three-dimensional protein structures. In the present study, we have investigated the molecular interactions in α-helices and β-sheets, using ab initio wave function-based methods, the Hartree-Fock method (HF) and the second-order Møller-Plesset perturbation theory (MP2), density functional theory, and molecular mechanics. The characteristic interactions essential for forming the secondary structures are discussed quantitatively.
Magnetic nanoparticles in fluid environment: combining molecular dynamics and Lattice-Boltzmann
Energy Technology Data Exchange (ETDEWEB)
Melenev, Petr, E-mail: melenev@icmm.ru [Ural Federal University, 4, Turgeneva str., 620000 Ekaterinburg (Russian Federation); Institute of Continuous Media Mechanics, 1, Koroleva str., 614013 Perm (Russian Federation)
2017-06-01
Hydrodynamic interactions between magnetic nanoparticles suspended in the Newtonian liquid are accounted for using a combination of the lattice Boltzmann method and molecular dynamics simulations. Nanoparticle is modelled by the system of molecular dynamics material points (which form structure resembles raspberry) coupled to the lattice Boltzmann fluid. The hydrodynamic coupling between the colloids is studied by simulations of the thermo-induced rotational diffusion of two raspberry objects. It was found that for the considered range of model parameters the approaching of the raspberries leads to slight retard of the relaxation process. The presence of the weak magnetic dipolar interaction between the objects leads to modest decrease of the relaxation time and the extent of the acceleration of the diffusion is intensified along with magnetic forces. - Highlights: • The combination of molecular dynamics and lattice Boltzmann method is utilized for the reveal of the role of hydrodynamic interaction in rotational dynamics of colloid particles. • The verification of the model parameters is done based on the comparison with the results of Langevin dynamics. • For the task of free rotational diffusion of the pair of colloid particles the influence of the hydrodynamic interactions on the relaxation time is examined in the case of nonmagnetic particles and at the presence of weak dipolar interaction.
Big bang nucleosynthesis with a stiff fluid
International Nuclear Information System (INIS)
Dutta, Sourish; Scherrer, Robert J.
2010-01-01
Models that lead to a cosmological stiff fluid component, with a density ρ S that scales as a -6 , where a is the scale factor, have been proposed recently in a variety of contexts. We calculate numerically the effect of such a stiff fluid on the primordial element abundances. Because the stiff fluid energy density decreases with the scale factor more rapidly than radiation, it produces a relatively larger change in the primordial helium-4 abundance than in the other element abundances, relative to the changes produced by an additional radiation component. We show that the helium-4 abundance varies linearly with the density of the stiff fluid at a fixed fiducial temperature. Taking ρ S10 and ρ R10 to be the stiff fluid energy density and the standard density in relativistic particles, respectively, at T=10 MeV, we find that the change in the primordial helium abundance is well-fit by ΔY p =0.00024(ρ S10 /ρ R10 ). The changes in the helium-4 abundance produced by additional radiation or by a stiff fluid are identical when these two components have equal density at a 'pivot temperature', T * , where we find T * =0.55 MeV. Current estimates of the primordial 4 He abundance give the constraint on a stiff fluid energy density of ρ S10 /ρ R10 <30.
International Nuclear Information System (INIS)
Hopkins, Paul; Schmidt, Matthias
2010-01-01
Using a fundamental measure density functional theory we investigate both bulk and inhomogeneous systems of the binary non-additive hard sphere model. For sufficiently large (positive) non-additivity the mixture phase separates into two fluid phases with different compositions. We calculate bulk fluid-fluid coexistence curves for a range of size ratios and non-additivity parameters and find that they compare well to simulation results from the literature. Using the Ornstein-Zernike equation, we investigate the asymptotic, r→∞, decay of the partial pair correlation functions, g ij (r). At low densities a structural crossover occurs in the asymptotic decay between two different damped oscillatory modes with different wavelengths corresponding to the two intra-species hard-core diameters. On approaching the fluid-fluid critical point there is a Fisher-Widom crossover from exponentially damped oscillatory to monotonic asymptotic decay. Using the density functional we calculate the density profiles for the planar free fluid-fluid interface between coexisting fluid phases. We show that the type of asymptotic decay of g ij (r) not only determines the asymptotic decay of the interface profiles, but is also relevant for intermediate and even short-ranged behaviour. We also determine the surface tension of the free fluid interface, finding that it increases with non-additivity, and that on approaching the critical point mean-field scaling holds.
Singh, Ram Chandra; Ram, Jokhan
2011-11-01
The effects of quadrupole moments on the isotropic-nematic (IN) phase transitions are studied using the density-functional theory (DFT) for a Gay-Berne (GB) fluid for a range of length-to-breadth parameters ? in the reduced temperature range ? . The pair-correlation functions of the isotropic phase, which enter into the DFT as input parameters are found by solving the Percus-Yevick integral equation theory. The method used involves an expansion of angle-dependent functions appearing in the integral equations in terms of spherical harmonics and the harmonic coefficients are obtained by an iterative algorithm. All the terms of harmonic coefficients which involve l indices up to less than or equal to 6 are considered. The numerical accuracy of the results depends on the number of spherical harmonic coefficients considered for each orientation-dependent function. As the length-to-breadth ratio of quadrupolar GB molecules is increased, the IN transition is seen to move to lower density (and pressure) at a given temperature. It has been observed that the DFT is good to study the IN transitions in such fluids. The theoretical results have also been compared with the computer simulation results wherever they are available.
Mansø, Mads; Petersen, Anne Ugleholdt; Wang, Zhihang; Erhart, Paul; Nielsen, Mogens Brøndsted; Moth-Poulsen, Kasper
2018-05-16
Molecular photoswitches can be used for solar thermal energy storage by photoisomerization into high-energy, meta-stable isomers; we present a molecular design strategy leading to photoswitches with high energy densities and long storage times. High measured energy densities of up to 559 kJ kg -1 (155 Wh kg -1 ), long storage lifetimes up to 48.5 days, and high quantum yields of conversion of up to 94% per subunit are demonstrated in norbornadiene/quadricyclane (NBD/QC) photo-/thermoswitch couples incorporated into dimeric and trimeric structures. By changing the linker unit between the NBD units, we can at the same time fine-tune light-harvesting and energy densities of the dimers and trimers so that they exceed those of their monomeric analogs. These new oligomers thereby meet several of the criteria to be met for an optimum molecule to ultimately enter actual devices being able to undergo closed cycles of solar light-harvesting, energy storage, and heat release.
International Nuclear Information System (INIS)
Fraser, D.G.; Refson, K.
1992-01-01
The molecular dynamics calculations reported above give calculated P-V-T properties for H 2 O up to 1500 K and 100 GPa, which agree remarkably well with the available experimental data. We also observe the phase transition to a crystalline, orientationally disordered cubic ice structure. No account was taken of molecular flexibility in these calculations nor of potential dissociation at high pressures as suggested by Hamman (1981). However, we note that the closest next-nearest-neighbour O-H approach remains significantly greater than the TIP4P fixed O-H bond length within the water molecule for all pressures studied. The equation of state proposed here should be useful for estimating the properties of H 2 O at up to 1500 K and 100 G Pa (1 Mbar) and is much easier to use in practice than modified Redlich Kwong equations. Extension of these methods to the studies of other fluids and of fluid mixtures at high temperatures and pressures will require good potential models for the species involved, and this is likely to involve a combination of good ab initio work and semiempirical modelling. Once developed, these models should allow robust predictions of thermodynamic properties beyond the range of the experimental data on the basis of fundamental molecular information
International Nuclear Information System (INIS)
Liebenberg, D.H.; Mills, R.L.; Bronson, J.C.
1977-01-01
Hydrogen isotopes play an important role in energy technologies, in particular, the compression to high densities for initiation of controlled thermonuclear fusion energy. At high densities the properties of the compressed hydrogen isotopes depart drastically from ideal thermodynamic predictions. The measurement of accurate data including the author's own recent measurements of n-H 2 and n-D 2 in the range 75 to 300 K and 0.2 to 2.0 GPa (2 to 20 kbar) is reviewed. An equation-of-state of the Benedict type is fit to these data with a double-process least-squares computer program. The results are reviewed and compared with existing data and with a variety of theoretical work reported for fluid hydrogens. A new heuristic correlation is presented for simplicity in predicting volumes and sound velocity at high pressures. 9 figures, 1 table
Supercritical fluid reverse micelle separation
Fulton, J.L.; Smith, R.D.
1993-11-30
A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W[sub o] that determines the maximum size of the reverse micelles. The maximum ratio W[sub o] of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions. 27 figures.
A measurement of the turbulence-driven density distribution in a non-star-forming molecular cloud
Energy Technology Data Exchange (ETDEWEB)
Ginsburg, Adam; Darling, Jeremy [CASA, University of Colorado, 389-UCB, Boulder, CO 80309 (United States); Federrath, Christoph, E-mail: Adam.G.Ginsburg@gmail.com [Monash Centre for Astrophysics, School of Mathematical Sciences, Monash University, Vic 3800 (Australia)
2013-12-10
Molecular clouds are supersonically turbulent. This turbulence governs the initial mass function and the star formation rate. In order to understand the details of star formation, it is therefore essential to understand the properties of turbulence, in particular the probability distribution of density in turbulent clouds. We present H{sub 2}CO volume density measurements of a non-star-forming cloud along the line of sight toward W49A. We use these measurements in conjunction with total mass estimates from {sup 13}CO to infer the shape of the density probability distribution function. This method is complementary to measurements of turbulence via the column density distribution and should be applicable to any molecular cloud with detected CO. We show that turbulence in this cloud is probably compressively driven, with a compressive-to-total Mach number ratio b=M{sub C}/M>0.4. We measure the standard deviation of the density distribution, constraining it to the range 1.5 < σ {sub s} < 1.9, assuming that the density is lognormally distributed. This measurement represents an essential input into star formation laws. The method of averaging over different excitation conditions to produce a model of emission from a turbulent cloud is generally applicable to optically thin line observations.
2017-05-05
Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--17-9724 Equilibrium Structures and Absorption Spectra for SixOy Molecular Clusters...TELEPHONE NUMBER (include area code) b. ABSTRACT c. THIS PAGE 18. NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Equilibrium Structures and Absorption...and electronic excited-state absorption spectra for eqilibrium structures of SixOy molecular clusters using density function theory (DFT) and time
Thermal conductivity of the Lennard-Jones fluid: An empirical correlation
International Nuclear Information System (INIS)
Bugel, Mathilde; Galliero, Guillaume
2008-01-01
In this work, is presented an empirical correlation on the thermal conductivity of the Lennard-Jones fluid based on extensive non-equilibrium molecular dynamics simulations results (103 points). Finite size and cutoff radius effects are investigated and taken into account to develop the correlation. This last, composed of low-density, residual and critical enhancement contributions, is built for a wide range of thermodynamics states, even at the vicinity of the critical point, and yields an average absolute deviation of 1.29% compared to our simulations. In addition, a careful analysis of the different contributions to the microscopic flux is carried out which sheds light on the underlying mechanism of the results. Finally, are discussed the limitations of the proposed model when applied to real simple fluids and mixtures using a standard corresponding states scheme and the van der Waals one-fluid approximation
Thermodynamics of Fluid Polyamorphism
Directory of Open Access Journals (Sweden)
Mikhail A. Anisimov
2018-01-01
Full Text Available Fluid polyamorphism is the existence of different condensed amorphous states in a single-component fluid. It is either found or predicted, usually at extreme conditions, for a broad group of very different substances, including helium, carbon, silicon, phosphorous, sulfur, tellurium, cerium, hydrogen, and tin tetraiodide. This phenomenon is also hypothesized for metastable and deeply supercooled water, presumably located a few degrees below the experimental limit of homogeneous ice formation. We present a generic phenomenological approach to describe polyamorphism in a single-component fluid, which is completely independent of the molecular origin of the phenomenon. We show that fluid polyamorphism may occur either in the presence or in the absence of fluid phase separation depending on the symmetry of the order parameter. In the latter case, it is associated with a second-order transition, such as in liquid helium or liquid sulfur. To specify the phenomenology, we consider a fluid with thermodynamic equilibrium between two distinct interconvertible states or molecular structures. A fundamental signature of this concept is the identification of the equilibrium fraction of molecules involved in each of these alternative states. However, the existence of the alternative structures may result in polyamorphic fluid phase separation only if mixing of these structures is not ideal. The two-state thermodynamics unifies all the debated scenarios of fluid polyamorphism in different areas of condensed-matter physics, with or without phase separation, and even goes beyond the phenomenon of polyamorphism by generically describing the anomalous properties of fluids exhibiting interconversion of alternative molecular states.
International Nuclear Information System (INIS)
Ko, Soon Heum; Kim, Na Yong; Nikitopoulos, Dimitris E.; Moldovan, Dorel; Jha, Shantenu
2014-01-01
Numerical approaches are presented to minimize the statistical errors inherently present due to finite sampling and the presence of thermal fluctuations in the molecular region of a hybrid computational fluid dynamics (CFD) - molecular dynamics (MD) flow solution. Near the fluid-solid interface the hybrid CFD-MD simulation approach provides a more accurate solution, especially in the presence of significant molecular-level phenomena, than the traditional continuum-based simulation techniques. It also involves less computational cost than the pure particle-based MD. Despite these advantages the hybrid CFD-MD methodology has been applied mostly in flow studies at high velocities, mainly because of the higher statistical errors associated with low velocities. As an alternative to the costly increase of the size of the MD region to decrease statistical errors, we investigate a few numerical approaches that reduce sampling noise of the solution at moderate-velocities. These methods are based on sampling of multiple simulation replicas and linear regression of multiple spatial/temporal samples. We discuss the advantages and disadvantages of each technique in the perspective of solution accuracy and computational cost.
Line-shape theory and molecular dynamics in collision-induced light scattering
International Nuclear Information System (INIS)
Balucani, U.; Tognetti, V.; Vallauri, R.
1979-01-01
Molecular-dynamics studies in argon at 148 amagats are presented for gaining information on the dynamical properties responsible for the depolarized light scattering from simple fluids. The total and pair-correlation functions are computed within the simple dipole--induced-dipole model of polarizability anisotropy. The pair spectral shape is derived. These results are compared with a theoretical analysis based on a continued-fraction approach. The necessary frequency moments are calculated both in the low-density limit and taking into account first-order density corrections, and compared with the molecular-dynamics data. The agreement between the theoretical spectra and molecular-dynamics data shows the validity of the memory-function approach. The comparison with the real experimental results allows one to test the relevant physical contributions to the polarizability anisotropy
Mutoru, J W; Smith, W; O'Hern, C S; Firoozabadi, A
2013-01-14
Understanding the transport properties of molecular fluids in the critical region is important for a number of industrial and natural systems. In the literature, there are conflicting reports on the behavior of the self diffusion coefficient D(s) in the critical region of single-component molecular systems. For example, D(s) could decrease to zero, reach a maximum, or remain unchanged and finite at the critical point. Moreover, there is no molecular-scale understanding of the behavior of diffusion coefficients in molecular fluids in the critical regime. We perform extensive molecular dynamics simulations in the critical region of single-component fluids composed of medium-chain n-alkanes-n-pentane, n-decane, and n-dodecane-that interact via anisotropic united-atom potentials. For each system, we calculate D(s), and average molecular cluster sizes κ(cl) and numbers N(cl) at various cluster lifetimes τ, as a function of density ρ in the range 0.2ρ(c) ≤ ρ ≤ 2.0ρ(c) at the critical temperature T(c). We find that D(s) decreases with increasing ρ but remains finite at the critical point. Moreover, for any given τ critical point.
Directory of Open Access Journals (Sweden)
Fuchs A.
2006-12-01
Full Text Available koWe briefly review the molecular simulation methods which can be used to predict thermophysical properties of fluids and fluid mixtures. It is shown in this paper, on the one hand, how the Gibbs Ensemble Monte Carlo Method allows phase behavior predictions for real fluids under conditions for which experimental data are difficult or impossible to obtain. On the other hand, the molecular dynamics methods used for predicting transport properties of molecular fluids are described. Finally we discuss possible future applications of these methods. Dans cet article, nous passons brièvement en revue les méthodes de simulation moléculaire applicables à la prédiction des propriétés thermophysiques des fluides et des mélanges. Nous montrons, d'une part, comment la méthode de Monte-Carlo dans l'ensemble de Gibbs permet de prédire le comportement de phase de fluides réels dans des conditions telles que l'acquisition de données expérimentales serait difficile, voire impossible. D'autre part, nous décrivons les méthodes de dynamique moléculaire utilisées pour prédire les propriétés de transport de fluides moléculaires. Enfin, nous discutons le potentiel de ces méthodes pour les applications futures.
A Molecular Dynamics Simulation of the Turbulent Couette Minimal Flow Unit
Smith, Edward
2016-11-01
What happens to turbulent motions below the Kolmogorov length scale? In order to explore this question, a 300 million molecule Molecular Dynamics (MD) simulation is presented for the minimal Couette channel in which turbulence can be sustained. The regeneration cycle and turbulent statistics show excellent agreement to continuum based computational fluid dynamics (CFD) at Re=400. As MD requires only Newton's laws and a form of inter-molecular potential, it captures a much greater range of phenomena without requiring the assumptions of Newton's law of viscosity, thermodynamic equilibrium, fluid isotropy or the limitation of grid resolution. The fundamental nature of MD means it is uniquely placed to explore the nature of turbulent transport. A number of unique insights from MD are presented, including energy budgets, sub-grid turbulent energy spectra, probability density functions, Lagrangian statistics and fluid wall interactions. EPSRC Post Doctoral Prize Fellowship.
Ge, Zhenpeng; Wang, Yi
2017-04-20
Molecular dynamics simulations of nanoparticles (NPs) are increasingly used to study their interactions with various biological macromolecules. Such simulations generally require detailed knowledge of the surface composition of the NP under investigation. Even for some well-characterized nanoparticles, however, this knowledge is not always available. An example is nanodiamond, a nanoscale diamond particle with surface dominated by oxygen-containing functional groups. In this work, we explore using the harmonic restraint method developed by Venable et al., to estimate the surface charge density (σ) of nanodiamonds. Based on the Gouy-Chapman theory, we convert the experimentally determined zeta potential of a nanodiamond to an effective charge density (σ eff ), and then use the latter to estimate σ via molecular dynamics simulations. Through scanning a series of nanodiamond models, we show that the above method provides a straightforward protocol to determine the surface charge density of relatively large (> ∼100 nm) NPs. Overall, our results suggest that despite certain limitation, the above protocol can be readily employed to guide the model construction for MD simulations, which is particularly useful when only limited experimental information on the NP surface composition is available to a modeler.
Kawasumi, Yusuke; Kawabata, Tomoyoshi; Sugai, Yusuke; Usui, Akihito; Hosokai, Yoshiyuki; Sato, Miho; Saito, Haruo; Ishibashi, Tadashi; Hayashizaki, Yoshie; Funayama, Masato
2013-10-01
Recent studies have reported that drowning victims frequently have fluid accumulation in the paranasal sinuses, most notably the maxillary and sphenoid sinuses. However, in our previous study, many non-drowning victims also had fluid accumulation in the sinuses. Therefore, we evaluated the qualitative difference in fluid accumulation between drowning and non-drowning cases in the present study. Thirty-eight drowning and 73 non-drowning cases were investigated retrospectively. The fluid volume and density of each case were calculated using a DICOM workstation. The drowning cases were compared with the non-drowning cases using the Mann-Whitney U-test because the data showed non-normal distribution. The median fluid volume was 1.82 (range 0.02-11.7) ml in the drowning cases and 0.49 (0.03-8.7) ml in the non-drowning cases, and the median fluid density was 22 (-14 to 66) and 39 (-65 to 77) HU, respectively. Both volume and density differed significantly between the drowning and non-drowning cases (p=0.001, p=0.0007). Regarding cut-off levels in the ROC analysis, the points on the ROC curve closest (0, 1) were 1.03ml (sensitivity 68%, specificity 68%, PPV 53%, NPV 81%) and 27.5 HU (61%, 70%, 51%, 77%). The Youden indices were 1.03ml and 37.8 HU (84%, 51%, 47%, 86%). When the cut-off level was set at 1.03ml and 27.5HU, the sensitivity was 42%, specificity 45%, PPV 29% and NPV 60%. When the cut-off level was set at 1.03ml and 37.8HU, sensitivity was 58%, specificity 32%, PPV 31% and NPV 59%. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.
Statistical properties of the dense hydrogen plasma: An ab initio molecular dynamics investigation
International Nuclear Information System (INIS)
Kohanoff, J.; Hansen, J.P.
1995-12-01
The hydrogen plasma is studied in the very high density (atomic and metallic) regime by extensive ab initio Molecular Dynamics simulations. Protons are treated classically, and electrons in the Born-Oppenheimer framework, within the local density approximation (LDA). Densities and temperatures studied fall within the strong coupling regime of the protons. We address the question of the validity of linear screening, and we find it to yield a reasonably good description up to r s approx. 0.5, but already too crude for r s = 1 (with r s = (3/4πρ) 1/3 the ion sphere radius). Finite-size and Brillouin zone sampling effects in metallic systems are studied and shown to be very delicate also in the fluid (liquid metal) phase. We analyse the low-temperature phase diagram and the melting transition. A remarkably fast decrease of the melting temperature with decreasing density is found, up to a point when it becomes comparable to the Fermi temperature of the protons. The possible vicinity of a triple point bcc-hcp(fcc)- liquid is discussed in the region of r s approx. 1.1 and T approx. 100 - 200K. The fluid phase is studied in detail for several temperatures. Proton-electron correlations show a weak temperature dependence, and proton-proton correlations exhibit a well-defined first coordination shell, thus characterizing fluid H in this regime as an atomic liquid. Diffusion coefficients are compared to the values for the one-component plasma. Vibrational densities of states (VDOS) show a plasmon renormalization due to electron screening, and the presence of a plasmon-coupled single-particle mode up to very high temperatures. Collective modes are studied through dynamical structure factors. In close relationship with the VDOS, the simulations reveal the remarkable persistent of a weakly damped high-frequency ion acoustic mode, even under conditions of strong electron screening. The possibility of using this observation as a diagnostic for the plasma phase transition to the
International Nuclear Information System (INIS)
Truckenbrodt, E.
1980-01-01
The second volume contains the chapter 4 to 6. Whereas chapter 1 deals with the introduction into the mechanics of fluids and chapter 2 with the fundamental laws of fluid and thermal fluid dynamics, in chapter 3 elementary flow phenomena in fluids with constant density are treated. Chapter 4 directly continues chapter 3 and describes elementary flow phenomena in fluids with varying density. Fluid statics again is treated as a special case. If compared with the first edition the treatment of unsteady laminar flow and of pipe flow for a fluid with varying density were subject to a substantial extension. In chapter 5 rotation-free and rotating potential flows are presented together. By this means it is achieved to explain the behaviour of the multidimensional fictionless flow in closed form. A subchapter describes some related problems of potential theory like the flow along a free streamline and seepage flow through a porous medium. The boundary layer flows in chapter 6 are concerned with the flow and temperature boundary layer in laminar and turbulent flows at a fired wall. In it differential and integral methods are applied of subchapter reports on boundary layer flows without a fixed boundary, occurring e.g. in an open jet and in a wake flow. The problems of intermittence and of the Coanda effect are briefly mentioned. (orig./MH)
Cao, Xiaofang; Rong, Chunying; Zhong, Aiguo; Lu, Tian; Liu, Shubin
2018-01-15
Molecular acidity is one of the important physiochemical properties of a molecular system, yet its accurate calculation and prediction are still an unresolved problem in the literature. In this work, we propose to make use of the quantities from the information-theoretic (IT) approach in density functional reactivity theory and provide an accurate description of molecular acidity from a completely new perspective. To illustrate our point, five different categories of acidic series, singly and doubly substituted benzoic acids, singly substituted benzenesulfinic acids, benzeneseleninic acids, phenols, and alkyl carboxylic acids, have been thoroughly examined. We show that using IT quantities such as Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy, information gain, Onicescu information energy, and relative Rényi entropy, one is able to simultaneously predict experimental pKa values of these different categories of compounds. Because of the universality of the quantities employed in this work, which are all density dependent, our approach should be general and be applicable to other systems as well. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.
Two and Three-Dimensional Nonlocal DFT for Inhomogeneous Fluids I: Algorithms and Parallelization
Energy Technology Data Exchange (ETDEWEB)
Frink, Laura J. Douglas; Salinger, Andrew
1999-08-09
Fluids adsorbed near surfaces, macromolecules, and in porous materials are inhomogeneous, inhibiting spatially varying density distributions. This inhomogeneity in the fluid plays an important role in controlling a wide variety of complex physical phenomena including wetting, self-assembly, corrosion, and molecular recognition. One of the key methods for studying the properties of inhomogeneous fluids in simple geometries has been density functional theory (DFT). However, there has been a conspicuous lack of calculations in complex 2D and 3D geometries. The computational difficulty arises from the need to perform nested integrals that are due to nonlocal terms in the free energy functional These integral equations are expensive both in evaluation time and in memory requirements; however, the expense can be mitigated by intelligent algorithms and the use of parallel computers. This paper details our efforts to develop efficient numerical algorithms so that no local DFT calculations in complex geometries that require two or three dimensions can be performed. The success of this implementation will enable the study of solvation effects at heterogeneous surfaces, in zeolites, in solvated (bio)polymers, and in colloidal suspensions.
Towards the design of new and improved drilling fluid additives using molecular dynamics simulations
Directory of Open Access Journals (Sweden)
Richard L. Anderson
2010-03-01
Full Text Available During exploration for oil and gas, a technical drilling fluid is used to lubricate the drill bit, maintain hydrostatic pressure, transmit sensor readings, remove rock cuttings and inhibit swelling of unstable clay based reactive shale formations. Increasing environmental awareness and resulting legislation has led to the search for new, improved biodegradable drilling fluid components. In the case of additives for clay swelling inhibition, an understanding of how existing effective additives interact with clays must be gained to allow the design of improved molecules. Owing to the disordered nature and nanoscopic dimension of the interlayer pores of clay minerals, computer simulations have become an increasingly useful tool for studying clay-swelling inhibitor interactions. In this work we briefly review the history of the development of technical drilling fluids, the environmental impact of drilling fluids and the use of computer simulations to study the interactions between clay minerals and swelling inhibitors. We report on results from some recent large-scale molecular dynamics simulation studies on low molecular weight water-soluble macromolecular inhibitor molecules. The structure and interactions of poly(propylene oxide-diamine, poly(ethylene glycol and poly(ethylene oxide-diacrylate inhibitor molecules with montmorillonite clay are studied.Durante a exploração de óleo e gás um fluido de perfuração é usado para lubrificar 'bit' da perfuradora, manter a pressão hidrostática, transmitir sensores de leitura, remover resíduos da rocha e inibir o inchamento da argila instável baseada nas formações dos folhelhos. O aumento das preocupações ambientais bem como a legislação resultante levou à procura de novos fluidos de perfuração com componentes biodegradáveis. No caso dos aditivos para inibir o inchamento das argilas o entendimento das interações entre os aditivos e as argilas tem que ser adquirido para permitir o
Droplet spreading driven by van der Waals force: a molecular dynamics study
Wu, Congmin
2010-07-07
The dynamics of droplet spreading is investigated by molecular dynamics simulations for two immiscible fluids of equal density and viscosity. All the molecular interactions are modeled by truncated Lennard-Jones potentials and a long-range van der Waals force is introduced to act on the wetting fluid. By gradually increasing the coupling constant in the attractive van der Waals interaction between the wetting fluid and the substrate, we observe a transition in the initial stage of spreading. There exists a critical value of the coupling constant, above which the spreading is pioneered by a precursor film. In particular, the dynamically determined critical value quantitatively agrees with that determined by the energy criterion that the spreading coefficient equals zero. The latter separates partial wetting from complete wetting. In the regime of complete wetting, the radius of the spreading droplet varies with time as R(t) ∼ √t, a behavior also found in molecular dynamics simulations where the wetting dynamics is driven by the short-range Lennard-Jones interaction between liquid and solid. © 2010 IOP Publishing Ltd.
DEFF Research Database (Denmark)
Fasano, Andrea; Rasmussen, Henrik K.
2017-01-01
A third order accurate, in time and space, finite element scheme for the numerical simulation of three- dimensional time-dependent flow of the molecular stress function type of fluids in a generalized formu- lation is presented. The scheme is an extension of the K-BKZ Lagrangian finite element me...
Transport of particles, drops, and small organisms in density stratified fluids
Ardekani, Arezoo M.; Doostmohammadi, Amin; Desai, Nikhil
2017-10-01
Sedimenting particles and motile organisms are ubiquitously found in oceans and lakes, where density stratification naturally occurs due to temperature or salinity gradients. We explore the effects of stratification on the fundamental hydrodynamics of settling particles, rising drops, and small organisms. The results of our direct numerical simulations of the sedimentation of particles show that the presence of vertical density gradients in the water column can substantially affect the settling dynamics of a particle, interaction between a pair of particles, and settling rates and microstructure of suspension of particles. We show that elongation of particles affects both the settling orientation and the settling rate of particles in stratified fluids, which will have direct consequences on the vertical flux of particulate matter and carbon flux in the ocean. We further demonstrate an unexpected effect of buoyancy, potentially affecting a broad range of processes at pycnoclines in oceans and lakes. In particular, stratification has a major effect on the flow field, energy expenditure, and nutrient uptake of small organisms. In addition, the role of stratification in pattern formation of bioconvection plumes of algal cells and in biogenic mixing is investigated. In particular, the numerical approach allows for considering the effects of background turbulence and hydrodynamic perturbations produced by swimming organisms, shedding light on the contribution of organisms in the mixing process in aqueous environments.
International Nuclear Information System (INIS)
Jog, C.J.; Solomon, P.M.
1984-01-01
We examine the consequences of treating a galactic disk as a two-fluid system for the stability of the entire disk and for the stability and form of the gas in the disk. We find that the existence of even a small fraction of the total disk surface density in a cold fluid (that is, the gas) makes it much harder to stabilize the entire two-fluid disk. (C/sub s/,min)/sub 2-f/, the critical stellar velocity dispersion for a two-fluid disk in an increasing function of μ/sub g//μ/sub s/, the gas fraction, and μ/sub t//kappa, where μ/sub g/, μ/sub s/, and μ/sub t/ are the gaseous, stellar, and total disk surface densities and kappa is the epicyclic frequency. In the Galaxy, we find that (C/sub s/,min)/sub 2-f/ as a function of R peaks when μ/sub t//kappa peaks-at galactocentric radii of Rapprox.5-7 kpc; two-fluid instabilities are most likely to occur in this region. This region is coincident with the peak in the molecular cloud distribution in the Galaxy. At the higher effective gas density resulting from the growth of a two-fluid instability, the gas may become unstble, even when originally the gas by itself is stable. The wavelength of a typical (induced) gas instability in the inner galaxy is approx.400 pc, and it contains approx.10 7 M/sub sun/ of interstellar matter; these instabilities may be identified with clusters of giant molecular clouds. We suggest that many of the spiral features seen in gas-rich spiral galaxies may be material arms or arm segments resulting from sheared two-fluid gravitational instabilities. The analysis presented here is applicable to any general disk galaxy consisting of stars and gas
Stochastic characteristics and Second Law violations of atomic fluids in Couette flow
Raghavan, Bharath V.; Karimi, Pouyan; Ostoja-Starzewski, Martin
2018-04-01
Using Non-equilibrium Molecular Dynamics (NEMD) simulations, we study the statistical properties of an atomic fluid undergoing planar Couette flow, in which particles interact via a Lennard-Jones potential. We draw a connection between local density contrast and temporal fluctuations in the shear stress, which arise naturally through the equivalence between the dissipation function and entropy production according to the fluctuation theorem. We focus on the shear stress and the spatio-temporal density fluctuations and study the autocorrelations and spectral densities of the shear stress. The bispectral density of the shear stress is used to measure the degree of departure from a Gaussian model and the degree of nonlinearity induced in the system owing to the applied strain rate. More evidence is provided by the probability density function of the shear stress. We use the Information Theory to account for the departure from Gaussian statistics and to develop a more general probability distribution function that captures this broad range of effects. By accounting for negative shear stress increments, we show how this distribution preserves the violations of the Second Law of Thermodynamics observed in planar Couette flow of atomic fluids, and also how it captures the non-Gaussian nature of the system by allowing for non-zero higher moments. We also demonstrate how the temperature affects the band-width of the shear-stress and how the density affects its Power Spectral Density, thus determining the conditions under which the shear-stress acts is a narrow-band or wide-band random process. We show that changes in the statistical characteristics of the parameters of interest occur at a critical strain rate at which an ordering transition occurs in the fluid causing shear thinning and affecting its stability. A critical strain rate of this kind is also predicted by the Loose-Hess stability criterion.
The energy density distribution of an ideal gas and Bernoulli’s equations
Santos, Leonardo S. F.
2018-05-01
This work discusses the energy density distribution in an ideal gas and the consequences of Bernoulli’s equation and the corresponding relation for compressible fluids. The aim of this work is to study how Bernoulli’s equation determines the energy flow in a fluid, although Bernoulli’s equation does not describe the energy density itself. The model from molecular dynamic considerations that describes an ideal gas at rest with uniform density is modified to explore the gas in motion with non-uniform density and gravitational effects. The difference between the component of the speed of a particle that is parallel to the gas speed and the gas speed itself is called ‘parallel random speed’. The pressure from the ‘parallel random speed’ is denominated as parallel pressure. The modified model predicts that the energy density is the sum of kinetic and potential gravitational energy densities plus two terms with static and parallel pressures. The application of Bernoulli’s equation and the corresponding relation for compressible fluids in the energy density expression has resulted in two new formulations. For incompressible and compressible gas, the energy density expressions are written as a function of stagnation, static and parallel pressures, without any dependence on kinetic or gravitational potential energy densities. These expressions of the energy density are the main contributions of this work. When the parallel pressure was uniform, the energy density distribution for incompressible approximation and compressible gas did not converge to zero for the limit of null static pressure. This result is rather unusual because the temperature tends to zero for null pressure. When the gas was considered incompressible and the parallel pressure was equal to static pressure, the energy density maintained this unusual behaviour with small pressures. If the parallel pressure was equal to static pressure, the energy density converged to zero for the limit of the
PREDICTION OF THERMODYNAMIC PROPERTIES OF COMPLEX FLUIDS
International Nuclear Information System (INIS)
Marc Donohue
2006-01-01
The goal of this research has been to generalize Density Functional Theory (DFT) for complex molecules, i.e. molecules whose size, shape, and interaction energies cause them to show significant deviations from mean-field behavior. We considered free energy functionals and minimized them for systems with different geometries and dimensionalities including confined fluids (such as molecular layers on surfaces and molecules in nano-scale pores), systems with directional interactions and order-disorder transitions, amphiphilic dimers, block copolymers, and self-assembled nano-structures. The results of this procedure include equations of equilibrium for these systems and the development of computational tools for predicting phase transitions and self-assembly in complex fluids. DFT was developed for confined fluids. A new phenomenon, surface compression of confined fluids, was predicted theoretically and confirmed by existing experimental data and by simulations. The strong attraction to a surface causes adsorbate molecules to attain much higher densities than that of a normal liquid. Under these conditions, adsorbate molecules are so compressed that they repel each other. This phenomenon is discussed in terms of experimental data, results of Monte Carlo simulations, and theoretical models. Lattice version of DFT was developed for modeling phase transitions in adsorbed phase including wetting, capillary condensation, and ordering. Phase behavior of amphiphilic dimers on surfaces and in solutions was modeled using lattice DFT and Monte Carlo simulations. This study resulted in predictive models for adsorption isotherms and for local density distributions in solutions. We have observed a wide variety of phase behavior for amphiphilic dimers, including formation of lamellae and micelles. Block copolymers were modeled in terms of configurational probabilities and in the approximation of random mixing entropy. Probabilities of different orientations for the segments were
Correlation energy generating potentials for molecular hydrogen
International Nuclear Information System (INIS)
Sharma, B.S.; Thakkar, A.J.
1985-01-01
A variety of local correlation energy functionals are currently in use. All of them depend, to some extent, on modeling the correlation energy of a homogeneous electron fluid. Since atomic and molecular charge densities are neither uniform nor slowly varying, it is important to attempt to use known high accuracy wave functions to learn about correlation energy functionals appropriate to such systems. We have extended the definition of the correlation energy generating potentials V/sub c/ introduced by Ros. A charge density response to correlation has been allowed for by inclusion of an electron--nuclear component V/sup e/n/sub c/ in addition to the electron--electron component V/sup e/e/sub c/. Two different definitions of V/sup e/n/sub c/ are given. We present the first calculations of V/sub c/ for a molecular system: H 2 . The results show that V/sup e/n/sub c/, in either definition, is by no means negligible. Moreover, V/sup e/e/sub c/ and both forms of V/sup e/n/sub c/ show significant nonlocal dependence on the charge density. Calculations with ten different model correlation energy functionals show that none of them is particularly sensitive to the charge density. However, they are quite sensitive to the parametrization of the electron fluid correlation energy. The schemes which include self-interaction corrections (SIC) are found to be superior to those of Kohn--Sham type. The correlation energy generating potentials implied by the SIC type and empirical correlation energy functionals are found to correspond roughly to averages of one of the accurate potentials
Melting slope of MgO from molecular dynamics and density functional theory
Tangney, Paul; Scandolo, Sandro
2009-09-01
We combine density functional theory (DFT) with molecular dynamics simulations based on an accurate atomistic force field to calculate the pressure derivative of the melting temperature of magnesium oxide at ambient pressure—a quantity for which a serious disagreement between theory and experiment has existed for almost 15 years. We find reasonable agreement with previous DFT results and with a very recent experimental determination of the slope. We pay particular attention to areas of possible weakness in theoretical calculations and conclude that the long-standing discrepancy with experiment could only be explained by a dramatic failure of existing density functionals or by flaws in the original experiment.
Low-temperature susceptibility of concentrated magnetic fluids
Pshenichnikov, Alexander F.; Lebedev, Alexander V.
2004-09-01
The initial susceptibility of concentrated magnetic fluids (ferrocolloids) has been experimentally investigated at low temperatures. The results obtained indicate that the interparticle dipole-dipole interactions can increase the susceptibility by several times as compared to the Langevin value. It is shown that good agreement between recent theoretical models and experimental observations can be achieved by introducing a correction for coefficients in the series expansion of susceptibility in powers of density and aggregation parameter. A modified equation for equilibrium susceptibility is offered to sum over corrections made by Kalikmanov (Statistical Physics of Fluids, Springer-Verlag, Berlin, 2001) and by B. Huke and M. Lücke (Phys. Rev. E 67, 051403, 2003). The equation gives good quantitative agreement with the experimental data in the wide range of temperature and magnetic particles concentration. It has been found that in some cases the magnetic fluid solidification occurs at temperature several tens of kelvins higher than the crystallization temperature of the carrier liquid. The solidification temperature of magnetic fluids is independent of particle concentration (i.e., magneto-dipole interparticle interactions) and dependent on the surfactant type and carrier liquid. This finding allows us to suggest that molecular interactions and generation of some large-scale structure from colloidal particles in magnetic fluids are responsible for magnetic fluid solidification. If the magnetic fluid contains the particles with the Brownian relaxation mechanism of the magnetic moment, the solidification manifests itself as the peak on the "susceptibility-temperature" curve. This fact proves the dynamic nature of the observed peak: it arises from blocking the Brownian mechanism of the magnetization relaxation.
Molecular Dynamics Analyses on Microscopic Contact Angle - Effect of Wall Atom Configuration
International Nuclear Information System (INIS)
Takahiro Ito; Yosuke Hirata; Yutaka Kukita
2006-01-01
Boiling or condensing phenomena of liquid on the solid surface is greatly affected by the wetting condition of the liquid to the solid. Although the contact angle is one of the most important parameter to represent the wetting condition, the behavior of the contact angle is not understood well, especially in the dynamic condition. In this study we made molecular dynamics simulations to investigate the microscopic contact angle behavior under several conditions on the numerical density of the wall atoms. In the analyses, when the number density of the wall is lower, the changing rate of the dynamics contact angles for the variation of ΔV was higher than those for the case where the wall density is higher. This is mainly due to the crystallization of the fluid near the wall and subsequent decrease in the slip between the fluid and the wall. The analyses also show that the static contact angle decreases with increase in the number density of the wall. This was mainly induced by the increase in the number density of the wall itself. (authors)
Wyrick, Jonathan; Einstein, T. L.; Bartels, Ludwig
2015-03-01
We present a method of analyzing the results of density functional modeling of molecular adsorption in terms of an analogue of molecular orbitals. This approach permits intuitive chemical insight into the adsorption process. Applied to a set of anthracene derivates (anthracene, 9,10-anthraquinone, 9,10-dithioanthracene, and 9,10-diselenonanthracene), we follow the electronic states of the molecules that are involved in the bonding process and correlate them to both the molecular adsorption geometry and the species' diffusive behavior. We additionally provide computational code to easily repeat this analysis on any system.
High-Density Livestock Production and Molecularly Characterized MRSA Infections in Pennsylvania
Casey, Joan A.; Shopsin, Bo; Cosgrove, Sara E.; Nachman, Keeve E.; Curriero, Frank C.; Rose, Hannah R.
2014-01-01
Background: European studies suggest that living near high-density livestock production increases the risk of sequence type (ST) 398 methicillin-resistant Staphylococcus aureus (MRSA) colonization. To our knowledge, no studies have evaluated associations between livestock production and human infection by other strain types. Objectives: We evaluated associations between MRSA molecular subgroups and high-density livestock production. Methods: We conducted a yearlong 2012 prospective study on a stratified random sample of patients with culture-confirmed MRSA infection; we oversampled patients from the Geisinger Health System with exposure to high-density livestock production in Pennsylvania. Isolates were characterized using S. aureus protein A (spa) typing and detection of Panton-Valentine leukocidin (PVL) and scn genes. We compared patients with one of two specific MRSA strains with patients with all other strains of MRSA isolates, using logistic regression that accounted for the sampling design, for two different exposure models: one based on the location of the animals (livestock model) and the other on crop field application of manure (crop field model). Results: Of 196 MRSA isolates, we identified 30 spa types, 47 PVL-negative and 15 scn-negative isolates, and no ST398 MRSA. Compared with quartiles 1–3 combined, the highest quartiles of swine livestock and dairy/veal crop field exposures were positively associated with community-onset-PVL-negative MRSA (CO-PVL-negative MRSA vs. all other MRSA), with adjusted odds ratios of 4.24 (95% CI: 1.60, 11.25) and 4.88 (95% CI: 1.40, 17.00), respectively. The association with CO-PVL-negative MRSA infection increased across quartiles of dairy/veal livestock exposure (trend p = 0.05). Conclusions: Our findings suggest that other MRSA strains, beyond ST398, may be involved in livestock-associated MRSA infection in the United States. Citation: Casey JA, Shopsin B, Cosgrove SE, Nachman KE, Curriero FC, Rose HR, Schwartz BS
Geysermans, P; Elyeznasni, N; Russier, V
2005-11-22
We present a study of the structure in the interface between two immiscible liquids by density-functional theory and molecular-dynamics calculations. The liquids are modeled by Lennard-Jones potentials, which achieve immiscibility by suppressing the attractive interaction between unlike particles. The density profiles of the liquids display oscillations only in a limited part of the simple liquid-phase diagram (rho,T). When approaching the liquid-vapor coexistence, a significant depletion appears while the layering behavior of the density profile vanishes. By analogy with the liquid-vapor interface and the analysis of the adsorption this behavior is suggested to be strongly related to the drying transition.
Chaplin, Vernon H.; Bellan, Paul M.
2015-12-01
A time-dependent two-fluid model has been developed to understand axial variations in the plasma parameters in a very high density (peak ne≳ 5 ×1019 m-3 ) argon inductively coupled discharge in a long 1.1 cm radius tube. The model equations are written in 1D with radial losses to the tube walls accounted for by the inclusion of effective particle and energy sink terms. The ambipolar diffusion equation and electron energy equation are solved to find the electron density ne(z ,t ) and temperature Te(z ,t ) , and the populations of the neutral argon 4s metastable, 4s resonant, and 4p excited state manifolds are calculated to determine the stepwise ionization rate and calculate radiative energy losses. The model has been validated through comparisons with Langmuir probe ion saturation current measurements; close agreement between the simulated and measured axial plasma density profiles and the initial density rise rate at each location was obtained at pA r=30 -60 mTorr . We present detailed results from calculations at 60 mTorr, including the time-dependent electron temperature, excited state populations, and energy budget within and downstream of the radiofrequency antenna.
Langenbach, K.; Heilig, M.; Horsch, M.; Hasse, H.
2018-03-01
A new method for predicting homogeneous bubble nucleation rates of pure compounds from vapor-liquid equilibrium (VLE) data is presented. It combines molecular dynamics simulation on the one side with density gradient theory using an equation of state (EOS) on the other. The new method is applied here to predict bubble nucleation rates in metastable liquid carbon dioxide (CO2). The molecular model of CO2 is taken from previous work of our group. PC-SAFT is used as an EOS. The consistency between the molecular model and the EOS is achieved by adjusting the PC-SAFT parameters to VLE data obtained from the molecular model. The influence parameter of density gradient theory is fitted to the surface tension of the molecular model. Massively parallel molecular dynamics simulations are performed close to the spinodal to compute bubble nucleation rates. From these simulations, the kinetic prefactor of the hybrid nucleation theory is estimated, whereas the nucleation barrier is calculated from density gradient theory. This enables the extrapolation of molecular simulation data to the whole metastable range including technically relevant densities. The results are tested against available experimental data and found to be in good agreement. The new method does not suffer from typical deficiencies of classical nucleation theory concerning the thermodynamic barrier at the spinodal and the bubble size dependence of surface tension, which is typically neglected in classical nucleation theory. In addition, the density in the center of critical bubbles and their surface tension is determined as a function of their radius. The usual linear Tolman correction to the capillarity approximation is found to be invalid.
Langenbach, K; Heilig, M; Horsch, M; Hasse, H
2018-03-28
A new method for predicting homogeneous bubble nucleation rates of pure compounds from vapor-liquid equilibrium (VLE) data is presented. It combines molecular dynamics simulation on the one side with density gradient theory using an equation of state (EOS) on the other. The new method is applied here to predict bubble nucleation rates in metastable liquid carbon dioxide (CO 2 ). The molecular model of CO 2 is taken from previous work of our group. PC-SAFT is used as an EOS. The consistency between the molecular model and the EOS is achieved by adjusting the PC-SAFT parameters to VLE data obtained from the molecular model. The influence parameter of density gradient theory is fitted to the surface tension of the molecular model. Massively parallel molecular dynamics simulations are performed close to the spinodal to compute bubble nucleation rates. From these simulations, the kinetic prefactor of the hybrid nucleation theory is estimated, whereas the nucleation barrier is calculated from density gradient theory. This enables the extrapolation of molecular simulation data to the whole metastable range including technically relevant densities. The results are tested against available experimental data and found to be in good agreement. The new method does not suffer from typical deficiencies of classical nucleation theory concerning the thermodynamic barrier at the spinodal and the bubble size dependence of surface tension, which is typically neglected in classical nucleation theory. In addition, the density in the center of critical bubbles and their surface tension is determined as a function of their radius. The usual linear Tolman correction to the capillarity approximation is found to be invalid.
International Nuclear Information System (INIS)
Stauss, Sven; Terashima, Kazuo; Muneoka, Hitoshi; Urabe, Keiichiro
2015-01-01
Plasma-based fabrication of novel nanomaterials and nanostructures is indispensible for the development of next-generation electronic devices and for green energy applications. In particular, controlling the interactions between plasmas and materials interfaces, and the plasma fluctuations, is crucial for further development of plasma-based processes and bottom-up growth of nanomaterials. Electric discharge microplasmas generated in supercritical fluids represent a special class of high-pressure plasmas, where fluctuations on the molecular scale influence the discharge properties and the possible bottom-up growth of nanomaterials. This review discusses an anomaly observed for direct current microplasmas generated near the critical point, a local decrease in the breakdown voltage. This anomalous behavior is suggested to be caused by the concomitant decrease of the ionization potential due to the formation of clusters near the critical point, and the formation of extended electron mean free paths caused by the high-density fluctuation near the critical point. It is also shown that in the case of dielectric barrier microdischarges generated close to the critical point, the high-density fluctuation of the supercritical fluid persists. The final part of the review discusses the application of discharges generated in supercritical fluids to synthesis of nanomaterials, in particular, molecular diamond—so-called diamondoids—by microplasmas generated inside conventional batch-type and continuous flow microreactors
Sun, Hongbing; Feistel, Rainer; Koch, Manfred; Markoe, Andrew
2008-10-01
A set of fitted polynomial equations for calculating the physical variables density, entropy, heat capacity and potential temperature of a thermal saline fluid for a temperature range of 0-374 °C, pressure range of 0.1-100 MPa and absolute salinity range of 0-40 g/kg is established. The freshwater components of the equations are extracted from the recently released tabulated data of freshwater properties of Wagner and Pruß [2002. The IAPWS formulation 1995 for the thermodynamic properties of ordinary water substance for general and scientific use. Journal of Physical and Chemical Reference Data 31, 387-535]. The salt water component of the equation is based on the near-linear relationship between density, salinity and specific heat capacity and is extracted from the data sets of Feistel [2003. A new extended Gibbs thermodynamic potential of seawater. Progress in Oceanography 58, 43-114], Bromley et al. [1970. Heat capacities and enthalpies of sea salt solutions to 200 °C. Journal of Chemical and Engineering Data 15, 246-253] and Grunberg [1970. Properties of sea water concentrates. In: Third International Symposium on Fresh Water from the Sea, vol. 1, pp. 31-39] in a temperature range 0-200 °C, practical salinity range 0-40, and varying pressure and is also calibrated by the data set of Millero et al. [1981. Summary of data treatment for the international high pressure equation of state for seawater. UNESCO Technical Papers in Marine Science 38, 99-192]. The freshwater and salt water components are combined to establish a workable multi-polynomial equation, whose coefficients were computed through standard linear regression analysis. The results obtained in this way for density, entropy and potential temperature are comparable with those of existing models, except that our new equations cover a wider temperature—(0-374 °C) than the traditional (0-40 °C) temperature range. One can apply these newly established equations to the calculation of in-situ or
Thermophysical properties of supercritical fluids and fluid mixtures
International Nuclear Information System (INIS)
Sengers, J.V.
1991-07-01
This research is concerned with the development of a quantitative scientific description of the thermodynamic and transport properties of supercritical and subcritical fluids and fluid mixtures. It is known that the thermophysical properties of fluids and fluid mixtures asymptotically close to the critical point satisfy scaling laws with universal critical exponents and universal scaling functions. However, the range of validity of these asymptotic scaling laws is quite small. As a consequence, the impact of the modern theory of critical phenomena on chemical engineering has been limited. On the other hand, an a priori estimate of the range of temperatures and densities, where critical fluctuations become significant, can be made on the basis of the so-called Ginzburg criterion. A recent analysis of this criterion suggests that this range is actually quite large and for a fluid like carbon dioxide can easily extend to 100 degrees or so above the critical temperature. Hence, the use of traditional engineering equations like cubic equations is not scientifically justified in a very wide range of temperatures and densities around the critical point. We have therefore embarked on a scientific approach to deal with the global effects of critical fluctuations on the thermophysical properties of fluids and fluid mixtures. For this purpose it is not sufficient to consider the asymptotic critical fluctuations but we need to deal also with the nonasymptotic critical fluctuations. The goal is to develop scientifically based questions that account for the crossover of the thermophysical properties from their asymptotic singular behavior in the near vicinity of the critical point to their regular behavior very far away from the critical point
Dimensional crossover in fluids under nanometer-scale confinement.
Das, Amit; Chakrabarti, J
2012-05-01
Several earlier studies have shown signatures of crossover in various static and dynamics properties of a confined fluid when the confining dimension decreases to about a nanometer. The density fluctuations govern the majority of such properties of a fluid. Here, we illustrate the crossover in density fluctuation in a confined fluid, to provide a generic understanding of confinement-induced crossover of fluid properties, using computer simulations. The crossover can be understood as a manifestation of changes in the long-wavelength behavior of fluctuation in density due to geometrical constraints. We further show that the confining potential significantly affects the crossover behavior.
A Thermodynamically-Consistent Non-Ideal Stochastic Hard-Sphere Fluid
Energy Technology Data Exchange (ETDEWEB)
Donev, A; Alder, B J; Garcia, A L
2009-08-03
A grid-free variant of the Direct Simulation Monte Carlo (DSMC) method is proposed, named the Isotropic DSMC (I-DSMC) method, that is suitable for simulating collision-dominated dense fluid flows. The I-DSMC algorithm eliminates all grid artifacts from the traditional DSMC algorithm and is Galilean invariant and microscopically isotropic. The stochastic collision rules in I-DSMC are modified to introduce a non-ideal structure factor that gives consistent compressibility, as first proposed in [Phys. Rev. Lett. 101:075902 (2008)]. The resulting Stochastic Hard Sphere Dynamics (SHSD) fluid is empirically shown to be thermodynamically identical to a deterministic Hamiltonian system of penetrable spheres interacting with a linear core pair potential, well-described by the hypernetted chain (HNC) approximation. We develop a kinetic theory for the SHSD fluid to obtain estimates for the transport coefficients that are in excellent agreement with particle simulations over a wide range of densities and collision rates. The fluctuating hydrodynamic behavior of the SHSD fluid is verified by comparing its dynamic structure factor against theory based on the Landau-Lifshitz Navier-Stokes equations. We also study the Brownian motion of a nano-particle suspended in an SHSD fluid and find a long-time power-law tail in its velocity autocorrelation function consistent with hydrodynamic theory and molecular dynamics calculations.
Thermal conductivity of the Lennard-Jones chain fluid model.
Galliero, Guillaume; Boned, Christian
2009-12-01
Nonequilibrium molecular dynamics simulations have been performed to estimate, analyze, and correlate the thermal conductivity of a fluid composed of short Lennard-Jones chains (up to 16 segments) over a large range of thermodynamic conditions. It is shown that the dilute gas contribution to the thermal conductivity decreases when the chain length increases for a given temperature. In dense states, simulation results indicate that the residual thermal conductivity of the monomer increases strongly with density, but is weakly dependent on the temperature. Compared to the monomer value, it has been noted that the residual thermal conductivity of the chain was slightly decreasing with its length. Using these results, an empirical relation, including a contribution due to the critical enhancement, is proposed to provide an accurate estimation of the thermal conductivity of the Lennard-Jones chain fluid model (up to 16 segments) over the domain 0.8values of the Lennard-Jones chain fluid model merge on the same "universal" curve when plotted as a function of the excess entropy. Furthermore, it is shown that the reduced configurational thermal conductivity of the Lennard-Jones chain fluid model is approximately proportional to the reduced excess entropy for all fluid states and all chain lengths.
Molecular structures from density functional calculations with simulated annealing
International Nuclear Information System (INIS)
Jones, R.O.
1991-01-01
The geometrical structure of any aggregate of atoms is one of its basic properties and, in principle, straightforward to predict. One chooses a structure, determines the total energy E of the system of electrons and ions, and repeats the calculation for all possible geometries. The ground state structure is that with the lowest energy. A quantum mechanical calculation of the exact wave function Ψ would lead to the total energy, but this is practicable only in very small molecules. Furthermore, the number of local minima in the energy surface increases dramatically with increasing molecular size. While traditional ab initio methods have had many impressive successes, the difficulties have meant that they have focused on systems with relatively few local minima, or have used experiments or experience to limit the range of geometries studied. On the other hand, calculations for much larger molecules and extended systems are often forced to use simplifying assumptions about the interatomic forces that limit their predictive capability. The approach described here avoids both of these extremes: Total energies of predictive value are calculated without using semi-empirical force laws, and the problem of multiple minima in the energy surface is addressed. The density functional formalism, with a local density approximation for the exchange-correlation energy, allows one to calculate the total energy for a given geometry in an efficient, if approximate, manner. Calculations for heavier elements are not significantly more difficult than for those in the first row and provide an ideal way to study bonding trends. When coupled with finite-temperature molecular dynamics, this formalism can avoid many of the energetically unfavorable minima in the energy surface. We show here that the method leads to surprising and exciting results. (orig.)
Fluids with highly directional attractive forces. III. Multiple attraction sites
International Nuclear Information System (INIS)
Wertheim, M.S.
1986-01-01
The authors derive a reformulation of statistical thermodynamics for fluids of molecules which interact by highly directional attraction. The molecular model consists of a repulsive core and several sites of very short-ranged attraction. The authors explore the relationship between graph cancellation in the fugacity expansion and three types of steric incompatibility between repulsive and attractive interactions involving several molecules. The steric effects are used to best advantage in a limited regrouping of bonds. This controls the density parameters which appear when articulation points are eliminated in the graphical representation. Each density parameter is a singlet density for a species consisting of molecules with a specified set of sites bonded. The densities satisfy subsidiary conditions of internal consistency. These conditions are equivalent to a minimization of the Helmholtz free energy A. Graphical expressions for A and for the pressure are derived. Analogs of the s-particle direct correlation functions and of the Ornstein-Zernike equation are found
Nishimoto, Yoshio; Fedorov, Dmitri G.
2018-02-01
The exactly analytic gradient is derived and implemented for the fragment molecular orbital (FMO) method combined with density-functional tight-binding (DFTB) using adaptive frozen orbitals. The response contributions which arise from freezing detached molecular orbitals on the border between fragments are computed by solving Z-vector equations. The accuracy of the energy, its gradient, and optimized structures is verified on a set of representative inorganic materials and polypeptides. FMO-DFTB is applied to optimize the structure of a silicon nano-wire, and the results are compared to those of density functional theory and experiment. FMO accelerates the DFTB calculation of a boron nitride nano-ring with 7872 atoms by a factor of 406. Molecular dynamics simulations using FMO-DFTB applied to a 10.7 μm chain of boron nitride nano-rings, consisting of about 1.2 × 106 atoms, reveal the rippling and twisting of nano-rings at room temperature.
Watson, Linda C.; Martini, Paul; Lisenfeld, Ute; Böker, Torsten; Schinnerer, Eva
2016-01-01
Studying star formation beyond the optical radius of galaxies allows us to test empirical relations in extreme conditions with low average gas density and low molecular fraction. Previous studies discovered galaxies with extended ultraviolet (XUV) discs, which often contain star-forming regions with lower Hα-to-far-UV (FUV) flux ratios compared to inner disc star-forming regions. However, most previous studies lack measurements of molecular gas, which is presumably the component of the interstellar medium out of which stars form. We analysed published CO measurements and upper limits for 15 star-forming regions in the XUV or outer disc of three nearby spiral galaxies and a new CO upper limit from the IRAM (Institut de Radioastronomie Millimétrique) 30 m telescope in one star-forming region at r = 3.4r25 in the XUV disc of NGC 4625. We found that the star-forming regions are in general consistent with the same molecular-hydrogen Kennicutt-Schmidt law that applies within the optical radius, independent of whether we used Hα or FUV as the star formation rate (SFR) tracer. However, a number of the CO detections are significantly offset towards higher SFR surface density for their molecular-hydrogen surface density. Deeper CO data may enable us to use the presence or absence of molecular gas as an evolutionary probe to break the degeneracy between age and stochastic sampling of the initial mass function as the explanation for the low Hα-to-FUV flux ratios in XUV discs.
Supercritical fluid molecular spray film deposition and powder formation
Smith, Richard D.
1986-01-01
Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercritical fluid solution at an elevated pressure and then rapidly expanding the solution through a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. Upon expansion and supersonic interaction with background gases in the low pressure region, any clusters of solvent are broken up and the solvent is vaporized and pumped away. Solute concentration in the solution is varied primarily by varying solution pressure to determine, together with flow rate, the rate of deposition and to control in part whether a film or powder is produced and the granularity of each. Solvent clustering and solute nucleation are controlled by manipulating the rate of expansion of the solution and the pressure of the lower pressure region. Solution and low pressure region temperatures are also controlled.
Puglisi, Andrea
2015-01-01
This brief offers a concise presentation of granular fluids from the point of view of non-equilibrium statistical physics. The emphasis is on fluctuations, which can be large in granular fluids due to the small system size (the number of grains is many orders of magnitude smaller than in molecular fluids). Firstly, readers will be introduced to the most intriguing experiments on fluidized granular fluids. Then granular fluid theory, which goes through increasing levels of coarse-graining and emerging collective phenomena, is described. Problems and questions are initially posed at the level of kinetic theory, which describes particle densities in full or reduced phase-space. Some answers become clear through hydrodynamics, which describes the evolution of slowly evolving fields. Granular fluctuating hydrodynamics, which builds a bridge to the most recent results in non-equilibrium statistical mechanics, is also introduced. Further and more interesting answers come when the dynamics of a massive intruder are...
Vapor-liquid equilibrium and critical asymmetry of square well and short square well chain fluids.
Li, Liyan; Sun, Fangfang; Chen, Zhitong; Wang, Long; Cai, Jun
2014-08-07
The critical behavior of square well fluids with variable interaction ranges and of short square well chain fluids have been investigated by grand canonical ensemble Monte Carlo simulations. The critical temperatures and densities were estimated by a finite-size scaling analysis with the help of histogram reweighting technique. The vapor-liquid coexistence curve in the near-critical region was determined using hyper-parallel tempering Monte Carlo simulations. The simulation results for coexistence diameters show that the contribution of |t|(1-α) to the coexistence diameter dominates the singular behavior in all systems investigated. The contribution of |t|(2β) to the coexistence diameter is larger for the system with a smaller interaction range λ. While for short square well chain fluids, longer the chain length, larger the contribution of |t|(2β). The molecular configuration greatly influences the critical asymmetry: a short soft chain fluid shows weaker critical asymmetry than a stiff chain fluid with same chain length.
Singh, Jalim; Jose, Prasanth
Results of molecular dynamics simulations of a system of Kremer and Grest linear polymer melts are presented at moderate and high number density. A detailed study of molecular pair distribution function shows that potential of mean force between the molecules has form of Gaussian with an attractive tail at number density ρ = 0.85 (in Lennard-Jones units), which is due to the dominating attractive interactions from temperature T = 0.7. This system shows gelation assisted glass transition, which is interpreted from peaks of molecular structure factor at small wave-numbers. At low temperature, this system phase separate to form dense domains whose local density is high; these domains show many dynamical features of glass transition in monomer and molecular level of relaxation indicating glass transition is assisted by gelation in this system. In the same system, at ρ = 1.0, repulsive interactions dominate, structure does not change even at low temperatures; the system exhibits dynamic heterogeneity and known to undergo glass transition. In this work, we compare and contrast the structure and dynamics of the system near its glass transition. Also, we computed correlation length of systems from the peak value of four-point structural dynamic susceptibility. HPC facility at IIT Mandi.
International Nuclear Information System (INIS)
Chao Yan; Martire, D.E.
1992-01-01
This report discusses a molecular theory of chromatography for blocklike solutes in isotropic stationary phases as an extension to the anisotopic phase approach. Its it applied to gas, liquid, and supercritical fluid chromatography
Energy Technology Data Exchange (ETDEWEB)
Sissay, Adonay [Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Abanador, Paul; Mauger, François; Gaarde, Mette; Schafer, Kenneth J. [Department of Physics and Astronomy, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Lopata, Kenneth, E-mail: klopata@lsu.edu [Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Center for Computation and Technology, Louisiana State University, Baton Rouge, Louisiana 70803 (United States)
2016-09-07
Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.
International Nuclear Information System (INIS)
Sissay, Adonay; Abanador, Paul; Mauger, François; Gaarde, Mette; Schafer, Kenneth J.; Lopata, Kenneth
2016-01-01
Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.
DEFF Research Database (Denmark)
Frutiger, Jerome; Abildskov, Jens; Sin, Gürkan
is vital. Multi-criteria database search and Computer Aided Molecular Design(CAMD) can be applied to generate, test and evaluate promising pure component/mixture candidate as process fluids to help optimize cycle design and performance. The problem formulation for the development of novel working fluids...... is anadvanced CAMD challenge both in terms of data and computational demand, because includes process related as wellas property related equations.In CAMD problems the identification of target properties is often based on expert knowledge. To support identification of relevant target properties, in this study...... allows the ranking ofsignificance of properties and also the identification of a set of properties which are relevant for the design of a workingfluids.In this study the CAMD problem for the development of novel working fluids for organic Rankine cycles (ORC) isformulated as a mathematical optimization...
Effects of molecular elongation on liquid crystalline phase behaviour: isotropic-nematic transition
Singh, Ram Chandra; Ram, Jokhan
2003-08-01
We present the density-functional approach to study the isotropic-nematic transitions and calculate the values of freezing parameters of the Gay-Berne liquid crystal model, concentrating on the effects of varying the molecular elongation, x0. For this, we have solved the Percus-Yevick integral equation theory to calculate the pair-correlation functions of a fluid the molecules of which interact via a Gay-Berne pair potential. These results have been used in the density-functional theory as an input to locate the isotropic-nematic transition and calculate freezing parameters for a range of length-to-width parameters 3.0⩽ x0⩽4.0 at reduced temperatures 0.95 and 1.25. We observed that as x0 is increased, the isotropic-nematic transition is seen to move to lower density at a given temperature. We find that the density-functional theory is good to study the freezing transitions in such fluids. We have also compared our results with computer simulation results wherever they are available.
Variational methods in molecular modeling
2017-01-01
This book presents tutorial overviews for many applications of variational methods to molecular modeling. Topics discussed include the Gibbs-Bogoliubov-Feynman variational principle, square-gradient models, classical density functional theories, self-consistent-field theories, phase-field methods, Ginzburg-Landau and Helfrich-type phenomenological models, dynamical density functional theory, and variational Monte Carlo methods. Illustrative examples are given to facilitate understanding of the basic concepts and quantitative prediction of the properties and rich behavior of diverse many-body systems ranging from inhomogeneous fluids, electrolytes and ionic liquids in micropores, colloidal dispersions, liquid crystals, polymer blends, lipid membranes, microemulsions, magnetic materials and high-temperature superconductors. All chapters are written by leading experts in the field and illustrated with tutorial examples for their practical applications to specific subjects. With emphasis placed on physical unders...
Hoy, Erik P.; Mazziotti, David A.; Seideman, Tamar
2017-11-01
Can an electronic device be constructed using only a single molecule? Since this question was first asked by Aviram and Ratner in the 1970s [Chem. Phys. Lett. 29, 277 (1974)], the field of molecular electronics has exploded with significant experimental advancements in the understanding of the charge transport properties of single molecule devices. Efforts to explain the results of these experiments and identify promising new candidate molecules for molecular devices have led to the development of numerous new theoretical methods including the current standard theoretical approach for studying single molecule charge transport, i.e., the non-equilibrium Green's function formalism (NEGF). By pairing this formalism with density functional theory (DFT), a wide variety of transport problems in molecular junctions have been successfully treated. For some systems though, the conductance and current-voltage curves predicted by common DFT functionals can be several orders of magnitude above experimental results. In addition, since density functional theory relies on approximations to the exact exchange-correlation functional, the predicted transport properties can show significant variation depending on the functional chosen. As a first step to addressing this issue, the authors have replaced density functional theory in the NEGF formalism with a 2-electron reduced density matrix (2-RDM) method, creating a new approach known as the NEGF-RDM method. 2-RDM methods provide a more accurate description of electron correlation compared to density functional theory, and they have lower computational scaling compared to wavefunction based methods of similar accuracy. Additionally, 2-RDM methods are capable of capturing static electron correlation which is untreatable by existing NEGF-DFT methods. When studying dithiol alkane chains and dithiol benzene in model junctions, the authors found that the NEGF-RDM predicts conductances and currents that are 1-2 orders of magnitude below
Turesson, Martin; Szparaga, Ryan; Ma, Ke; Woodward, Clifford E; Forsman, Jan
2014-05-14
A new classical density functional approach is developed to accurately treat a coarse-grained model of room temperature aromatic ionic liquids. Our major innovation is the introduction of charge-charge correlations, which are treated in a simple phenomenological way. We test this theory on a generic coarse-grained model for aromatic RTILs with oligomeric forms for both cations and anions, approximating 1-alkyl-3-methyl imidazoliums and BF₄⁻, respectively. We find that predictions by the new density functional theory for fluid structures at charged surfaces are very accurate, as compared with molecular dynamics simulations, across a range of surface charge densities and lengths of the alkyl chain. Predictions of interactions between charged surfaces are also presented.
Gong, Yuezheng; Zhao, Jia; Wang, Qi
2017-10-01
A quasi-incompressible hydrodynamic phase field model for flows of fluid mixtures of two incompressible viscous fluids of distinct densities and viscosities is derived by using the generalized Onsager principle, which warrants the variational structure, the mass conservation and energy dissipation law. We recast the model in an equivalent form and discretize the equivalent system in space firstly to arrive at a time-dependent ordinary differential and algebraic equation (DAE) system, which preserves the mass conservation and energy dissipation law at the semi-discrete level. Then, we develop a temporal discretization scheme for the DAE system, where the mass conservation and the energy dissipation law are once again preserved at the fully discretized level. We prove that the fully discretized algorithm is unconditionally energy stable. Several numerical examples, including drop dynamics of viscous fluid drops immersed in another viscous fluid matrix and mixing dynamics of binary polymeric solutions, are presented to show the convergence property as well as the accuracy and efficiency of the new scheme.
Molecular Rayleigh Scattering Diagnostic for Dynamic Temperature, Velocity, and Density Measurements
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.
Skarmoutsos, Ioannis; Eddaoudi, Mohamed; Maurin, Guillaume
2018-01-01
.e. the Metal-Organic Framework SIFSIX-2-Cu-i. These computations unveil an unprecedented molecular symmetry dependence of the translational and rotational dynamics of fluids confined in channel-like nanoporous materials. In particular this peculiar behaviour
Acoustic Streaming and Its Suppression in Inhomogeneous Fluids
DEFF Research Database (Denmark)
Karlsen, Jonas Tobias; Qiu, Wei; Augustsson, Per
2018-01-01
We present a theoretical and experimental study of boundary-driven acoustic streaming in an inhomogeneous fluid with variations in density and compressibility. In a homogeneous fluid this streaming results from dissipation in the boundary layers (Rayleigh streaming). We show...... that in an inhomogeneous fluid, an additional nondissipative force density acts on the fluid to stabilize particular inhomogeneity configurations, which markedly alters and even suppresses the streaming flows. Our theoretical and numerical analysis of the phenomenon is supported by ultrasound experiments performed...
Hansen, J S; Daivis, Peter J; Todd, B D
2009-10-01
In this paper we present equilibrium molecular-dynamics results for the shear, rotational, and spin viscosities for fluids composed of linear molecules. The density dependence of the shear viscosity follows a stretched exponential function, whereas the rotational viscosity and the spin viscosities show approximately power-law dependencies. The frequency-dependent shear and spin viscosities are also studied. It is found that viscoelastic behavior is first manifested in the shear viscosity and that the real part of the spin viscosities features a maximum for nonzero frequency. The calculated transport coefficients are used together with the extended Navier-Stokes equations to investigate the effect of the coupling between the intrinsic angular momentum and linear momentum for highly confined fluids. Both steady and oscillatory flows are studied. It is shown, for example, that the fluid flow rate for Poiseuille flow is reduced by up to 10% in a 2 nm channel for a buta-triene fluid at density 236 kg m(-3) and temperature 306 K. The coupling effect may, therefore, become very important for nanofluidic applications.
Bonding and structure in dense multi-component molecular mixtures.
Meyer, Edmund R; Ticknor, Christopher; Bethkenhagen, Mandy; Hamel, Sebastien; Redmer, Ronald; Kress, Joel D; Collins, Lee A
2015-10-28
We have performed finite-temperature density functional theory molecular dynamics simulations on dense methane, ammonia, and water mixtures (CH4:NH3:H2O) for various compositions and temperatures (2000 K ≤ T ≤ 10,000 K) that span a set of possible conditions in the interiors of ice-giant exoplanets. The equation-of-state, pair distribution functions, and bond autocorrelation functions (BACF) were used to probe the structure and dynamics of these complex fluids. In particular, an improvement to the choice of the cutoff in the BACF was developed that allowed analysis refinements for density and temperature effects. We note the relative changes in the nature of these systems engendered by variations in the concentration ratios. A basic tenet emerges from all these comparisons that varying the relative amounts of the three heavy components (C,N,O) can effect considerable changes in the nature of the fluid and may in turn have ramifications for the structure and composition of various planetary layers.
Supersonic beams at high particle densities: model description beyond the ideal gas approximation.
Christen, Wolfgang; Rademann, Klaus; Even, Uzi
2010-10-28
Supersonic molecular beams constitute a very powerful technique in modern chemical physics. They offer several unique features such as a directed, collision-free flow of particles, very high luminosity, and an unsurpassed strong adiabatic cooling during the jet expansion. While it is generally recognized that their maximum flow velocity depends on the molecular weight and the temperature of the working fluid in the stagnation reservoir, not a lot is known on the effects of elevated particle densities. Frequently, the characteristics of supersonic beams are treated in diverse approximations of an ideal gas expansion. In these simplified model descriptions, the real gas character of fluid systems is ignored, although particle associations are responsible for fundamental processes such as the formation of clusters, both in the reservoir at increased densities and during the jet expansion. In this contribution, the various assumptions of ideal gas treatments of supersonic beams and their shortcomings are reviewed. It is shown in detail that a straightforward thermodynamic approach considering the initial and final enthalpy is capable of characterizing the terminal mean beam velocity, even at the liquid-vapor phase boundary and the critical point. Fluid properties are obtained using the most accurate equations of state available at present. This procedure provides the opportunity to naturally include the dramatic effects of nonideal gas behavior for a large variety of fluid systems. Besides the prediction of the terminal flow velocity, thermodynamic models of isentropic jet expansions permit an estimate of the upper limit of the beam temperature and the amount of condensation in the beam. These descriptions can even be extended to include spinodal decomposition processes, thus providing a generally applicable tool for investigating the two-phase region of high supersaturations not easily accessible otherwise.
Vermorel, Romain; Oulebsir, Fouad; Galliero, Guillaume
2017-09-14
The computation of diffusion coefficients in molecular systems ranks among the most useful applications of equilibrium molecular dynamics simulations. However, when dealing with the problem of fluid diffusion through vanishingly thin interfaces, classical techniques are not applicable. This is because the volume of space in which molecules diffuse is ill-defined. In such conditions, non-equilibrium techniques allow for the computation of transport coefficients per unit interface width, but their weak point lies in their inability to isolate the contribution of the different physical mechanisms prone to impact the flux of permeating molecules. In this work, we propose a simple and accurate method to compute the diffusional transport coefficient of a pure fluid through a planar interface from equilibrium molecular dynamics simulations, in the form of a diffusion coefficient per unit interface width. In order to demonstrate its validity and accuracy, we apply our method to the case study of a dilute gas diffusing through a smoothly repulsive single-layer porous solid. We believe this complementary technique can benefit to the interpretation of the results obtained on single-layer membranes by means of complex non-equilibrium methods.
Two-equation and multi-fluid turbulence models for Rayleigh–Taylor mixing
International Nuclear Information System (INIS)
Kokkinakis, I.W.; Drikakis, D.; Youngs, D.L.; Williams, R.J.R.
2015-01-01
Highlights: • We present a new improved version of the K–L model. • The improved K–L is found in good agreement with the multi-fluid model and ILES. • The study concerns Rayleigh–Taylor flows at initial density ratios 3:1 and 20:1. - Abstract: This paper presents a new, improved version of the K–L model, as well as a detailed investigation of K–L and multi-fluid models with reference to high-resolution implicit large eddy simulations of compressible Rayleigh–Taylor mixing. The accuracy of the models is examined for different interface pressures and specific heat ratios for Rayleigh–Taylor flows at initial density ratios 3:1 and 20:1. It is shown that the original version of the K–L model requires modifications in order to provide comparable results to the multi-fluid model. The modifications concern the addition of an enthalpy diffusion term to the energy equation; the formulation of the turbulent kinetic energy (source) term in the K equation; and the calculation of the local Atwood number. The proposed modifications significantly improve the results of the K–L model, which are found in good agreement with the multi-fluid model and implicit large eddy simulations with respect to the self-similar mixing width; peak turbulent kinetic energy growth rate, as well as volume fraction and turbulent kinetic energy profiles. However, a key advantage of the two-fluid model is that it can represent the degree of molecular mixing in a direct way, by transferring mass between the two phases. The limitations of the single-fluid K–L model as well as the merits of more advanced Reynolds-averaged Navier–Stokes models are also discussed throughout the paper.
International Nuclear Information System (INIS)
Bocquet, L.; Hansen, J.P.; Piasecki, J.
1994-01-01
The friction coefficient γ exerted by a hard-sphere fluid on an infinitely massive Brownian sphere is calculated for several size ratios Σ/σ where Σ and σ are the diameters of the Brownian and fluid spheres, respectively. The exact microscopic expression derived in part I of this work from kinetic theory is transformed and shown to be proportional to the time integral of the autocorrelation function of the momentum transferred from the fluid to the Brownian sphere during instantaneous collisions. Three different methods are described to extract the friction coefficient from molecular dynamics simulations carried out on finite systems. The three independent methods lead to estimates of γ which agree within statistical errors (typically 5%). The results are compared to the predictions of Enskog theory and of the hydrodynamic Stokes law. The former breaks down as the size ratio and/or the packing fraction of the fluid increase. Somewhat surprisingly, Stokes' law is found to hold with stick boundary conditions, in the range 1 ≤ Σ/σ ≤ 4.5 explored in the present simulations, with a hydrodynamic diameter d=Σ. The analysis of the molecular dynamics data on the basis of Stokes' law with slip boundary conditions is less conclusive, although the right trend is found as Σ/σ increases
Equilibrium and nonequilibrium dynamics of soft sphere fluids.
Ding, Yajun; Mittal, Jeetain
2015-07-14
We use computer simulations to test the freezing-point scaling relationship between equilibrium transport coefficients (self-diffusivity, viscosity) and thermodynamic parameters for soft sphere fluids. The fluid particles interact via the inverse-power potential (IPP), and the particle softness is changed by modifying the exponent of the distance-dependent potential term. In the case of IPP fluids, density and temperature are not independent variables and can be combined to obtain a coupling parameter to define the thermodynamic state of the system. We find that the rescaled coupling parameter, based on its value at the freezing point, can approximately collapse the diffusivity and viscosity data for IPP fluids over a wide range of particle softness. Even though the collapse is far from perfect, the freezing-point scaling relationship provides a convenient and effective way to compare the structure and dynamics of fluid systems with different particle softness. We further show that an alternate scaling relationship based on two-body excess entropy can provide an almost perfect collapse of the diffusivity and viscosity data below the freezing transition. Next, we perform nonequilibrium molecular dynamics simulations to calculate the shear-dependent viscosity and to identify the distinct role of particle softness in underlying structural changes associated with rheological properties. Qualitatively, we find a similar shear-thinning behavior for IPP fluids with different particle softness, though softer particles exhibit stronger shear-thinning tendency. By investigating the distance and angle-dependent pair correlation functions in these systems, we find different structural features in the case of IPP fluids with hard-sphere like and softer particle interactions. Interestingly, shear-thinning in hard-sphere like fluids is accompanied by enhanced translational order, whereas softer fluids exhibit loss of order with shear. Our results provide a systematic evaluation
Pitch-catch only ultrasonic fluid densitometer
Greenwood, M.S.; Harris, R.V.
1999-03-23
The present invention is an ultrasonic fluid densitometer that uses a material wedge and pitch-catch only ultrasonic transducers for transmitting and receiving ultrasonic signals internally reflected within the material wedge. Density of a fluid is determined by immersing the wedge into the fluid and measuring reflection of ultrasound at the wedge-fluid interface. 6 figs.
On-line monitoring of monoclonal antibody formation in high density perfusion culture using FIA.
Fenge, C; Fraune, E; Freitag, R; Scheper, T; Schügerl, K
1991-05-01
An automated flow injection system for on-line analysis of proteins in real fermentation fluids was developed by combining the principles of stopped-flow, merging zones flow injection analysis (FIA) with antigen-antibody reactions. IgG in the sample reacted with its corresponding antibody (a-IgG) in the reagent solution. Formation of insoluble immunocomplexes resulted in an increase of the turbidity which was determined photometrically. This system was used to monitor monoclonal antibody production in high cell density perfusion culture of hybridoma cells. Perfusion was performed with a newly developed static filtration unit equipped with hydrophilic microporous tubular membranes. Different sampling devices were tested to obtain a cell-free sample stream for on-line product analysis of high molecular weight (e.g., monoclonal antibodies) and low molecular weight (e.g., glucose, lactate) medium components. In fermentation fluids a good correlation (coefficient: 0.996) between the FIA method and an ELISA test was demonstrated. In a high density perfusion cultivation process mAb formation was successfully monitored on-line over a period of 400 h using a reliable sampling system. Glucose and lactate were measured over the same period of time using a commercially available automatic analyser based on immobilized enzyme technology.
Range-separated density-functional theory for molecular excitation energies
International Nuclear Information System (INIS)
Rebolini, E.
2014-01-01
Linear-response time-dependent density-functional theory (TDDFT) is nowadays a method of choice to compute molecular excitation energies. However, within the usual adiabatic semi-local approximations, it is not able to describe properly Rydberg, charge-transfer or multiple excitations. Range separation of the electronic interaction allows one to mix rigorously density-functional methods at short range and wave function or Green's function methods at long range. When applied to the exchange functional, it already corrects most of these deficiencies but multiple excitations remain absent as they need a frequency-dependent kernel. In this thesis, the effects of range separation are first assessed on the excitation energies of a partially-interacting system in an analytic and numerical study in order to provide guidelines for future developments of range-separated methods for excitation energy calculations. It is then applied on the exchange and correlation TDDFT kernels in a single-determinant approximation in which the long-range part of the correlation kernel vanishes. A long-range frequency-dependent second-order correlation kernel is then derived from the Bethe-Salpeter equation and added perturbatively to the range-separated TDDFT kernel in order to take into account the effects of double excitations. (author)
Raju, Muralikrishna
The interaction of dense fluids (water, polar organic solvents, room temperature ionic liquids, etc.) with solid substrates controls many chemical processes encountered in nature and industry. The key features of fluid-solid interfaces (FSIs) are the high mobility and often reactivity of the fluid phase, and the structural control provided by the solid phase. In this dissertation we apply molecular modeling methods to study FSIs in the following systems: 1. Dissociation of water on titania surfaces. We studied the adsorption and dissociation of water at 300 K on the following TiO2 surfaces: anatase (101), (100), (112), (001) and rutile (110) at various water coverages, using a recently developed ReaxFF reactive force field. The molecular and dissociative adsorption configurations predicted by ReaxFF for various water coverages agree with previous theoretical studies and experiment. 2. Mechanisms of Oriented Attachment in TiO2 nanocrystals. Oriented attachment (OA) of nanocrystals is now widely recognized as a key process in the solution-phase growth of hierarchical nanostructures. However, the microscopic origins of OA remain unclear. Using the same ReaxFF Ti/O/H reactive force field employed in the previous study, we perform molecular dynamics simulations to study the aggregation of various titanium dioxide (anatase) nanocrystals in vacuum and humid environments. 3. Li interactions in carbon based materials. Graphitic carbon is still the most ubiquitously used anode material in Li-ion batteries. In spite of its ubiquity, there are few theoretical studies that fully capture the energetics and kinetics of Li in graphite and related nanostructures at experimentally relevant length/time-scales and Li-ion concentrations. In this study we describe development and application of a ReaxFF reactive force field to describe Li interactions in perfect and defective carbon based materials using atomistic simulations. We develop force-field parameters for Li-C systems using van
Evans, Cherice; Findley, Gary L.
The quasi-free electron energy V0 (ρ) is important in understanding electron transport through a fluid, as well as for modeling electron attachment reactions in fluids. Our group has developed an isotropic local Wigner-Seitz model that allows one to successfully calculate the quasi-free electron energy for a variety of atomic and molecular fluids from low density to the density of the triple point liquid with only a single adjustable parameter. This model, when coupled with the quasi-free electron energy data and the thermodynamic data for the fluids, also can yield optimized intermolecular potential parameters and the zero kinetic energy electron scattering length. In this poster, we give a review of the isotropic local Wigner-Seitz model in comparison to previous theoretical models for the quasi-free electron energy. All measurements were performed at the University of Wisconsin Synchrotron Radiation Center. This work was supported by a Grants from the National Science Foundation (NSF CHE-0956719), the Petroleum Research Fund (45728-B6 and 5-24880), the Louisiana Board of Regents Support Fund (LEQSF(2006-09)-RD-A33), and the Professional Staff Congress City University of New York.
Brenner, Howard
2011-12-01
This paper presents a unified theory of phoretic phenomena in single-component fluids. Simple formulas are given for the phoretic velocities of small inert force-free non-Brownian particles migrating through otherwise quiescent single-component gases and liquids and animated by a gradient in the fluid's temperature (thermophoresis), pressure (barophoresis), density (pycnophoresis), or any combination thereof. The ansatz builds upon a recent paper [Phys. Rev. E 84, 046309 (2011)] concerned with slip of the fluid's mass velocity at solid surfaces--that is, with phenomena arising from violations of the classical no-slip fluid-mechanical boundary condition. Experimental and other data are cited in support of the phoretic model developed herein.
Supercritical fluid molecular spray thin films and fine powders
Smith, Richard D.
1988-01-01
Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercritical fluid solution at an elevated pressure and then rapidly expanding the solution through a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. The solvent is vaporized and pumped away. Solution pressure is varied to determine, together with flow rate, the rate of deposition and to control in part whether a film or powder is produced and the granularity of each. Solution temperature is varied in relation to formation of a two-phase system during expansion to control porosity of the film or powder. A wide variety of film textures and powder shapes are produced of both organic and inorganic compounds. Films are produced with regular textural feature dimensions of 1.0-2.0 .mu.m down to a range of 0.01 to 0.1 .mu.m. Powders are formed in very narrow size distributions, with average sizes in the range of 0.02 to 5 .mu.m.
Novel changes in discoidal high density lipoprotein morphology: a molecular dynamics study.
Catte, Andrea; Patterson, James C; Jones, Martin K; Jerome, W Gray; Bashtovyy, Denys; Su, Zhengchang; Gu, Feifei; Chen, Jianguo; Aliste, Marcela P; Harvey, Stephen C; Li, Ling; Weinstein, Gilbert; Segrest, Jere P
2006-06-15
ApoA-I is a uniquely flexible lipid-scavenging protein capable of incorporating phospholipids into stable particles. Here we report molecular dynamics simulations on a series of progressively smaller discoidal high density lipoprotein particles produced by incremental removal of palmitoyloleoylphosphatidylcholine via four different pathways. The starting model contained 160 palmitoyloleoylphosphatidylcholines and a belt of two antiparallel amphipathic helical lipid-associating domains of apolipoprotein (apo) A-I. The results are particularly compelling. After a few nanoseconds of molecular dynamics simulation, independent of the starting particle and method of size reduction, all simulated double belts of the four lipidated apoA-I particles have helical domains that impressively approximate the x-ray crystal structure of lipid-free apoA-I, particularly between residues 88 and 186. These results provide atomic resolution models for two of the particles produced by in vitro reconstitution of nascent high density lipoprotein particles. These particles, measuring 95 angstroms and 78 angstroms by nondenaturing gradient gel electrophoresis, correspond in composition and in size/shape (by negative stain electron microscopy) to the simulated particles with molar ratios of 100:2 and 50:2, respectively. The lipids of the 100:2 particle family form minimal surfaces at their monolayer-monolayer interface, whereas the 50:2 particle family displays a lipid pocket capable of binding a dynamic range of phospholipid molecules.
Acoustic Streaming and Its Suppression in Inhomogeneous Fluids.
Karlsen, Jonas T; Qiu, Wei; Augustsson, Per; Bruus, Henrik
2018-02-02
We present a theoretical and experimental study of boundary-driven acoustic streaming in an inhomogeneous fluid with variations in density and compressibility. In a homogeneous fluid this streaming results from dissipation in the boundary layers (Rayleigh streaming). We show that in an inhomogeneous fluid, an additional nondissipative force density acts on the fluid to stabilize particular inhomogeneity configurations, which markedly alters and even suppresses the streaming flows. Our theoretical and numerical analysis of the phenomenon is supported by ultrasound experiments performed with inhomogeneous aqueous iodixanol solutions in a glass-silicon microchip.
The turbulent mixing of non-Newtonian fluids
Demianov, A. Yu; Doludenko, A. N.; Inogamov, N. A.; Son, E. E.
2013-07-01
The turbulence caused by the Rayleigh-Taylor instability represents a complicated phenomenon. It is usually related to the major hydrodynamic activities, the tangling of the media contact boundary, merging, separation and intermixing of originally smoothed initial structures. An important role in the theory of the Rayleigh-Taylor instability is played by the discontinuity of density on a contact interface between two homogeneous (in terms of density) fluids. A numerical modeling of the intermixing of two fluids with different rheology whose densities differ twice as a result of the Rayleigh-Taylor instability has been carried out. The coefficients of turbulent intermixing in a multimode statement of the problem for the Bingham, dilatant and pseudo-plastic fluids have been obtained.
Density Fluctuation in Aqueous Solutions and Molecular Origin of Salting-Out Effect for CO2
International Nuclear Information System (INIS)
Ho, Tuan Anh; Ilgen, Anastasia
2017-01-01
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 2 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.
Schellart, W. P.
Analogue models of lithospheric deformation and fluid dynamic models of mantle flow mostly use some kind of syrup such as honey or glucose syrup to simulate the low-viscosity sub-lithospheric mantle. This paper describes detailed rheological tests and density measurements of three brands of glucose
Piezooptic behavior of certain fluids
International Nuclear Information System (INIS)
Weiss, J.D.
1985-01-01
In this paper we present an analysis of pressure--volume data for certain optical fluids, which characterizes them by two parameters: their bulk moduli and the pressure derivative of their bulk moduli, both evaluated at zero pressure. We then relate their refractive-index changes to density and pressure using this analysis and the Lorentz-Lorenz equation with a density-dependent polarizability. An example of the use of such fluids in a fiber-optic pressure gauge being developed at Sandia is also discussed
Humidity-insensitive water evaporation from molecular complex fluids.
Salmon, Jean-Baptiste; Doumenc, Frédéric; Guerrier, Béatrice
2017-09-01
We investigated theoretically water evaporation from concentrated supramolecular mixtures, such as solutions of polymers or amphiphilic molecules, using numerical resolutions of a one-dimensional model based on mass transport equations. Solvent evaporation leads to the formation of a concentrated solute layer at the drying interface, which slows down evaporation in a long-time-scale regime. In this regime, often referred to as the falling rate period, evaporation is dominated by diffusive mass transport within the solution, as already known. However, we demonstrate that, in this regime, the rate of evaporation does not also depend on the ambient humidity for many molecular complex fluids. Using analytical solutions in some limiting cases, we first demonstrate that a sharp decrease of the water chemical activity at high solute concentration leads to evaporation rates which depend weakly on the humidity, as the solute concentration at the drying interface slightly depends on the humidity. However, we also show that a strong decrease of the mutual diffusion coefficient of the solution enhances considerably this effect, leading to nearly independent evaporation rates over a wide range of humidity. The decrease of the mutual diffusion coefficient indeed induces strong concentration gradients at the drying interface, which shield the concentration profiles from humidity variations, except in a very thin region close to the drying interface.
Molecular simulation of the thermophysical properties of N-functionalized alkylimidazoles.
Turner, C Heath; Cooper, Alex; Zhang, Zhongtao; Shannon, Matthew S; Bara, Jason E
2012-06-07
Molecular simulations are used to probe the thermophysical properties of a series of N-functionalized alkylimidazoles, ranging from N-methylimidazole to N-heptylimidazole. These compounds have been previously synthesized, and their solvation properties have been shown to be potentially useful for CO(2) capture from industrial sources. In this work, we use first-principles calculations to fit electrostatic charges to the molecular models, which are then used to perform a series of molecular dynamics simulations. Over a range of different temperatures, we benchmark the simulated densities and heat capacities against experimental measurements. Also, we predict the Henry's constants for CO(2) absorption and probe the solvents' structures using molecular simulation techniques, such as fractional free volume analysis and void distributions. We find that our simulations are able to closely reproduce the experimental benchmarks and add additional insight into the molecular structure of these fluids, with respect to their observed solvent properties.
Polymer Drilling Fluid with Micron-Grade Cenosphere for Deep Coal Seam
Directory of Open Access Journals (Sweden)
Peng Xu
2015-01-01
Full Text Available Traditional shallow coal seam uses clean water, solid-free system, and foam system as drilling fluid, while they are not suitable for deep coal seam drilling due to mismatching density, insufficient bearing capacity, and poor reservoir protection effect. According to the existing problems of drilling fluid, micron-grade cenosphere with high bearing capacity and ultralow true density is selected as density regulator; it, together with polymer “XC + CMC” and some other auxiliary agents, is jointly used to build micron-grade polymer drilling fluid with cenosphere which is suitable for deep coal seam. Basic performance test shows that the drilling fluid has good rheological property, low filtration loss, good density adjustability, shear thinning, and thixotropy; besides, drilling fluid flow is in line with the power law rheological model. Compared with traditional drilling fluid, dispersion stability basically does not change within 26 h; settlement stability evaluated with two methods only shows a small amount of change; permeability recovery rate evaluated with Qinshui Basin deep coal seam core exceeds 80%. Polymer drilling fluid with cenosphere provides a new thought to solve the problem of drilling fluid density and pressure for deep coal seam drilling and also effectively improves the performance of reservoir protection ability.
Orbital free molecular dynamics; Approche sans orbitale des plasmas denses
Energy Technology Data Exchange (ETDEWEB)
Lambert, F
2007-08-15
The microscopic properties of hot and dense plasmas stay a field essentially studied thanks to classical theories like the One Component Plasma, models which rely on free parameters, particularly ionization. In order to investigate these systems, we have used, in this PhD work, a semi-classical model, without free parameters, that is based on coupling consistently classical molecular dynamics for the nuclei and orbital free density functional theory for the electrons. The electronic fluid is represented by a free energy entirely determined by the local density. This approximation was validated by a comparison with an ab initio technique, quantum molecular dynamics. This one is identical to the previous except for the description of the free energy that depends on a quantum-independent-particle model. Orbital free molecular dynamics was then used to compute equation of state of boron and iron plasmas in the hot and dense regime. Furthermore, comparisons with classical theories were performed on structural and dynamical properties. Finally, equation of state and transport coefficients mixing laws were studied by direct simulation of a plasma composed of deuterium and copper. (author)
Rosnik, Andreana M; Curutchet, Carles
2015-12-08
Over the past decade, both experimentalists and theorists have worked to develop methods to describe pigment-protein coupling in photosynthetic light-harvesting complexes in order to understand the molecular basis of quantum coherence effects observed in photosynthesis. Here we present an improved strategy based on the combination of quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations and excited-state calculations to predict the spectral density of electronic-vibrational coupling. We study the water-soluble chlorophyll-binding protein (WSCP) reconstituted with Chl a or Chl b pigments as the system of interest and compare our work with data obtained by Pieper and co-workers from differential fluorescence line-narrowing spectra (Pieper et al. J. Phys. Chem. B 2011, 115 (14), 4042-4052). Our results demonstrate that the use of QM/MM MD simulations where the nuclear positions are still propagated at the classical level leads to a striking improvement of the predicted spectral densities in the middle- and high-frequency regions, where they nearly reach quantitative accuracy. This demonstrates that the so-called "geometry mismatch" problem related to the use of low-quality structures in QM calculations, not the quantum features of pigments high-frequency motions, causes the failure of previous studies relying on similar protocols. Thus, this work paves the way toward quantitative predictions of pigment-protein coupling and the comprehension of quantum coherence effects in photosynthesis.
International Nuclear Information System (INIS)
Inoue, Tsuyoshi; Inutsuka, Shu-ichiro
2009-01-01
Formation of interstellar clouds as a consequence of thermal instability is studied using two-dimensional two-fluid magnetohydrodynamic simulations. We consider the situation of converging, supersonic flows of warm neutral medium in the interstellar medium that generate a shocked slab of thermally unstable gas in which clouds form. We find, as speculated in Paper I, that in the shocked slab magnetic pressure dominates thermal pressure and the thermal instability grows in the isochorically cooling, thermally unstable slab that leads to the formation of H I clouds whose number density is typically n ∼ -3 , even if the angle between magnetic field and converging flows is small. We also find that even if there is a large dispersion of magnetic field, evolution of the shocked slab is essentially determined by the angle between the mean magnetic field and converging flows. Thus, the direct formation of molecular clouds by piling up warm neutral medium does not seem to be a typical molecular cloud formation process, unless the direction of supersonic converging flows is biased to the orientation of mean magnetic field by some mechanism. However, when the angle is small, the H I shell generated as a result of converging flows is massive and possibly evolves into molecular clouds, provided gas in the massive H I shell is piled up again along the magnetic field line. We expect that another subsequent shock wave can again pile up the gas of the massive shell and produce a larger cloud. We thus emphasize the importance of multiple episodes of converging flows, as a typical formation process of molecular clouds.
Bradas, James C.; Fennelly, Alphonsus J.; Smalley, Larry L.
1987-01-01
It is shown that a generalized (or 'power law') inflationary phase arises naturally and inevitably in a simple (Bianchi type-I) anisotropic cosmological model in the self-consistent Einstein-Cartan gravitation theory with the improved stress-energy-momentum tensor with the spin density of Ray and Smalley (1982, 1983). This is made explicit by an analytical solution of the field equations of motion of the fluid variables. The inflation is caused by the angular kinetic energy density due to spin. The model further elucidates the relationship between fluid vorticity, the angular velocity of the inertially dragged tetrads, and the precession of the principal axes of the shear ellipsoid. Shear is not effective in damping the inflation.
Fluid-bed process for SYNROC production
International Nuclear Information System (INIS)
Ackerman, F.J.; Grens, J.Z.; Ryerson, F.J.; Hoenig, C.L.; Bazan, F.; Peters, P.E.; Smith, R.; Campbell, J.H.
1983-01-01
SYNROC is a titanate-based ceramic waste developed for the immobilization of high-level nuclear reactor waste. Lawrence Livermore National Laboratory (LLNL) has investigated a fluid-bed technique for the large-scale production of SYNROC precursor powders. Making SYNROC in a fluid bed permits slurry drying, calcination and reduction-oxidation reactions to be carried out in a single unit. We present the results of SYNROC fluid-bed studies from two fluid-bed units 10 cm in diameter: an internally heated fluid-bed unit developed by Exxon Idaho and an externally heated unit constructed at LLNL. Bed operation over a range of temperatures, feed rates, fluidizing rates, and redox conditions indicate that SYNROC powders of a high density and a uniform particle size can be produced. These powders facilitate the densification step and yield dense ceramics (greater than 95% theoretical density) with well-developed phases and low leaching rates
DEFF Research Database (Denmark)
da Providëncia, J.; Jalkanen, Karl J.; Bohr, Henrik
2013-01-01
relativistic fluid of elementary particles is studied. We find that the magnetic field of spin polarized matter with densities of 2 to 30, where 0 is the equilibrium density of nuclear matter, is rather huge, of the order of 1017 Gauss. Finally we look at the chiral nature of nuclear forces and interactions...... as they possibly relate to chirality of nuclei (atoms) in molecules as a source of chirality in amino acids and hence in life. Previous works have not investigated the nuclear forces as a possible bias which initiated the bias towards L-amino acids as the building blocks on proteins, and later life....
Coulomb interactions in charged fluids.
Vernizzi, Graziano; Guerrero-García, Guillermo Iván; de la Cruz, Monica Olvera
2011-07-01
The use of Ewald summation schemes for calculating long-range Coulomb interactions, originally applied to ionic crystalline solids, is a very common practice in molecular simulations of charged fluids at present. Such a choice imposes an artificial periodicity which is generally absent in the liquid state. In this paper we propose a simple analytical O(N(2)) method which is based on Gauss's law for computing exactly the Coulomb interaction between charged particles in a simulation box, when it is averaged over all possible orientations of a surrounding infinite lattice. This method mitigates the periodicity typical of crystalline systems and it is suitable for numerical studies of ionic liquids, charged molecular fluids, and colloidal systems with Monte Carlo and molecular dynamics simulations.
Shah, Rucha; Thomas, Raison; Mehta, Dhoom Singh
2014-02-01
To investigate a possible link between periodontitis and atherogenesis by examining the levels of anti-oxidized low density lipoprotien (ox LDL) and low density lipoprotien (LDL) in gingival crevicular fluid (GCF) and serum of healthy subjects and chronic periodontitis patients. Sixty male subjects (35-55 years) were grouped into 30 healthy individuals and 30 subjects with chronic periodontitis. Serum and GCF samples were obtained from each subject and were assessed for anti-ox LDL and LDL levels. A significant difference (p chronic periodontitis groups. Also the ratio of GCF anti-ox LDL to GCF LDL was significantly higher (p chronic periodontitis patients as compared to the healthy group. A significant rise in ox LDL level in otherwise systemically healthy chronic periodontitis patients may put these subjects at an increased risk of developing atherosclerosis.
International Nuclear Information System (INIS)
Johnson, E.
1977-01-01
A theory for site-site pair distribution functions of molecular fluids is derived from the Ornstein-Zernike equation. Atom-atom pair distribution functions of this theory which were obtained by using different approximations for the Percus-Yevick site-site direct correlation functions are compared
Viscous coupled fluids in inflationary cosmology
Energy Technology Data Exchange (ETDEWEB)
Brevik, I., E-mail: iver.h.brevik@ntnu.no [Norwegian University of Science and Technology (Norway); Timoshkin, A. V., E-mail: timoshkinAV@tspu.edu.ru [Tomsk State Pedagogical University (Russian Federation)
2016-04-15
We consider the inflation produced by two coupled fluids in a flat Friedmann–Robertson–Walker universe. Different cosmological models for describing inflation with the use of an inhomogeneous equation of state for the fluid are investigated. The gravitational equations for energy and matter are solved, and analytic representations for the Hubble parameter and the energy density are obtained. Corrections to the energy density for matter inducing the inflation and the coupling to energy are discussed. We analyze the description of inflation induced by nonconstant equation-of-state parameters from fluid viscosity. The correspondence between the spectral index and the tensor-to-scalar ratio recently observed by the Planck satellite is considered.
PULSE RADIOLYSIS IN SUPERCRITICAL RARE GAS FLUIDS
International Nuclear Information System (INIS)
HOLROYD, R.
2007-01-01
Recently, supercritical fluids have become quite popular in chemical and semiconductor industries for applications in chemical synthesis, extraction, separation processes, and surface cleaning. These applications are based on: the high dissolving power due to density build-up around solute molecules, and the ability to tune the conditions of a supercritical fluid, such as density and temperature, that are most suitable for a particular reaction. The rare gases also possess these properties and have the added advantage of being supercritical at room temperature. Information about the density buildup around both charged and neutral species can be obtained from fundamental studies of volume changes in the reactions of charged species in supercritical fluids. Volume changes are much larger in supercritical fluids than in ordinary solvents because of their higher compressibility. Hopefully basic studies, such as discussed here, of the behavior of charged species in supercritical gases will provide information useful for the utilization of these solvents in industrial applications
Mammographic Breast Density and Breast Cancer Molecular Subtypes: The Kenyan-African Aspect
Directory of Open Access Journals (Sweden)
Asim Jamal Shaikh
2018-01-01
Full Text Available Introduction. Data examining mammographic breast density (MBD among patients in Sub-Saharan Africa are sparse. We evaluated how MBD relates to breast cancer characteristics in Kenyan women undergoing diagnostic mammography. Methods. This cross-sectional study included women with pathologically confirmed breast cancers (n=123. Pretreatment mammograms of the unaffected breast were assessed to estimate absolute dense area (cm2, nondense area (cm2, and percent density (PD. Relationships between density measurements and clinical characteristics were evaluated using analysis of covariance. Results. Median PD and dense area were 24.9% and 85.3 cm2. Higher PD and dense area were observed in younger women (P<0.01. Higher dense and nondense areas were observed in obese women (P-trend < 0.01. Estrogen receptor (ER positive patients (73% had higher PD and dense area than ER-negative patients (P≤0.02. Triple negative breast cancer (TNBC patients (17% had lower PD and dense area (P≤0.01 compared with non-TNBCs. No associations were observed between MBD and tumor size and grade. Conclusions. Our findings show discordant relationships between MBD and molecular tumor subtypes to those previously observed in Western populations. The relatively low breast density observed at diagnosis may have important implications for cancer prevention initiatives in Kenya. Subsequent larger studies are needed to confirm these findings.
Viscosity kernel of molecular fluids
DEFF Research Database (Denmark)
Puscasu, Ruslan; Todd, Billy; Daivis, Peter
2010-01-01
, temperature, and chain length dependencies of the reciprocal and real-space viscosity kernels are presented. We find that the density has a major effect on the shape of the kernel. The temperature range and chain lengths considered here have by contrast less impact on the overall normalized shape. Functional...... forms that fit the wave-vector-dependent kernel data over a large density and wave-vector range have also been tested. Finally, a structural normalization of the kernels in physical space is considered. Overall, the real-space viscosity kernel has a width of roughly 3–6 atomic diameters, which means...
Common intersection points in dense fluids via equations of state
International Nuclear Information System (INIS)
Parsafar, G. A.; Noorian, R.
2001-01-01
Some new of state which are derived for dense fluids in recent years, namely the linear isotherm regularity, the dense system equation of state, Ihm-Song-Mason equation of state, and a newly derived semi-empirical equation of state have used to investigate the common intersection point of isobaric expansivity (α p ) in dense fluids. We have shown that the accuracy of these equations of state in predicting such a common intersection point is reduced from the new semi-imperial equation of state, dense system equation of state, linear isotherm regularity, to Ihm-Song-Mason equation of state. respectively. Form physical point of view, the van der Waals equation of state is used to investigate such an intersection point. It is shown that the van der Waals repulsion forces and temperature dependency of the effective molecular diameter are important for existence of this common point. Finally, we have shown that the common intersection points of the isotherms of thermal pressure coefficient, the isotherms of heat capacity at constant volume, and the iso chores of internal pressure for a fluid are related to each other. Also, the common intersection points of the reduced bulk modulus and 1/(Tα p ) for isotherms of a fluid both appear at the same density
International Nuclear Information System (INIS)
Roman-Duval, Julia; Jackson, James; Federrath, Christoph; Klessen, Ralf S.; Brunt, Christopher; Heyer, Mark
2011-01-01
Turbulence plays a major role in the formation and evolution of molecular clouds. Observationally, turbulent velocities are convolved with the density of an observed region. To correct for this convolution, we investigate the relation between the turbulence spectrum of model clouds, and the statistics of their synthetic observations obtained from principal component analysis (PCA). We apply PCA to spectral maps generated from simulated density and velocity fields, obtained from hydrodynamic simulations of supersonic turbulence, and from fractional Brownian motion (fBm) fields with varying velocity, density spectra, and density dispersion. We examine the dependence of the slope of the PCA pseudo-structure function, α PCA , on intermittency, on the turbulence velocity (β v ) and density (β n ) spectral indexes, and on density dispersion. We find that PCA is insensitive to β n and to the log-density dispersion σ s , provided σ s ≤ 2. For σ s > 2, α PCA increases with σ s due to the intermittent sampling of the velocity field by the density field. The PCA calibration also depends on intermittency. We derive a PCA calibration based on fBm structures with σ s ≤ 2 and apply it to 367 13 CO spectral maps of molecular clouds in the Galactic Ring Survey. The average slope of the PCA structure function, (α PCA ) = 0.62 ± 0.2, is consistent with the hydrodynamic simulations and leads to a turbulence velocity exponent of (β v ) = 2.06 ± 0.6 for a non-intermittent, low density dispersion flow. Accounting for intermittency and density dispersion, the coincidence between the PCA slope of the GRS clouds and the hydrodynamic simulations suggests β v ≅ 1.9, consistent with both Burgers and compressible intermittent turbulence.
Pokrovski, Gleb S.; Roux, Jacques; Ferlat, Guillaume; Jonchiere, Romain; Seitsonen, Ari P.; Vuilleumier, Rodolphe; Hazemann, Jean-Louis
2013-04-01
The molecular structure and stability of species formed by silver in aqueous saline solutions typical of hydrothermal settings were quantified using in situ X-ray absorption spectroscopy (XAS) measurements, quantum-chemical modeling of near-edge absorption spectra (XANES) and extended fine structure spectra (EXAFS), and first-principles molecular dynamics (FPMD). Results show that in nitrate-bearing acidic solutions to at least 200 °C, silver speciation is dominated by the hydrated Ag+ cation surrounded by 4-6 water molecules in its nearest coordination shell with mean Ag-O distances of 2.32 ± 0.02 Å. In NaCl-bearing acidic aqueous solutions of total Cl concentration from 0.7 to 5.9 mol/kg H2O (m) at temperatures from 200 to 450 °C and pressures to 750 bar, the dominant species are the di-chloride complex AgCl2- with Ag-Cl distances of 2.40 ± 0.02 Å and Cl-Ag-Cl angle of 160 ± 10°, and the tri-chloride complex AgCl32- of a triangular structure and mean Ag-Cl distances of 2.60 ± 0.05 Å. With increasing temperature, the contribution of the tri-chloride species decreases from ˜50% of total dissolved Ag in the most concentrated solution (5.9m Cl) at 200 °C to less than 10-20% at supercritical temperatures for all investigated solutions, so that AgCl2- becomes by far the dominant Ag-bearing species at conditions typical of hydrothermal-magmatic fluids. Both di- and tri-chloride species exhibit outer-sphere interactions with the solvent as shown by the detection, using FPMD modeling, of H2O, Cl-, and Na+ at distances of 3-4 Å from the silver atom. The species fractions derived from XAS and FPMD analyses, and total AgCl(s) solubilities, measured in situ in this work from the absorption edge height of XAS spectra, are in accord with thermodynamic predictions using the stability constants of AgCl2- and AgCl32- from Akinfiev and Zotov (2001) and Zotov et al. (1995), respectively, which are based on extensive previous AgCl(s) solubility measurements. These data
Critical asymmetry in renormalization group theory for fluids.
Zhao, Wei; Wu, Liang; Wang, Long; Li, Liyan; Cai, Jun
2013-06-21
The renormalization-group (RG) approaches for fluids are employed to investigate critical asymmetry of vapour-liquid equilibrium (VLE) of fluids. Three different approaches based on RG theory for fluids are reviewed and compared. RG approaches are applied to various fluid systems: hard-core square-well fluids of variable ranges, hard-core Yukawa fluids, and square-well dimer fluids and modelling VLE of n-alkane molecules. Phase diagrams of simple model fluids and alkanes described by RG approaches are analyzed to assess the capability of describing the VLE critical asymmetry which is suggested in complete scaling theory. Results of thermodynamic properties obtained by RG theory for fluids agree with the simulation and experimental data. Coexistence diameters, which are smaller than the critical densities, are found in the RG descriptions of critical asymmetries of several fluids. Our calculation and analysis show that the approach coupling local free energy with White's RG iteration which aims to incorporate density fluctuations into free energy is not adequate for VLE critical asymmetry due to the inadequate order parameter and the local free energy functional used in the partition function.
Structure of solvent-free grafted nanoparticles: Molecular dynamics and density-functional theory
Chremos, Alexandros
2011-01-01
The structure of solvent-free oligomer-grafted nanoparticles has been investigated using molecular dynamics simulations and density-functional theory. At low temperatures and moderate to high oligomer lengths, the qualitative features of the core particle pair probability, structure factor, and the oligomer brush configuration obtained from the simulations can be explained by a density-functional theory that incorporates the configurational entropy of the space-filling oligomers. In particular, the structure factor at small wave numbers attains a value much smaller than the corresponding hard-sphere suspension, the first peak of the pair distribution function is enhanced due to entropic attractions among the particles, and the oligomer brush expands with decreasing particle volume fraction to fill the interstitial space. At higher temperatures, the simulations reveal effects that differ from the theory and are likely caused by steric repulsions of the expanded corona chains. © 2011 American Institute of Physics.
Soler, J. D.; Ade, P. A. R.; Angilè, F. E.; Ashton, P.; Benton, S. J.; Devlin, M. J.; Dober, B.; Fissel, L. M.; Fukui, Y.; Galitzki, N.; Gandilo, N. N.; Hennebelle, P.; Klein, J.; Li, Z.-Y.; Korotkov, A. L.; Martin, P. G.; Matthews, T. G.; Moncelsi, L.; Netterfield, C. B.; Novak, G.; Pascale, E.; Poidevin, F.; Santos, F. P.; Savini, G.; Scott, D.; Shariff, J. A.; Thomas, N. E.; Tucker, C. E.; Tucker, G. S.; Ward-Thompson, D.
2017-07-01
We statistically evaluated the relative orientation between gas column density structures, inferred from Herschel submillimetre observations, and the magnetic field projected on the plane of sky, inferred from polarized thermal emission of Galactic dust observed by the Balloon-borne Large-Aperture Submillimetre Telescope for Polarimetry (BLASTPol) at 250, 350, and 500 μm, towards the Vela C molecular complex. First, we find very good agreement between the polarization orientations in the three wavelength-bands, suggesting that, at the considered common angular resolution of 3.´0 that corresponds to a physical scale of approximately 0.61 pc, the inferred magnetic field orientation is not significantly affected by temperature or dust grain alignment effects. Second, we find that the relative orientation between gas column density structures and the magnetic field changes progressively with increasing gas column density, from mostly parallel or having no preferred orientation at low column densities to mostly perpendicular at the highest column densities. This observation is in agreement with previous studies by the Planck collaboration towards more nearby molecular clouds. Finally, we find a correspondencebetween (a) the trends in relative orientation between the column density structures and the projected magnetic field; and (b) the shape of the column density probability distribution functions (PDFs). In the sub-regions of Vela C dominated by one clear filamentary structure, or "ridges", where the high-column density tails of the PDFs are flatter, we find a sharp transition from preferentially parallel or having no preferred relative orientation at low column densities to preferentially perpendicular at highest column densities. In the sub-regions of Vela C dominated by several filamentary structures with multiple orientations, or "nests", where the maximum values of the column density are smaller than in the ridge-like sub-regions and the high-column density
Soft particles at a fluid interface
Mehrabian, Hadi; Harting, Jens; Snoeijer, Jacco H.
2015-11-01
Particles added to a fluid interface can be used as a surface stabilizer in the food, oil and cosmetic industries. As an alternative to rigid particles, it is promising to consider highly deformable particles that can adapt their conformation at the interface. In this study, we compute the shapes of soft elastic particles using molecular dynamics simulations of a cross-linked polymer gel, complemented by continuum calculations based on the linear elasticity. It is shown that the particle shape is not only affected by the Young's modulus of the particle, but also strongly depends on whether the gel is partially or completely wetting the fluid interface. We find that the molecular simulations for the partially wetting case are very accurately described by the continuum theory. By contrast, when the gel is completely wetting the fluid interface the linear theory breaks down and we reveal that molecular details have a strong influence on the equilibrium shape.
International Nuclear Information System (INIS)
Kang, Hongbo; Zhang, Yuwen; Yang, Mo; Li, Ling
2012-01-01
The intent of this study is to examine nonequilibrium heat transfer in a copper–argon nanofluid by molecular dynamics simulation. Two different methods, the physical definition method and the curve fitting method, are introduced to calculate the coupling factor between nanoparticles and base fluid. The results show that the coupling factors obtained by these two methods are consistent. The coupling factor is proportional to the volume fraction of the nanoparticle and inversely proportional to nanoparticle diameter. In the temperature range of 90–200 K, the coupling factor is not affected by temperature. The nanoparticle aggregation results in a decrease of the coupling factor. -- Highlights: ► Nonequilibrium heat transfer in a copper–argon nanofluid is investigated by molecular dynamics simulation. ► The coupling factor is proportion to the volume fraction of the nanoparticle and inverse proportion to nanoparticle diameter. ► In the temperature range of 90–200 K, there is no temperature effect on the coupling factor. ► The nanoparticle aggregation results in a decrease of the coupling factor.
Evaporation of Lennard-Jones fluids.
Cheng, Shengfeng; Lechman, Jeremy B; Plimpton, Steven J; Grest, Gary S
2011-06-14
Evaporation and condensation at a liquid/vapor interface are ubiquitous interphase mass and energy transfer phenomena that are still not well understood. We have carried out large scale molecular dynamics simulations of Lennard-Jones (LJ) fluids composed of monomers, dimers, or trimers to investigate these processes with molecular detail. For LJ monomers in contact with a vacuum, the evaporation rate is found to be very high with significant evaporative cooling and an accompanying density gradient in the liquid domain near the liquid/vapor interface. Increasing the chain length to just dimers significantly reduces the evaporation rate. We confirm that mechanical equilibrium plays a key role in determining the evaporation rate and the density and temperature profiles across the liquid/vapor interface. The velocity distributions of evaporated molecules and the evaporation and condensation coefficients are measured and compared to the predictions of an existing model based on kinetic theory of gases. Our results indicate that for both monatomic and polyatomic molecules, the evaporation and condensation coefficients are equal when systems are not far from equilibrium and smaller than one, and decrease with increasing temperature. For the same reduced temperature T/T(c), where T(c) is the critical temperature, these two coefficients are higher for LJ dimers and trimers than for monomers, in contrast to the traditional viewpoint that they are close to unity for monatomic molecules and decrease for polyatomic molecules. Furthermore, data for the two coefficients collapse onto a master curve when plotted against a translational length ratio between the liquid and vapor phase.
Tavares, Ludmyla S.; Carvalho, Thays C.; Romão, Wanderson; Vaz, Boniek G.; Chaves, Andréa R.
2018-03-01
This study proposes a new direct and fast method of analysis employing paper spray mass spectrometry (PS-MS). The paper used in the proposed method was modified with molecularly imprinted polymers (MIP) to create a specific site for cocaine analysis in oral fluid. MIP membrane was successfully synthetized and employed. The developed method showed to be linear in a concentration range from LOQ to 100 ng mL-1. The experimental value of LOQ obtained was 1 ng mL-1. The inter-day and intra-day precision and accuracy of the PS-MS method presented values lower than 15%. The total recoveries were also evaluated. The PS-MS method for the analysis of cocaine in oral fluid showed to be very promising and the validation parameters showed a good correlation with the literature. [Figure not available: see fulltext.
International Nuclear Information System (INIS)
Goto, R.; Hatori, T.; Miura, H.; Ito, A.; Sato, M.
2015-01-01
Two-fluid and the finite Larmor effects on linear and nonlinear growth of the Rayleigh-Taylor instability in a two-dimensional slab are studied numerically with special attention to high-wave-number dynamics and nonlinear structure formation at a low β-value. The two effects stabilize the unstable high wave number modes for a certain range of the β-value. In nonlinear simulations, the absence of the high wave number modes in the linear stage leads to the formation of the density field structure much larger than that in the single-fluid magnetohydrodynamic simulation, together with a sharp density gradient as well as a large velocity difference. The formation of the sharp velocity difference leads to a subsequent Kelvin-Helmholtz-type instability only when both the two-fluid and finite Larmor radius terms are incorporated, whereas it is not observed otherwise. It is shown that the emergence of the secondary instability can modify the outline of the turbulent structures associated with the primary Rayleigh-Taylor instability
International Nuclear Information System (INIS)
Rodriguez, Juan I; Thompson, David C; Anderson, James S M; Thomson, Jordan W; Ayers, Paul W
2008-01-01
We present a novel approach for performing multi-dimensional integration of arbitrary functions. The method starts with Smolyak-type sparse grids as cubature formulae on the unit cube and uses a transformation of coordinates based on the conditional distribution method to adapt those formulae to real space. Our method is tested on integrals in one, two, three and six dimensions. The three dimensional integration formulae are used to evaluate atomic interaction energies via the Gordon-Kim model. The six dimensional integration formulae are tested in conjunction with the nonlocal exchange-correlation energy functional proposed by Lee and Parr. This methodology is versatile and powerful; we contemplate application to frozen-density embedding, next-generation molecular-mechanics force fields, 'kernel-type' exchange-correlation energy functionals and pair-density functional theory
DEFF Research Database (Denmark)
Frutiger, Jerome; Abildskov, Jens; Sin, Gürkan
Computer Aided Molecular Design (CAMD) is an important tool to generate, test and evaluate promising chemical products. CAMD can be used in thermodynamic cycle for the design of pure component or mixture working fluids in order to improve the heat transfer capacity of the system. The safety......, there is no information about the reliability of the data. Furthermore, the global optimality of the GC parameters estimation is often not ensured....
Sherlin, Y. Sheeba; Vijayakumar, T.; Roy, S. D. D.; Jayakumar, V. S.
2018-05-01
Molecular geometry of Parkinson's drug 2-(3,4-Dihydroxyphenyl)ethylamine hydrochloride (Dopamine, DA) has been evaluated and compared with experimental XRD data. Molecular docking and vibrational spectral analysis of DA have been carried out using FT-Raman and FT-IR spectra aided by Density Functional Theory at B3LYP/6-311++G(d,p). The present investigation deals with the analysis of structural and spectral features responsible for drug activities, nature of hydrogen bonding interactions of the molecule and the correlation of Parkinson's nature with its molecular structural features.
Mixing and Processing of Complex Biological Fluids
National Research Council Canada - National Science Library
Liepmann, Dorian
2003-01-01
... of microfluidic control on the makeup and molecular structure of biological fluids. For this project, we focused on two critical fluids that are biologically significant and that are of critical importance to DoD...
Phase equilibria of binary mixtures by molecular simulation and cubic equations of state
Directory of Open Access Journals (Sweden)
Cabral V.F.
2001-01-01
Full Text Available Molecular simulation data were used to study the performance of equations of state (EoS and combining rules usually employed in thermodynamic property calculations. The Monte Carlo method and the Gibbs ensemble technique were used for determining composition and densities of vapor and liquid phases in equilibrium for binary mixtures of Lennard-Jones fluids. Simulation results are compared to data in the literature and to those calculated by the t-PR-LJ EoS. The use of adequate combining rules has been shown to be very important for the satisfactory representation of molecular simulation data.
Kauffmann, Jens; Goldsmith, Paul F.; Melnick, Gary; Tolls, Volker; Guzman, Andres; Menten, Karl M.
2017-09-01
Trends observed in galaxies, such as the Gao & Solomon relation, suggest a linear relationship between the star formation rate and the mass of dense gas available for star formation. Validation of such trends requires the establishment of reliable methods to trace the dense gas in galaxies. One frequent assumption is that the HCN (J = 1-0) transition is unambiguously associated with gas at H2 densities ≫ 104 cm-3. If so, the mass of gas at densities ≫ 104 cm-3 could be inferred from the luminosity of this emission line, LHCN (1-0). Here we use observations of the Orion A molecular cloud to show that the HCN (J = 1-0) line traces much lower densities 103 cm-3 in cold sections of this molecular cloud, corresponding to visual extinctions AV ≈ 6 mag. We also find that cold and dense gas in a cloud like Orion produces too little HCN emission to explain LHCN (1-0) in star forming galaxies, suggesting that galaxies might contain a hitherto unknown source of HCN emission. In our sample of molecules observed at frequencies near 100 GHz (also including 12CO, 13CO, C18O, CN, and CCH), N2H+ is the only species clearly associated with relatively dense gas.
International Nuclear Information System (INIS)
Vikas
2011-01-01
Evolution of the helium atom in a strong time-dependent (TD) magnetic field (B) of strength up to 10 11 G is investigated through a quantum fluid dynamics (QFD) based current-density functional theory (CDFT). The TD-QFD-CDFT computations are performed through numerical solution of a single generalized nonlinear Schroedinger equation employing vector exchange-correlation potentials and scalar exchange-correlation density functionals that depend both on the electronic charge-density and the current-density. The results are compared with that obtained from a B-TD-QFD-DFT approach (based on conventional TD-DFT) under similar numerical constraints but employing only scalar exchange-correlation potential dependent on electronic charge-density only. The B-TD-QFD-DFT approach, at a particular TD magnetic field-strength, yields electronic charge- and current-densities as well as exchange-correlation potential resembling with that obtained from the time-independent studies involving static (time-independent) magnetic fields. However, TD-QFD-CDFT electronic charge- and current-densities along with the exchange-correlation potential and energy differ significantly from that obtained using B-TD-QFD-DFT approach, particularly at field-strengths >10 9 G, representing dynamical effects of a TD field. The work concludes that when a helium atom is subjected to a strong TD magnetic field of order >10 9 G, the conventional TD-DFT based approach differs 'dynamically' from the CDFT based approach under similar computational constraints. (author)
Molecular Simulation of Adsorption in Microporous Materials
Directory of Open Access Journals (Sweden)
Yiannourakou M.
2013-11-01
Full Text Available The development of industrial software, the decreasing cost of computing time, and the availability of well-tested forcefields make molecular simulation increasingly attractive for chemical engineers. We present here several applications of Monte-Carlo simulation techniques, applied to the adsorption of fluids in microporous solids such as zeolites and model carbons (pores < 2 nm. Adsorption was computed in the Grand Canonical ensemble with the MedeA®-GIBBS software, using energy grids to decrease computing time. MedeA®-GIBBS has been used for simulations in the NVT or NPT ensembles to obtain the density and fugacities of fluid phases. Simulation results are compared with experimental pure component isotherms in zeolites (hydrocarbon gases, water, alkanes, aromatics, ethanethiol, etc., and mixtures (methane-ethane, n-hexane-benzene, over a large range of temperatures. Hexane/benzene selectivity inversions between silicalite and Na-faujasites are well predicted with published forcefields, providing an insight on the underlying mechanisms. Also, the adsorption isotherms in Na-faujasites for light gases or ethane-thiol are well described. Regarding organic adsorbents, models of mature kerogen or coal were built in agreement with known chemistry of these systems. Obtaining realistic kerogen densities with the simple relaxation approach considered here is encouraging for the investigation of other organic systems. Computing excess sorption curves in qualitative agreement with those recently measured on dry samples of gas shale is also favorable. Although still preliminary, such applications illustrate the strength of molecular modeling in understanding complex systems in conditions where experiments are difficult.
Working fluid selection for organic Rankine cycles - Impact of uncertainty of fluid properties
DEFF Research Database (Denmark)
Frutiger, Jerome; Andreasen, Jesper Graa; Liu, Wei
2016-01-01
This study presents a generic methodology to select working fluids for ORC (Organic Rankine Cycles)taking into account property uncertainties of the working fluids. A Monte Carlo procedure is described as a tool to propagate the influence of the input uncertainty of the fluid parameters on the ORC...... modeloutput, and provides the 95%-confidence interval of the net power output with respect to the fluid property uncertainties. The methodology has been applied to a molecular design problem for an ORCusing a low-temperature heat source and consisted of the following four parts: 1) formulation...... of processmodels and constraints 2) selection of property models, i.e. Penge Robinson equation of state 3)screening of 1965 possible working fluid candidates including identification of optimal process parametersbased on Monte Carlo sampling 4) propagating uncertainty of fluid parameters to the ORC netpower output...
Rapid density-measurement system with vibrating-tube densimeter
International Nuclear Information System (INIS)
Kayukawa, Yohei; Hasumoto, Masaya; Watanabe, Koichi
2003-01-01
Concerning an increasing demand for environmentally friendly refrigerants including hydrocarbons, thermodynamic properties of such new refrigerants, especially densities, are essential information for refrigeration engineering. A rapid density-measurement system with vibrating-tube densimeter was developed in the present study with an aim to supply large numbers of high-quality PVT property data in a short period. The present system needs only a few minutes to obtain a single datum, and requires less than 20 cm 3 sample fluid. PVT properties in the entire fluid-phase, vapor-pressures, saturated-liquid densities for pure fluid are available. Liquid densities, bubble-point pressures and saturated-liquid densities for mixture can be obtained. The measurement range is from 240 to 380 K for temperature and up to 7 MPa for pressure. By employing a new calibration function, density can be precisely obtained even at lower densities. The densimeter is calibrated with pure water and iso-octane which is one of the density-standard fluids, and then measurement uncertainty was evaluated to be 0.1 kg m -3 or 0.024% whichever greater in density, 0.26 kPa or 0.022% whichever greater in pressure and 3 mK for temperature, respectively. The performance of the present measurement system was examined by measuring thermodynamic properties for refrigerant R134a. The experimental results were compared with available equation of state and confirmed to agree with it within ±0.05% for liquid densities while ±0.5% in pressure for the gas phase
Self-interaction corrected density functional calculations of molecular Rydberg states
International Nuclear Information System (INIS)
Gudmundsdóttir, Hildur; Zhang, Yao; Weber, Peter M.; Jónsson, Hannes
2013-01-01
A method is presented for calculating the wave function and energy of Rydberg excited states of molecules. A good estimate of the Rydberg state orbital is obtained using ground state density functional theory including Perdew-Zunger self-interaction correction and an optimized effective potential. The total energy of the excited molecule is obtained using the Delta Self-Consistent Field method where an electron is removed from the highest occupied orbital and placed in the Rydberg orbital. Results are presented for the first few Rydberg states of NH 3 , H 2 O, H 2 CO, C 2 H 4 , and N(CH 3 ) 3 . The mean absolute error in the energy of the 33 molecular Rydberg states presented here is 0.18 eV. The orbitals are represented on a real space grid, avoiding the dependence on diffuse atomic basis sets. As in standard density functional theory calculations, the computational effort scales as NM 2 where N is the number of orbitals and M is the number of grid points included in the calculation. Due to the slow scaling of the computational effort with system size and the high level of parallelism in the real space grid approach, the method presented here makes it possible to estimate Rydberg electron binding energy in large molecules
International Nuclear Information System (INIS)
Pooja,; Ahluwalia, P. K.; Pathania, Y.
2015-01-01
This paper presents the results from a molecular dynamics simulation of mixture of argon and krypton in the Poiseuille flow across a rough walled nanochannel. The roughness effect on liquid nanoflows has recently drawn attention The computational software used for carrying out the molecular dynamics simulations is LAMMPS. The fluid flow takes place between two parallel plates and is bounded by horizontal rough walls in one direction and periodic boundary conditions are imposed in the other two directions. Each fluid atom interacts with other fluid atoms and wall atoms through Leenard-Jones (LJ) potential with a cut off distance of 5.0. To derive the flow a constant force is applied whose value is varied from 0.1 to 0.3 and velocity profiles and temperature profiles are noted for these values of forces. The velocity profile and temperature profiles are also looked at different channel widths of nanochannel and at different densities of mixture. The velocity profile and temperature profile of rough walled nanochannel are compared with that of smooth walled nanochannel and it is concluded that mean velocity increases with increase in channel width, force applied and decrease in density also with introduction of roughness in the walls of nanochannel mean velocity again increases and results also agree with the analytical solution of a Poiseuille flow
Reimers, Jeffrey R; Cai, Zheng-Li; Bilić, Ante; Hush, Noel S
2003-12-01
As molecular electronics advances, efficient and reliable computation procedures are required for the simulation of the atomic structures of actual devices, as well as for the prediction of their electronic properties. Density-functional theory (DFT) has had widespread success throughout chemistry and solid-state physics, and it offers the possibility of fulfilling these roles. In its modern form it is an empirically parameterized approach that cannot be extended toward exact solutions in a prescribed way, ab initio. Thus, it is essential that the weaknesses of the method be identified and likely shortcomings anticipated in advance. We consider four known systematic failures of modern DFT: dispersion, charge transfer, extended pi conjugation, and bond cleavage. Their ramifications for molecular electronics applications are outlined and we suggest that great care is required when using modern DFT to partition charge flow across electrode-molecule junctions, screen applied electric fields, position molecular orbitals with respect to electrode Fermi energies, and in evaluating the distance dependence of through-molecule conductivity. The causes of these difficulties are traced to errors inherent in the types of density functionals in common use, associated with their inability to treat very long-range electron correlation effects. Heuristic enhancements of modern DFT designed to eliminate individual problems are outlined, as are three new schemes that each represent significant departures from modern DFT implementations designed to provide a priori improvements in at least one and possible all problem areas. Finally, fully semiempirical schemes based on both Hartree-Fock and Kohn-Sham theory are described that, in the short term, offer the means to avoid the inherent problems of modern DFT and, in the long term, offer competitive accuracy at dramatically reduced computational costs.
Hirakawa, Teruo; Suzuki, Teppei; Bowler, David R; Miyazaki, Tsuyoshi
2017-10-11
We discuss the development and implementation of a constant temperature (NVT) molecular dynamics scheme that combines the Nosé-Hoover chain thermostat with the extended Lagrangian Born-Oppenheimer molecular dynamics (BOMD) scheme, using a linear scaling density functional theory (DFT) approach. An integration scheme for this canonical-ensemble extended Lagrangian BOMD is developed and discussed in the context of the Liouville operator formulation. Linear scaling DFT canonical-ensemble extended Lagrangian BOMD simulations are tested on bulk silicon and silicon carbide systems to evaluate our integration scheme. The results show that the conserved quantity remains stable with no systematic drift even in the presence of the thermostat.
Fluid dynamics theoretical and computational approaches
Warsi, ZUA
2005-01-01
Important Nomenclature Kinematics of Fluid Motion Introduction to Continuum Motion Fluid Particles Inertial Coordinate Frames Motion of a Continuum The Time Derivatives Velocity and Acceleration Steady and Nonsteady Flow Trajectories of Fluid Particles and Streamlines Material Volume and Surface Relation between Elemental Volumes Kinematic Formulas of Euler and Reynolds Control Volume and Surface Kinematics of Deformation Kinematics of Vorticity and Circulation References Problems The Conservation Laws and the Kinetics of Flow Fluid Density and the Conservation of Mass Prin
Hydrodynamic 'memory' of binary fluid mixtures
International Nuclear Information System (INIS)
Kalashnik, M. V.; Ingel, L. Kh.
2006-01-01
A theoretical analysis is presented of hydrostatic adjustment in a two-component fluid system, such as seawater stratified with respect to temperature and salinity. Both linear approximation and nonlinear problem are investigated. It is shown that scenarios of relaxation to a hydrostatically balanced state in binary fluid mixtures may substantially differ from hydrostatic adjustment in fluids that can be stratified only with respect to temperature. In particular, inviscid two-component fluids have 'memory': a horizontally nonuniform disturbance in the initial temperature or salinity distribution does not vanish even at the final stage, transforming into a persistent thermohaline 'trace.' Despite stability of density stratification and convective stability of the fluid system by all known criteria, an initial temperature disturbance may not decay and may even increase in amplitude. Moreover, its sign may change (depending on the relative contributions of temperature and salinity to stable background density stratification). Hydrostatic adjustment may involve development of discontinuous distributions from smooth initial temperature or concentration distributions. These properties of two-component fluids explain, in particular, the occurrence of persistent horizontally or vertically nonuniform temperature and salinity distributions in the ocean, including discontinuous ones
Many-Body Effects on the Thermodynamics of Fluids, Mixtures, and Nanoconfined Fluids.
Desgranges, Caroline; Delhommelle, Jerome
2015-11-10
Using expanded Wang-Landau simulations, we show that taking into account the many-body interactions results in sharp changes in the grand-canonical partition functions of single-component systems, binary mixtures, and nanoconfined fluids. The many-body contribution, modeled with a 3-body Axilrod-Teller-Muto term, results in shifts toward higher chemical potentials of the phase transitions from low-density phases to high-density phases and accounts for deviations of more than, e.g., 20% of the value of the partition function for a single-component liquid. Using the statistical mechanics formalism, we analyze how this contribution has a strong impact on some properties (e.g., pressure, coexisting densities, and enthalpy) and a moderate impact on others (e.g., Gibbs or Helmholtz free energies). We also characterize the effect of the 3-body terms on adsorption isotherms and adsorption thermodynamic properties, thereby providing a full picture of the effect of the 3-body contribution on the thermodynamics of nanoconfined fluids.
Hamiltonian formalism for perfect fluids in general relativity
International Nuclear Information System (INIS)
Demaret, J.; Moncrief, V.
1980-01-01
Schutz's Hamiltonian theory of a relativistic perfect fluid, based on the velocity-potential version of classical perfect fluid hydrodynamics as formulated by Seliger and Whitham, is used to derive, in the framework of the Arnowitt, Deser, and Misner (ADM) method, a general partially reduced Hamiltonian for relativistic systems filled with a perfect fluid. The time coordinate is chosen, as in Lund's treatment of collapsing balls of dust, as minus the only velocity potential different from zero in the case of an irrotational and isentropic fluid. A ''semi-Dirac'' method can be applied to quantize astrophysical and cosmological models in the framework of this partially reduced formalism. If one chooses Taub's adapted comoving coordinate system, it is possible to derive a fully reduced ADM Hamiltonian, which is equal to minus the total baryon number of the fluid, generalizing a result previously obtained by Moncrief in the more particular framework of Taub's variational principle, valid for self-gravitating barotropic relativistic perfect fluids. An unconstrained Hamiltonian density is then explicitly derived for a fluid obeying the equation of state p=(gamma-1)rho (1 < or = γ < or = 2), which can adequately describe the phases of very high density attained in a catastrophic collapse or during the early stages of the Universe. This Hamiltonian density, shown to be equivalent to Moncrief's in the particular case of an isentropic fluid, can be simplified for fluid-filled class-A diagonal Bianchi-type cosmological models and appears as a suitable starting point for the study of the canonical quantization of these models
Quantum molecular dynamics simulations of warm dense lithium hydride: Examination of mixing rules
International Nuclear Information System (INIS)
Horner, D. A.; Kress, J. D.; Collins, L. A.
2008-01-01
We have performed a systematic study of lithium hydride (LiH) in a density range from half to twice solid for temperatures from 0.5 to 3.0 eV using quantum molecular dynamics (QMD) methods and have tested density and pressure mixing rules for obtaining equations of state and optical properties such as frequency-dependent absorption coefficients and Rosseland mean opacities. The QMD simulations for the full LiH fluid served as a benchmark against which to assess the rules. In general, the mixing rule based on the pressure matching produces superior equations of state and mean opacities for the mixture except at the very lowest temperatures and densities. However, the frequency-dependent absorption coefficients displayed considerable differences in some frequency ranges except at the highest temperatures and densities
Molecular adsorbates on HOPG: Toward modulation of graphene density of states
Groce, Michelle; Einstein, Theodore; Cullen, William
2013-03-01
Ordered molecular superlattices, particularly those made of planar aromatics with their attendant pi orbitals, have the potential to break the graphene sublattice degeneracy and create a band gap. Trimesic acid (TMA) is a promising candidate due to its self-assembly into symmetry-breaking superlattices nearly commensurate with that of graphene. We have used the graphite (0001) surface as a model system to explore the impact of TMA thin films on band structure. By examining correlations between STM topography and STS maps of corresponding regions, we are able to investigate the effects of TMA on the local density of states. Work supported by the University of Maryland NSF-MRSEC, DMR 0520471 and Shared Experimental Facilities.
International Nuclear Information System (INIS)
Mu, Tiancheng; Liu, Zhimin; Han, Buxing.; Li, Zhonghao; Zhang, Jianling; Zhang, Xiaogang
2003-01-01
The phase behavior, density, and constant-volume molar heat capacity (C v,m ) of ethane + n-pentane binary mixtures have been measured in the supercritical region and subcritical region at T=309.45 K. In addition, the isothermal compressibility (κ T ) has been calculated using the density data determined. For a mixed fluid with a composition close to the critical composition, C v,m and κ T increase sharply as the pressure approaches the critical point (CP), the dew point (DP), or the bubble point (BP). However, C v,m is not sensitive to pressure in the entire pressure range if the composition of the mixed fluid is far from the critical composition. To tune the properties of the binary mixtures effectively by pressure, both the composition and the pressure should be close to the critical point of the mixture. The intermolecular interactions in the mixture are also discussed on the basis of the experimental results
From cellulose to kerogen: molecular simulation of a geological process.
Atmani, Lea; Bichara, Christophe; Pellenq, Roland J-M; Van Damme, Henri; van Duin, Adri C T; Raza, Zamaan; Truflandier, Lionel A; Obliger, Amaël; Kralert, Paul G; Ulm, Franz J; Leyssale, Jean-Marc
2017-12-01
The process by which organic matter decomposes deep underground to form petroleum and its underlying kerogen matrix has so far remained a no man's land to theoreticians, largely because of the geological (Myears) timescale associated with the process. Using reactive molecular dynamics and an accelerated simulation framework, the replica exchange molecular dynamics method, we simulate the full transformation of cellulose into kerogen and its associated fluid phase under prevailing geological conditions. We observe in sequence the fragmentation of the cellulose crystal and production of water, the development of an unsaturated aliphatic macromolecular phase and its aromatization. The composition of the solid residue along the maturation pathway strictly follows what is observed for natural type III kerogen and for artificially matured samples under confined conditions. After expulsion of the fluid phase, the obtained microporous kerogen possesses the structure, texture, density, porosity and stiffness observed for mature type III kerogen and a microporous carbon obtained by saccharose pyrolysis at low temperature. As expected for this variety of precursor, the main resulting hydrocarbon is methane. The present work thus demonstrates that molecular simulations can now be used to assess, almost quantitatively, such complex chemical processes as petrogenesis in fossil reservoirs and, more generally, the possible conversion of any natural product into bio-sourced materials and/or fuel.
Directory of Open Access Journals (Sweden)
Janel Chua
2018-01-01
Full Text Available In this work, molecular dynamics (MD and molecular mechanics (MM simulations are used to study well-equilibrated models of 4,4′-bis(3,4-dicyanophenoxybiphenyl (BPh–1,3-bis(3-aminophenoxybenzene (m-APB phthalonitrile (PN system with a range of crosslink densities. A cross-linking technique is introduced to build a series of systems with different crosslink densities; several key properties of this material, including thermal expansion, mechanical properties and dielectric properties are studied and compared with experimental results. It is found that the coefficient of linear thermal expansion predicted by the model is in good agreement with experimental results and indicative of the good thermal stability of the PN polymeric system. The simulation also shows that this polymer has excellent mechanical property, whose strength increases with increasing crosslink density. Lastly and most importantly, the calculated dielectric constant—which shows that this polymer is an excellent insulating material—indicates that there is an inverse relation between cross-linking density and dielectric constant. The trend gave rise to an empirical quadratic function which can be used to predict the limits of attainable dielectric constant for highly crosslinked polymer systems. The current computational work provides strong evidence that this polymer is a promising material for aerospace applications and offers guidance for experimental studies of the effect of cross-linking density on the thermal, mechanical and dielectric properties of the material.
Dynamical density functional theory for dense atomic liquids
International Nuclear Information System (INIS)
Archer, A J
2006-01-01
Starting from Newton's equations of motion, we derive a dynamical density functional theory (DDFT) applicable to atomic liquids. The theory has the feature that it requires as input the Helmholtz free energy functional from equilibrium density functional theory. This means that, given a reliable equilibrium free energy functional, the correct equilibrium fluid density profile is guaranteed. We show that when the isothermal compressibility is small, the DDFT generates the correct value for the speed of sound in a dense liquid. We also interpret the theory as a dynamical equation for a coarse grained fluid density and show that the theory can be used (making further approximations) to derive the standard mode coupling theory that is used to describe the glass transition. The present theory should provide a useful starting point for describing the dynamics of inhomogeneous atomic fluids
Spinning fluids in general relativity
Ray, J. R.; Smalley, L. L.
1982-01-01
General relativity field equations are employed to examine a continuous medium with internal spin. A variational principle formerly applied in the special relativity case is extended to the general relativity case, using a tetrad to express the spin density and the four-velocity of the fluid. An energy-momentum tensor is subsequently defined for a spinning fluid. The equations of motion of the fluid are suggested to be useful in analytical studies of galaxies, for anisotropic Bianchi universes, and for turbulent eddies.
Mcfadden, G. B.; Coriell, S. R.
1986-01-01
The Ivantsov (1947) analysis of an isolated isothermal dendrite (with zero surface tension) growing into a supercooled liquid is extended to include the effects of the fluid flow due to volume contraction or expansion upon solidification. For an axisymmetric paraboloidal dendrite, an analytic solution to the Navier-Stokes equations is obtained. The magnitude of the flow is proportional to the relative density change epsilon, and the flow becomes negligible far from the surface of the dendrite. The temperature field consistent with this flow can also be found explicitly. The well-known expression that relates the dimensionless supercooling to the Peclet number in the absence of fluid flow is modified for nonzero epsilon, but the effect is of order epsilon and hence is seen to be minor for most values of epsilon and dimensionless supercooling that occur in practice.
International Nuclear Information System (INIS)
Koperwas, K.; Grzybowski, A.; Grzybowska, K.; Wojnarowska, Z.; Paluch, M.
2015-01-01
In this paper, we define and experimentally verify thermodynamic characteristics of the liquid-glass transition, taking into account a kinetic origin of the process. Using the density scaling law and the four-point measure of the dynamic heterogeneity of molecular dynamics of glass forming liquids, we investigate contributions of enthalpy, temperature, and density fluctuations to spatially heterogeneous molecular dynamics at the liquid-glass transition, finding an equation for the pressure coefficient of the glass transition temperature, dTg/dp. This equation combined with our previous formula for dTg/dp, derived solely from the density scaling criterion, implies a relationship among thermodynamic coefficients at Tg. Since this relationship and both the equations for dTg/dp are very well validated using experimental data at Tg, they are promising alternatives to the classical Prigogine-Defay ratio and both the Ehrenfest equations in case of the liquid-glass transition
Energy Technology Data Exchange (ETDEWEB)
Koperwas, K., E-mail: kkoperwas@us.edu.pl; Grzybowski, A.; Grzybowska, K.; Wojnarowska, Z.; Paluch, M. [Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice (Poland); Silesian Center for Education and Interdisciplinary Research, 75 Pulku Piechoty 1A, 41-500 Chorzow (Poland)
2015-07-14
In this paper, we define and experimentally verify thermodynamic characteristics of the liquid-glass transition, taking into account a kinetic origin of the process. Using the density scaling law and the four-point measure of the dynamic heterogeneity of molecular dynamics of glass forming liquids, we investigate contributions of enthalpy, temperature, and density fluctuations to spatially heterogeneous molecular dynamics at the liquid-glass transition, finding an equation for the pressure coefficient of the glass transition temperature, dTg/dp. This equation combined with our previous formula for dTg/dp, derived solely from the density scaling criterion, implies a relationship among thermodynamic coefficients at Tg. Since this relationship and both the equations for dTg/dp are very well validated using experimental data at Tg, they are promising alternatives to the classical Prigogine-Defay ratio and both the Ehrenfest equations in case of the liquid-glass transition.
Obliquely propagating dust-density waves
International Nuclear Information System (INIS)
Piel, A.; Arp, O.; Klindworth, M.; Melzer, A.
2008-01-01
Self-excited dust-density waves are experimentally studied in a dusty plasma under microgravity. Two types of waves are observed: a mode inside the dust volume propagating in the direction of the ion flow and another mode propagating obliquely at the boundary between the dusty plasma and the space charge sheath. The dominance of oblique modes can be described in the frame of a fluid model. It is shown that the results fom the fluid model agree remarkably well with a kinetic electrostatic model of Rosenberg [J. Vac. Sci. Technol. A 14, 631 (1996)]. In the experiment, the instability is quenched by increasing the gas pressure or decreasing the dust density. The critical pressure and dust density are well described by the models
Zbiri, M.; Johnson, M.R.; Kearley, G.J.; Mulder, F.M.
2009-01-01
We investigate the effect of structural fluctuations on charge transfer integrals, overlap integrals, and site energies in a system of two stacked molecular 2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6), which is a model system for conducting devices in organic photocell applications. A density
International Nuclear Information System (INIS)
Duarte Campos, Daniela F; Blaeser, Andreas; Weber, Michael; Fischer, Horst; Jäkel, Jörg; Neuss, Sabine; Jahnen-Dechent, Wilhelm
2013-01-01
Over the last decade, bioprinting technologies have begun providing important tissue engineering strategies for regenerative medicine and organ transplantation. The major drawback of past approaches has been poor or inadequate material-printing device and substrate combinations, as well as the relatively small size of the printed construct. Here, we hypothesise that cell-laden hydrogels can be printed when submerged in perfluorotributylamine (C 12 F 27 N), a hydrophobic high-density fluid, and that these cells placed within three-dimensional constructs remain viable allowing for cell proliferation and production of extracellular matrix. Human mesenchymal stem cells and MG-63 cells were encapsulated into agarose hydrogels, and subsequently printed in high aspect ratio in three dimensional structures that were supported in high density fluorocarbon. Three-dimensional structures with various shapes and sizes were manufactured and remained stable for more than six months. Live/dead and DAPI stainings showed viable cells 24 h after the printing process, as well as after 21 days in culture. Histological and immunohistochemical analyses after 14 and 21 days revealed viable cells with marked matrix production and signs of proliferation. The compressive strength values of the printed gels consequently increased during the two weeks in culture, revealing encouraging results for future applications in regenerative medicine. (paper)
Precollisional velocity correlations in a hard-disk fluid with dissipative collisions.
Soto, R; Piasecki, J; Mareschal, M
2001-09-01
Velocity correlations are studied in granular fluids, modeled by the inelastic hard sphere gas. Making a density expansion of the Bogoliubov-Born-Green-Kirkwood-Yvon hierarchy for the evolution of the reduced distributions, we predict the presence of precollisional velocity correlations. They are created by the propagation through correlated sequences of collisions (ring events) of the velocity correlations generated after dissipative collisions. The correlations have their origin in the dissipative character of collisions, being always present in granular fluids. The correlations, that manifest microscopically as an alignment of the velocities of a colliding pair produce modifications of collisional averages, in particular, the virial pressure. The pressure shows a reduction with respect to the elastic case as a consequence of the velocity alignment. Good qualitative agreement is obtained for the comparison of the numerical evaluations of the obtained analytical expressions and molecular dynamics results that showed evidence of precollisional velocity correlations [R. Soto and M. Mareschal, Phys. Rev. E 63, 041303 (2001)].
Thermal diffusion segregation of an impurity in a driven granular fluid
Energy Technology Data Exchange (ETDEWEB)
Reyes, Francisco Vega; Garzó, Vicente [Departamento de Física, Universidad de Extremadura, E-06071 Badajoz, Spain and Instituto de Computación Científica Avanzada (ICCAEx), Universidad de Extremadura, E-06071 Badajoz (Spain)
2014-12-09
We study segregation of an impurity in a driven granular fluid under two types of steady states. In the first state, the granular gas is driven by a stochastic volume force field with a Fourier-type profile while in the second state, the granular gas is sheared in such a way that inelastic cooling is balanced by viscous heating. We compare theoretical results derived from a solution of the (inelastic) Boltzmann equation at Navier-Stokes (NS) order with those obtained from the Direct Monte Carlo simulation (DSMC) method and molecular dynamics (MD) simulations. Good agreement is found between theory and simulation, which provides strong evidence of the reliability of NS granular hydrodynamics for these steady states (including the dynamics of the impurity), even at high inelasticity. In addition, preliminary results for thermal diffusion in granular fluids at moderate densities are also presented. As for dilute gases, excellent agreement is also found in this more general case.
Nothias, Louis-Félix; Boutet-Mercey, Stéphanie; Cachet, Xavier; De La Torre, Erick; Laboureur, Laurent; Gallard, Jean-François; Retailleau, Pascal; Brunelle, Alain; Dorrestein, Pieter C; Costa, Jean; Bedoya, Luis M; Roussi, Fanny; Leyssen, Pieter; Alcami, José; Paolini, Julien; Litaudon, Marc; Touboul, David
2017-10-27
A supercritical fluid chromatography-based targeted purification procedure using tandem mass spectrometry and molecular networking was developed to analyze, annotate, and isolate secondary metabolites from complex plant extract mixture. This approach was applied for the targeted isolation of new antiviral diterpene esters from Euphorbia semiperfoliata whole plant extract. The analysis of bioactive fractions revealed that unknown diterpene esters, including jatrophane esters and phorbol esters, were present in the samples. The purification procedure using semipreparative supercritical fluid chromatography led to the isolation and identification of two new jatrophane esters (13 and 14) and one known (15) and three new 4-deoxyphorbol esters (16-18). The structure and absolute configuration of compound 16 were confirmed by X-ray crystallography. This compound was found to display antiviral activity against Chikungunya virus (EC 50 = 0.45 μM), while compound 15 proved to be a potent and selective inhibitor of HIV-1 replication in a recombinant virus assay (EC 50 = 13 nM). This study showed that a supercritical fluid chromatography-based protocol and molecular networking can facilitate and accelerate the discovery of bioactive small molecules by targeting molecules of interest, while minimizing the use of toxic solvents.
Ferreira, Lizé-Mari; Eaby, Alan; Dillen, Jan
2017-12-15
The topology of the Coulomb potential density has been studied within the context of the theory of Atoms in Molecules and has been compared with the topologies of the electron density, the virial energy density and the Ehrenfest force density. The Coulomb potential density is found to be mainly structurally homeomorphic with the electron density. The Coulomb potential density reproduces the non-nuclear attractor which is observed experimentally in the molecular graph of the electron density of a Mg dimer, thus, for the first time ever providing an alternative and energetic foundation for the existence of this critical point. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.
Structural studies of fluid mercury using synchrotron radiation at SPring-8
International Nuclear Information System (INIS)
Hong Xinguo; Tamura, K.
2003-01-01
With the volume expansion by heating up toward the critical point, typical liquid metal mercury undergoes metal-nonmetal transition (M-NM) at a density around 9 g/cm 3 . To study the structure changes of fluid Hg during volume expansion, we have carried out X-ray diffraction measurements for expanded fluid mercury in a wide density region from liquid to dense vapour region using synchrotron radiation at SPring-8. We have succeeded in developing a new high-pressure vessel, up to 1700 degree C under 2000 bar and with 7 scattering windows for energy-dispersive X-ray diffraction (EDXD) measurements under high temperature and high pressure. It was found that the reliability of the structure factors, S(k), and the accuracy of the pair distribution functions, g(r), are much better. Reliable relations of the coordination number and the correlation distance with the density of fluid Hg were obtained. Structural model of volume expansion of fluid Hg is proposed based on our new results. Structural changes with decreasing density are discussed in relation to the M-NM transition in fluid Hg
Theory of nonlinear acoustic forces acting on fluids and particles in microsystems
DEFF Research Database (Denmark)
Karlsen, Jonas Tobias
fundamentally new capabilities in chemical, biomedical, or clinical studies of single cells and bioparticles. This thesis, entitled Theory of nonlinear acoustic forces acting on fluids and particles in microsystems, advances the fundamental understanding of acoustofluidics by addressing the origin...... of the nonlinear acoustic forces acting on fluids and particles. Classical results in nonlinear acoustics for the non-dissipative acoustic radiation force acting on a particle or an interface, as well as the dissipative acoustic force densities driving acoustic streaming, are derived and discussed in terms...... in the continuous fluid parameters of density and compressibility, e.g., due to a solute concentration field, the thesis presents novel analytical results on the acoustic force density acting on inhomogeneous fluids in acoustic fields. This inhomogeneity-induced acoustic force density is non-dissipative in origin...
Cosmological models described by a mixture of van der Waals fluid and dark energy
International Nuclear Information System (INIS)
Kremer, G.M.
2003-01-01
The Universe is modeled as a binary mixture whose constituents are described by a van der Waals fluid and by a dark energy density. The dark energy density is considered either as quintessence or as the Chaplygin gas. The irreversible processes concerning the energy transfer between the van der Waals fluid and the gravitational field are taken into account. This model can simulate (a) an inflationary period where the acceleration grows exponentially and the van der Waals fluid behaves like an inflaton, (b) an accelerated period where the acceleration is positive but it decreases and tends to zero whereas the energy density of the van der Waals fluid decays, (c) a decelerated period which corresponds to a matter dominated period with a non-negative pressure, and (d) a present accelerated period where the dark energy density outweighs the energy density of the van der Waals fluid
Principles of fluid-structure interaction
International Nuclear Information System (INIS)
Schumann, U.; Kernforschungszentrum Karlsruhe G.m.b.H.
1981-01-01
Fluid-structure interaction (FSI) is an important physical phenomenon which has attracted significant attention in nuclear reactor safety analysis. Here, simple explanations of the principle effects of FSI are given and illustrated by reference to numerical and experimental results. First, a very simple fluid-structure model is introduced which consists of a spring supported piston closing a fluid filled rigid pipe. The motion of the piston and the fluid is approximately described by one degree of freedom, respectively. Depending on the load frequency and material parameters one finds that the coupled system is characterized by virtual masses and stiffnesses or by the inverse properties which are termed virtual fluidities and compressibilities. Thus the two parts interact as if they are connected in series or in parallel. The two eigenfrequencies of the coupled system enclose the eigenfrequencies of the individual fluid and structure parts. Second, the great importance of Hamilton's principle for derivation of the coupled equations of motion is emphasized. From this principle upper and lower bounds for the effective density of a heterogeneous fluid-solid mixture are deduced. Continuum models for such mixtures contain a virtual density tensor. Finally, we discuss FSI for the case of a loss-of-coolant accident (LOCA) in a pressurized water reactor (PWR) in the first (subcooled) blowdown period. Here, the fluid imposes pressure loadings on internal structures like the core barrel and the motion of these structures influences the fluid motion. Recent experimental results obtained at the HDR are compared with numerical predictions of the FLUX 2-code. The fair agreement confirms that we have well understood the principal effects of FSI. (orig.) [de
MOLECULAR DESIGN OF COLLOIDS IN SUPERCRITICAL FLUIDS
Energy Technology Data Exchange (ETDEWEB)
Keith P. Johnston
2009-04-06
The environmentally benign, non-toxic, non-flammable fluids water and carbon dioxide (CO2) are the two most abundant and inexpensive solvents on earth. Emulsions of these fluids are of interest in many industrial processes, as well as CO2 sequestration and enhanced oil recovery. Until recently, formation of these emulsions required stabilization with fluorinated surfactants, which are expensive and often not environmentally friendly. In this work we overcame this severe limitation by developing a fundamental understanding of the properties of surfactants the CO2-water interface and using this knowledge to design and characterize emulsions stabilized with either hydrocarbon-based surfactants or nanoparticle stabilizers. We also discovered a new concept of electrostatic stabilization for CO2-based emulsions and colloids. Finally, we were able to translate our earlier work on the synthesis of silicon and germanium nanocrystals and nanowires from high temperatures and pressures to lower temperatures and ambient pressure to make the chemistry much more accessible.
Density Effects on Post-shock Turbulence Structure
Tian, Yifeng; Jaberi, Farhad; Livescu, Daniel; Li, Zhaorui; Michigan State University Collaboration; Los Alamos National Laboratory Collaboration; Texas A&M University-Corpus Christi Collaboration
2017-11-01
The effects of density variations due to mixture composition on post-shock turbulence structure are studied using turbulence-resolving shock-capturing simulations. This work extends the canonical Shock-Turbulence Interaction (STI) problem to involve significant variable density effects. The numerical method has been verified using a series of grid and LIA convergence tests, and is used to generate accurate post-shock turbulence data for a detailed flow study. Density effects on post-shock turbulent statistics are shown to be significant, leading to an increased amplification of turbulent kinetic energy (TKE). Eulerian and Lagrangian analyses show that the increase in the post-shock correlation between rotation and strain is weakened in the case with significant density variations (referred to as the ``multi-fluid'' case). Similar to previous single-fluid results and LIA predictions, the shock wave significantly changes the topology of the turbulent structures, exhibiting a symmetrization of the joint PDF of second and third invariant of the deviatoric part of velocity gradient tensor. In the multi-fluid case, this trend is more significant and mainly manifested in the heavy fluid regions. Lagrangian data are also used to study the evolution of turbulence structure away from the shock wave and assess the accuracy of Lagrangian dynamical models.
Nonminimal coupling of perfect fluids to curvature
International Nuclear Information System (INIS)
Bertolami, Orfeu; Lobo, Francisco S. N.; Paramos, Jorge
2008-01-01
In this work, we consider different forms of relativistic perfect fluid Lagrangian densities that yield the same gravitational field equations in general relativity (GR). A particularly intriguing example is the case with couplings of the form [1+f 2 (R)]L m , where R is the scalar curvature, which induces an extra force that depends on the form of the Lagrangian density. It has been found that, considering the Lagrangian density L m =p, where p is the pressure, the extra-force vanishes. We argue that this is not the unique choice for the matter Lagrangian density, and that more natural forms for L m do not imply the vanishing of the extra force. Particular attention is paid to the impact on the classical equivalence between different Lagrangian descriptions of a perfect fluid.
Inviscid linear stability analysis of two fluid columns of different densities subject to gravity
Prathama, Aditya; Pantano, Carlos
2017-11-01
We investigate the inviscid linear stability of vertical interface between two fluid columns of different densities under the influence of gravity. In this flow arrangement, the two free streams are continuously accelerating, in contrast to the canonical Kelvin-Helmholtz or Rayleigh-Taylor instabilities whose base flows are stationary (or weakly time dependent). In these classical cases, the temporal evolution of the interface can be expressed as Fourier or Laplace solutions in time. This is not possible in our case; instead, we employ the initial value problem method to solve the equations analytically. The results, expressed in terms of the well-known parabolic cylinder function, indicate that the instability grows as the exponential of a quadratic function of time. The analysis shows that in this accelerating Kelvin-Helmholtz configuration, the interface is unconditionally unstable at all wave modes, despite the presence of surface tension. Department of Energy, National Nuclear Security Administration (Award No. DE-NA0002382) and the California Institute of Technology.
Nanoscale Pore Features and Associated Fluid Behavior in Shale
Cole, D. R.; Striolo, A.
2017-12-01
Unconventional hydrocarbons occurring in economic abundance require greater than industry-standard levels of technology or investment to exploit. Geological formations that host unconventional oil and gas are extraordinarily heterogeneous and exhibit a wide range of physical and chemical features that can vary over many orders of magnitude in length scale. The size, distribution and connectivity of these confined geometries, the chemistry of the solid, the chemistry of the fluids and their physical properties collectively dictate how fluids migrate into and through these micro- and nano-environments, wet and ultimately react with the solid surfaces. Our current understanding of the rates and mechanisms of fluid and mass transport and interaction within these multiporosity systems at the molecular scale is far less robust than we would like. This presentation will take a two-fold approach to this topic area. First, a brief overview is provided that highlights the use of advanced electron microscopy and neutrons scattering methods to quantify the nature of the nanopore system that hosts hydrocarbons in representative gas shale formations such as the Utica, Marcellus and Eagle Ford. Second, results will be presented that leverage the application of state-of-the-art experimental, analytical and computational tools to assess key features of the fluid-matrix interaction relevant to shale settings. The multidisciplinary approaches highlighted will include neutron scattering and NMR experiments, thermodynamic measurements and molecular-level simulations to quantitatively assess molecular properties of C-O-H fluids confined to well-characterized porous media, subjected to temperatures and pressures relevant to subsurface energy systems. These studies conducted in concert are beginning to provide a fundamental understanding at the molecular level of how intrinsically different hydrocarbon-bearing fluids behave in confined geometries compared to bulk systems, and shed light
Periodic subsystem density-functional theory
International Nuclear Information System (INIS)
Genova, Alessandro; Pavanello, Michele; Ceresoli, Davide
2014-01-01
By partitioning the electron density into subsystem contributions, the Frozen Density Embedding (FDE) formulation of subsystem Density Functional Theory (DFT) has recently emerged as a powerful tool for reducing the computational scaling of Kohn–Sham DFT. To date, however, FDE has been employed to molecular systems only. Periodic systems, such as metals, semiconductors, and other crystalline solids have been outside the applicability of FDE, mostly because of the lack of a periodic FDE implementation. To fill this gap, in this work we aim at extending FDE to treat subsystems of molecular and periodic character. This goal is achieved by a dual approach. On one side, the development of a theoretical framework for periodic subsystem DFT. On the other, the realization of the method into a parallel computer code. We find that periodic FDE is capable of reproducing total electron densities and (to a lesser extent) also interaction energies of molecular systems weakly interacting with metallic surfaces. In the pilot calculations considered, we find that FDE fails in those cases where there is appreciable density overlap between the subsystems. Conversely, we find FDE to be in semiquantitative agreement with Kohn–Sham DFT when the inter-subsystem density overlap is low. We also conclude that to make FDE a suitable method for describing molecular adsorption at surfaces, kinetic energy density functionals that go beyond the GGA level must be employed
Periodic subsystem density-functional theory
Genova, Alessandro; Ceresoli, Davide; Pavanello, Michele
2014-11-01
By partitioning the electron density into subsystem contributions, the Frozen Density Embedding (FDE) formulation of subsystem Density Functional Theory (DFT) has recently emerged as a powerful tool for reducing the computational scaling of Kohn-Sham DFT. To date, however, FDE has been employed to molecular systems only. Periodic systems, such as metals, semiconductors, and other crystalline solids have been outside the applicability of FDE, mostly because of the lack of a periodic FDE implementation. To fill this gap, in this work we aim at extending FDE to treat subsystems of molecular and periodic character. This goal is achieved by a dual approach. On one side, the development of a theoretical framework for periodic subsystem DFT. On the other, the realization of the method into a parallel computer code. We find that periodic FDE is capable of reproducing total electron densities and (to a lesser extent) also interaction energies of molecular systems weakly interacting with metallic surfaces. In the pilot calculations considered, we find that FDE fails in those cases where there is appreciable density overlap between the subsystems. Conversely, we find FDE to be in semiquantitative agreement with Kohn-Sham DFT when the inter-subsystem density overlap is low. We also conclude that to make FDE a suitable method for describing molecular adsorption at surfaces, kinetic energy density functionals that go beyond the GGA level must be employed.
Adsorption of molecular hydrogen on nanostructered surfaces
International Nuclear Information System (INIS)
Uranga Piña, Llinersy; Martínez Mesa, Aliezer; Seifert, Gotthard
2015-01-01
Were investigated the effect of the structural characteristics of model nanoporous environments on the adsorption of molecular hydrogen. The adsorption properties of the target nanostructures (graphene and ZnO sheets, carbon foams, metal-organic frameworks) are evaluated in a broad range of thermodynamic conditions. The study is carried out within the density functional theory for quantum fluids at finite temperature (QLDFT), which allows to account for the many-body and quantum delocalization effects in a single theoretical framework. The exchange-correlation (excess) functional is derived from the empirical equation of state of the homogeneous system. We focus on the evaluation of hydrogen storage capacities of the substrates and on the emergence of quantum effects triggered by the confinement imposed by the host structure. The approach provides accurate estimates of the hydrogen storage capacities for realistic adsorptive media. The relation between the microscopic structure of the hydrogen fluid and the calculated adsorption properties is also addressed. (full text)
Energy Technology Data Exchange (ETDEWEB)
Mackie, Matt [Helsinki Institute of Physics, PL 64, FIN-00014 Helsingin yliopisto (Finland); Collin, Anssi [Helsinki Institute of Physics, PL 64, FIN-00014 Helsingin yliopisto (Finland); Suominen, Kalle-Antti [Helsinki Institute of Physics, PL 64, FIN-00014 Helsingin yliopisto (Finland); Javanainen, Juha [Department of Physics, University of Connecticut, Storrs, CT 06269-3046 (United States)
2003-08-01
Although photoassociation and the Feshbach resonance are feasible means in principle for creating a molecular Bose-Einstein condensate (MBEC) from an already quantum-degenerate gas of atoms, collision-induced mean-field shifts and irreversible decay place practical constraints on the efficient Raman delivery of stable molecules. Focusing on stimulated Raman adiabatic passage, we propose that the efficiency of both mechanisms for producing a stable MBEC can be improved by treating the density of the initial atom condensate as an optimization parameter.
Thermodynamic Fluid Equations-of-State
Directory of Open Access Journals (Sweden)
Leslie V. Woodcock
2018-01-01
Full Text Available As experimental measurements of thermodynamic properties have improved in accuracy, to five or six figures, over the decades, cubic equations that are widely used for modern thermodynamic fluid property data banks require ever-increasing numbers of terms with more fitted parameters. Functional forms with continuity for Gibbs density surface ρ(p,T which accommodate a critical-point singularity are fundamentally inappropriate in the vicinity of the critical temperature (Tc and pressure (pc and in the supercritical density mid-range between gas- and liquid-like states. A mesophase, confined within percolation transition loci that bound the gas- and liquid-state by third-order discontinuities in derivatives of the Gibbs energy, has been identified. There is no critical-point singularity at Tc on Gibbs density surface and no continuity of gas and liquid. When appropriate functional forms are used for each state separately, we find that the mesophase pressure functions are linear. The negative and positive deviations, for both gas and liquid states, on either side of the mesophase, are accurately represented by three or four-term virial expansions. All gaseous states require only known virial coefficients, and physical constants belonging to the fluid, i.e., Boyle temperature (TB, critical temperature (Tc, critical pressure (pc and coexisting densities of gas (ρcG and liquid (ρcL along the critical isotherm. A notable finding for simple fluids is that for all gaseous states below TB, the contribution of the fourth virial term is negligible within experimental uncertainty. Use may be made of a symmetry between gas and liquid states in the state function rigidity (dp/dρT to specify lower-order liquid-state coefficients. Preliminary results for selected isotherms and isochores are presented for the exemplary fluids, CO2, argon, water and SF6, with focus on the supercritical mesophase and critical region.
Self-diffusion coefficients and shear viscosity of inverse power fluids: from hard- to soft-spheres.
Heyes, D M; Brańka, A C
2008-07-21
Molecular dynamics computer simulation has been used to compute the self-diffusion coefficient, D, and shear viscosity, eta(s), of soft-sphere fluids, in which the particles interact through the soft-sphere or inverse power pair potential, phi(r) = epsilon(sigma/r)(n), where n measures the steepness or stiffness of the potential, and epsilon and sigma are a characteristic energy and distance, respectively. The simulations were carried out on monodisperse systems for a range of n values from the hard-sphere (n --> infinity) limit down to n = 4, and up to densities in excess of the fluid-solid co-existence value. A new analytical procedure is proposed which reproduces the transport coefficients at high densities, and can be used to extrapolate the data to densities higher than accurately accessible by simulation or experiment, and tending to the glass transition. This formula, DX(c-1) proportional, variant A/X + B, where c is an adjustable parameter, and X is either the packing fraction or the pressure, is a development of one proposed by Dymond. In the expression, -A/B is the value of X at the ideal glass transition (i.e., where D and eta(s)(-1) --> 0). Estimated values are presented for the packing fraction and the pressure at the glass transition for n values between the hard and soft particle limits. The above expression is also shown to reproduce the high density viscosity data of supercritical argon, krypton and nitrogen. Fits to the soft-sphere simulation transport coefficients close to solid-fluid co-existence are also made using the analytic form, ln(D) = alpha(X)X, and n-dependence of the alpha(X) is presented (X is either the packing fraction or the pressure).
QUASI-ONE DIMENSIONAL CLASSICAL FLUIDS
Directory of Open Access Journals (Sweden)
J.K.Percus
2003-01-01
Full Text Available We study the equilibrium statistical mechanics of simple fluids in narrow pores. A systematic expansion is made about a one-dimensional limit of this system. It starts with a density functional, constructed from projected densities, which depends upon projected one and two-body potentials. The nature of higher order corrections is discussed.
Song, Lingchun; Han, Jaebeom; Lin, Yen-lin; Xie, Wangshen; Gao, Jiali
2009-10-29
The explicit polarization (X-Pol) method has been examined using ab initio molecular orbital theory and density functional theory. The X-Pol potential was designed to provide a novel theoretical framework for developing next-generation force fields for biomolecular simulations. Importantly, the X-Pol potential is a general method, which can be employed with any level of electronic structure theory. The present study illustrates the implementation of the X-Pol method using ab initio Hartree-Fock theory and hybrid density functional theory. The computational results are illustrated by considering a set of bimolecular complexes of small organic molecules and ions with water. The computed interaction energies and hydrogen bond geometries are in good accord with CCSD(T) calculations and B3LYP/aug-cc-pVDZ optimizations.
Properties of molecular solids and fluids at high pressures and temperatures. [Final report
International Nuclear Information System (INIS)
Etters, R.D.
1985-01-01
Equilibrium structures and orientations, lattice vibrational and librational model frequencies, intramolecular vibron mode frequencies, sound velocities, equations of state, compressibilities, and structural and orientational phase transitions in molecular solids are determined over a wide range of pressures and temperatures. In the high temperature fluid phase the equations of state, vibron frequencies, the melting transition, specific heats, compressibilities, second virial coefficients, viscosities and other transport properties, and the nature of orientational and magnetic correlations are determined. The techniques used include several strategies to optimize multi-dimensional functions as a means to determine equilibrium structures and orientations, self consistent phonon lattice dynamics methods, constant pressure and constant volume Monte-Carlo strategies with continuously deformable boundary conditions, mean field approximations, and classical perturbation methods. Systems studied include N 2 , O 2 , CO, CO 2 , F 2 , N 2 O, benzine, nitromethane, HCL, HBr, and H 2 . 50 refs., 4 figs
Packing frustration in dense confined fluids.
Nygård, Kim; Sarman, Sten; Kjellander, Roland
2014-09-07
Packing frustration for confined fluids, i.e., the incompatibility between the preferred packing of the fluid particles and the packing constraints imposed by the confining surfaces, is studied for a dense hard-sphere fluid confined between planar hard surfaces at short separations. The detailed mechanism for the frustration is investigated via an analysis of the anisotropic pair distributions of the confined fluid, as obtained from integral equation theory for inhomogeneous fluids at pair correlation level within the anisotropic Percus-Yevick approximation. By examining the mean forces that arise from interparticle collisions around the periphery of each particle in the slit, we calculate the principal components of the mean force for the density profile--each component being the sum of collisional forces on a particle's hemisphere facing either surface. The variations of these components with the slit width give rise to rather intricate changes in the layer structure between the surfaces, but, as shown in this paper, the basis of these variations can be easily understood qualitatively and often also semi-quantitatively. It is found that the ordering of the fluid is in essence governed locally by the packing constraints at each single solid-fluid interface. A simple superposition of forces due to the presence of each surface gives surprisingly good estimates of the density profiles, but there remain nontrivial confinement effects that cannot be explained by superposition, most notably the magnitude of the excess adsorption of particles in the slit relative to bulk.
A History of constitutive modeling via molecular dynamics: Shock waves in fluids and gases
Directory of Open Access Journals (Sweden)
Holian B.L.
2011-01-01
Full Text Available From its inception in the mid-Fifties, the method of molecular-dynamics (MD computer simulations has been used to probe the foundations of statistical mechanics, first for equilibrium equation-of-state averages, and then for transport properties from equilibrium fluctuations. Traditional statistical mechanical theoreticians were shocked to see that this new-fangled computational physics approach was feasible, even with incredibly tiny samples (on the order of a hundred atoms. When direct measurement of transport coefficients by non-equilibrium molecular dynamics (NEMD was proposed in the early Seventies, even greater resistance was encountered from the traditionalists – though evidence for convergence with the equilibrium fluctuation method gradually accumulated. In the late Seventies and early Eighties, shock-wave simulations by NEMD made it possible to test directly the principal continuum constitutive theory for fluids, namely, Navier-Stokes viscous flow and Fourier’s Law of heat conduction. To everyone’s surprise – and the consternation of many – NEMD, once again, demonstrated that continuum theory applies at embarrassingly small (atomistic time and length scales. We pursue this early line of work into the modern era, showing how NEMD shock-wave simulations can still provide surprising insights and improvements upon our understanding of constitutive modeling.
The successive formation and disappearance of density structures in simple expanding systems
International Nuclear Information System (INIS)
Karimov, A R; Schamel, H
2015-01-01
The Lagrangian fluid description is employed to solve the initial value problem for one-dimensional, compressible fluid flows represented by the Euler–Poisson system. Exact nonlinear and time-dependent solutions are obtained, which exhibit a variety of transient phenomena such as a density collapse in finite space–time or the appearance and, for the first time, a successive dissolution of wavelet structures during the same event. The latter are superimposed on the gross density pattern in the course of the uni-directional expansion of an initially localized density hump. Whereas self-gravitating fluids will always experience collapse, neutral fluids and fluids with repulsive forces, such as a non-neutral, pure electron fluid, can exhibit an evolution of the second type, being determined by the initial conditions. For an electron fluid, being embedded in a neutralizing ion background, these nonlinearities are, however, strongly diminished due to the omnipresent plasma oscillations, which weaken and alternatively change the sign of the collective force. (paper)
Method of making supercritical fluid molecular spray films, powder and fibers
Smith, Richard D.
1988-01-01
Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercritical fluid solution at an elevated pressure and then rapidly expanding the solution through a heated nozzle having a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. In another embodiment, the temperature of the solution and nozzle is elevated above the melting point of the solute, which is preferably a polymer, and the solution is maintained at a pressure such that, during expansion, the solute precipitates out of solution within the nozzle in a liquid state. Alternatively, a secondary solvent mutually soluble with the solute and primary solvent and having a higher critical temperature than that of primary solvent is used in a low concentration (<20%) to maintain the solute in a transient liquid state. The solute is discharged in the form of long, thin fibers. The fibers are collected at sufficient distance from the orifice to allow them to solidify in the low pressure/temperature region.
Capillary condensation and orientational ordering of confined polar fluids.
Gramzow, Matthias; Klapp, Sabine H L
2007-01-01
The phase behavior and the orientational structure of polar model fluids confined to slit pores is investigated by means of density functional theory in a modified mean-field approximation. We focus on fluid states and further assume a uniform number density throughout the pore. Our results for spherical dipolar particles with additional van der Waals-like interactions (Stockmayer fluids) reveal complex fluid-fluid phase behavior involving condensation and first- and second-order isotropic-to-ferroelectric phase transitions, where the ferroelectric ordering occurs parallel to the confining walls. The relative importance of these phase transitions depends on two "tuning" parameters, that is the strength of the dipolar interactions (relative to the isotropic attractive ones) between fluid particles, and on the pore width. In particular, in narrow pores the condensation transition seen in bulk Stockmayer fluids is entirely suppressed. For dipolar hard spheres, on the other hand, the impact of confinement consists in a decrease of the isotropic-to-ferroelectric transition temperatures. We also demonstrate that the local orientational structure is inhomogeneous and anisotropic even in globally isotropic systems, in agreement with computer simulation results.
Effect of the particle to fluid density ratio on bedform development: An application of PTV
McKenna Neuman, C. L.; Gordon, M. D.
2009-05-01
The particle to fluid density ratio plays a key role in sediment transport and strongly governs the relative importance of the transport mode. In aeolian systems, this ratio is three orders of magnitude larger than for the transport of sedimentary particles in water, such that saltation is the dominant mode for diameters (250 microns) commonly found in ripples and dunes. The partitioning of fluid momentum to saltators, and therefore to the surface upon impact, is extremely important to the entrainment of sediment, the maintenance of transport, and the scaling of aeolian bedforms. This paper demonstrates the use of Particle Tracking Velocimetry in measuring the partitioning of momentum associated with particle collisions on beds of quartz sand (2630 kg m-3) typical of aeolian dunes, and acrylic particles (1210 kg m-3) similar to blowing snow (920 kg m-3). The experiments were carried out in the boundary layer wind tunnel at Trent University on full beds that were 13.8 m in length and 0.71 m in width. In the majority of experiments, the wind speeds were either at or just above the threshold for saltation so that we could distinguish discrete particle trajectories. Surface ripples formed in the majority of experiments and passed through the camera's field of view so that the height, length and rate of migration could be measured in relation to the distributions of particle impact speed and angle, as well as those for the number, speed and angle of the particles ejected. Although similar in height, the ripples comprised of acrylic particles were 2 to 4 times longer, much more asymmetric, and migrated significantly faster than those in sand. The particle impact and ejection speeds were very similar, although the sand particles approached and left the bed at substantially larger angles than observed for the lighter acrylic particles of similar diameter. In a separate experiment, glass beads were flung onto each bed material at 4 ms-1 in still air. It was discovered that
Asymmetric continuum extreme processes in solids and fluids
Teisseyre, Roman
2014-01-01
This book deals with a class of basic deformations in asymmetric continuum theory. It describes molecular deformations and transport velocities in fluids, strain deformations in solids as well as the molecular transport, important in fracture processes.
Continuous blood densitometry - Fluid shifts after graded hemorrhage in animals
Hinghofer-Szalkay, H.
1986-01-01
Rapid fluid shifts in four pigs and two dogs subjected to graded hemorrhage are investigated. Arterial blood density (BD), mean arterial pressure (MAP), central venous pressure (CVP), arterial plasma density (PD), hematocrit (Hct) and erythrocyte density were measured. The apparatus and mechancial oscillator technique for measuring density are described. Fluid shifts between red blood cells and blood plasma and alterations in the whole-body-to-large vessel Hct, F(cell) are studied using two models. The bases of the model calculations are discussed. A decrease in MAP, CVP, and BP is detected at the beginning of hemorrhaging; continued bleeding results in further BD decrease correlating with volume displacement. The data reveal that at 15 ml/kg blood loss the mean PD and BD dropped by 0.99 + or - 0.15 and 2.42 + or 0.26 g/liter, respectively, and the Hct dropped by 2.40 + or 0.47 units. The data reveal that inward-shifted fluid has a higher density than normal ultrafiltrate and/or there is a rise in the F(cell) ratio. It is noted that rapid fluid replacement ranged from 5.8 + or - 0.8 to 10.6 + or - 2.0 percent of the initial plasma volume.
Review of computational fluid dynamics (CFD) researches on nano fluid flow through micro channel
Dewangan, Satish Kumar
2018-05-01
Nanofluid is becoming a promising heat transfer fluids due to its improved thermo-physical properties and heat transfer performance. Micro channel heat transfer has potential application in the cooling high power density microchips in CPU system, micro power systems and many such miniature thermal systems which need advanced cooling capacity. Use of nanofluids enhances the effectiveness of t=scu systems. Computational Fluid Dynamics (CFD) is a very powerful tool in computational analysis of the various physical processes. It application to the situations of flow and heat transfer analysis of the nano fluids is catching up very fast. Present research paper gives a brief account of the methodology of the CFD and also summarizes its application on nano fluid and heat transfer for microchannel cases.
Directory of Open Access Journals (Sweden)
Prudence O Powell
Full Text Available Phytoglycogen (from certain mutant plants and animal glycogen are highly branched glucose polymers with similarities in structural features and molecular size range. Both appear to form composite α particles from smaller β particles. The molecular size distribution of liver glycogen is bimodal, with distinct α and β components, while that of phytoglycogen is monomodal. This study aims to enhance our understanding of the nature of the link between liver-glycogen β particles resulting in the formation of large α particles. It examines the time evolution of the size distribution of these molecules during acid hydrolysis, and the size dependence of the molecular density of both glucans. The monomodal distribution of phytoglycogen decreases uniformly in time with hydrolysis, while with glycogen, the large particles degrade significantly more quickly. The size dependence of the molecular density shows qualitatively different shapes for these two types of molecules. The data, combined with a quantitative model for the evolution of the distribution during degradation, suggest that the bonding between β into α particles is different between phytoglycogen and liver glycogen, with the formation of a glycosidic linkage for phytoglycogen and a covalent or strong non-covalent linkage, most probably involving a protein, for glycogen as most likely. This finding is of importance for diabetes, where α-particle structure is impaired.
Powell, Prudence O.; Sullivan, Mitchell A.; Sheehy, Joshua J.; Schulz, Benjamin L.; Warren, Frederick J.; Gilbert, Robert G.
2015-01-01
Phytoglycogen (from certain mutant plants) and animal glycogen are highly branched glucose polymers with similarities in structural features and molecular size range. Both appear to form composite α particles from smaller β particles. The molecular size distribution of liver glycogen is bimodal, with distinct α and β components, while that of phytoglycogen is monomodal. This study aims to enhance our understanding of the nature of the link between liver-glycogen β particles resulting in the formation of large α particles. It examines the time evolution of the size distribution of these molecules during acid hydrolysis, and the size dependence of the molecular density of both glucans. The monomodal distribution of phytoglycogen decreases uniformly in time with hydrolysis, while with glycogen, the large particles degrade significantly more quickly. The size dependence of the molecular density shows qualitatively different shapes for these two types of molecules. The data, combined with a quantitative model for the evolution of the distribution during degradation, suggest that the bonding between β into α particles is different between phytoglycogen and liver glycogen, with the formation of a glycosidic linkage for phytoglycogen and a covalent or strong non-covalent linkage, most probably involving a protein, for glycogen as most likely. This finding is of importance for diabetes, where α-particle structure is impaired. PMID:25799321
Goikoetxea, I; Meyer, J; Juaristi, J I; Alducin, M; Reuter, K
2014-04-18
We simulate the scattering of O2 from Ag(111) with classical dynamics simulations performed on a six-dimensional potential energy surface calculated within semilocal density-functional theory. The enigmatic experimental trends that originally required the conjecture of two types of repulsive walls, arising from a physisorption and chemisorption part of the interaction potential, are fully reproduced. Given the inadequate description of the physisorption properties in semilocal density-functional theory, our work casts severe doubts on the prevalent notion to use molecular scattering data as indirect evidence for the existence of such states.
Fluids in porous media. IV. Quench effect on chemical potential.
Qiao, C Z; Zhao, S L; Liu, H L; Dong, W
2017-06-21
It appears to be a common sense to measure the crowdedness of a fluid system by the densities of the species constituting it. In the present work, we show that this ceases to be valid for confined fluids under some conditions. A quite thorough investigation is made for a hard sphere (HS) fluid adsorbed in a hard sphere matrix (a quench-annealed system) and its corresponding equilibrium binary mixture. When fluid particles are larger than matrix particles, the quench-annealed system can appear much more crowded than its corresponding equilibrium binary mixture, i.e., having a much higher fluid chemical potential, even when the density of each species is strictly the same in both systems, respectively. We believe that the insight gained from this study should be useful for the design of functionalized porous materials.
New knowledge on the temperature-entropy saturation boundary slope of working fluids
International Nuclear Information System (INIS)
Su, Wen; Zhao, Li; Deng, Shuai
2017-01-01
The slope of temperature-entropy saturation boundary of working fluids has a significant effect on the thermodynamic performance of cycle processes. However, for the working fluids used in cycles, few studies have been conducted to analyze the saturated slope from the molecular structure and mixture composition. Thus, in this contribution, an analytical expression on the slope of saturated curve is obtained based on the highly accurate Helmholtz energy equation. 14 pure working fluids and three typical binary mixtures are employed to analyze the influence of molecular groups and mixture compositions on the saturated slope, according to the correlated parameters of Helmholtz energy equation. Based on the calculated results, a preliminary trend is demonstrated that with an increase of the number of molecular groups, the positive liquid slope of pure fluids increases and the vapor slope appears positive sign in a narrow temperature range. Particularly, for the binary mixtures, the liquid slope is generally located between the corresponding pure fluids', while the vapor slope can be infinity by mixing dry and wet fluids ingeniously. It can be proved through the analysis of mixtures' saturated slope that three types of vapor slope could be obtained by regulating the mixture composition. - Highlights: • The saturated slope is derived from the Helmholtz function for working fluids. • The effect of molecular structure on the saturated slope is analyzed. • The variation of saturated slope with the mixture composition is investigated.
Gyro-fluid and two-fluid theory and simulations of edge-localized-modes
Energy Technology Data Exchange (ETDEWEB)
Xu, X. Q.; Dimits, A.; Joseph, I.; Umansky, M. V. [Lawrence Livermore National Laboratory, Livermore, California 94551 (United States); Xi, P. W. [Lawrence Livermore National Laboratory, Livermore, California 94551 (United States); School of Physics, Peking University, Beijing (China); Xia, T. Y.; Gui, B. [Lawrence Livermore National Laboratory, Livermore, California 94551 (United States); Institute of Plasma Physics, Chinese Academy of Sciences, Hefei (China); Kim, S. S.; Park, G. Y.; Rhee, T.; Jhang, H. [WCI Center for Fusion Theory, National Fusion Research Institute, Daejon 305-333 (Korea, Republic of); Diamond, P. H. [WCI Center for Fusion Theory, National Fusion Research Institute, Daejon 305-333 (Korea, Republic of); Center for Astrophysics and Space Sciences and Department of Physics, University of California, San Diego, La Jolla, California 92093-0424 (United States); Dudson, B. [University of York, Heslington, York YO10 5DD (United Kingdom); Snyder, P. B. [General Atomics, San Diego, California 92186 (United States)
2013-05-15
This paper reports on the theoretical and simulation results of a gyro-Landau-fluid extension of the BOUT++ code, which contributes to increasing the physics understanding of edge-localized-modes (ELMs). Large ELMs with low-to-intermediate-n peeling-ballooning (P-B) modes are significantly suppressed due to finite Larmor radius (FLR) effects when the ion temperature increases. For type-I ELMs, it is found from linear simulations that retaining complete first order FLR corrections as resulting from the incomplete “gyroviscous cancellation” in Braginskii's two-fluid model is necessary to obtain good agreement with gyro-fluid results for high ion temperature cases (T{sub i}≽3 keV) when the ion density has a strong radial variation, which goes beyond the simple local model of ion diamagnetic stabilization of ideal ballooning modes. The maximum growth rate is inversely proportional to T{sub i} because the FLR effect is proportional to T{sub i}. The FLR effect is also proportional to toroidal mode number n, so for high n cases, the P-B mode is stabilized by FLR effects. Nonlinear gyro-fluid simulations show results that are similar to those from the two-fluid model, namely that the P-B modes trigger magnetic reconnection, which drives the collapse of the pedestal pressure. Due to the additional FLR-corrected nonlinear E × B convection of the ion gyro-center density, for a ballooning-dominated equilibrium the gyro-fluid model further limits the radial spreading of ELMs. In six-field two fluid simulations, the parallel thermal diffusivity is found to prevent the ELM encroachment further into core plasmas and therefore leads to steady state L-mode profiles. The simulation results show that most energy is lost via ion channel during an ELM event, followed by particle loss and electron energy loss. Because edge plasmas have significant spatial inhomogeneities and complicated boundary conditions, we have developed a fast non-Fourier method for the computation of
Simplified local density model for adsorption over large pressure ranges
International Nuclear Information System (INIS)
Rangarajan, B.; Lira, C.T.; Subramanian, R.
1995-01-01
Physical adsorption of high-pressure fluids onto solids is of interest in the transportation and storage of fuel and radioactive gases; the separation and purification of lower hydrocarbons; solid-phase extractions; adsorbent regenerations using supercritical fluids; supercritical fluid chromatography; and critical point drying. A mean-field model is developed that superimposes the fluid-solid potential on a fluid equation of state to predict adsorption on a flat wall from vapor, liquid, and supercritical phases. A van der Waals-type equation of state is used to represent the fluid phase, and is simplified with a local density approximation for calculating the configurational energy of the inhomogeneous fluid. The simplified local density approximation makes the model tractable for routine calculations over wide pressure ranges. The model is capable of prediction of Type 2 and 3 subcritical isotherms for adsorption on a flat wall, and shows the characteristic cusplike behavior and crossovers seen experimentally near the fluid critical point
The impact of treatment density and molecular weight for fractional laser-assisted drug delivery
DEFF Research Database (Denmark)
Haak, Christina S; Bhayana, Brijesh; Farinelli, William A
2012-01-01
Ablative fractional lasers (AFXL) facilitate uptake of topically applied drugs by creating narrow open micro-channels into the skin, but there is limited information on optimal laser settings for delivery of specific molecules. The objective of this study was to investigate the impact of laser...... treatment density (% of skin occupied by channels) and molecular weight (MW) for fractional CO(2) laser-assisted drug delivery. AFXL substantially increased intra- and transcutaneous delivery of polyethylene glycols (PEGs) in a MW range from 240 to 4300 Da (Nuclear Magnetic Resonance, p...
Ruban, Anatoly I
This is the first book in a four-part series designed to give a comprehensive and coherent description of Fluid Dynamics, starting with chapters on classical theory suitable for an introductory undergraduate lecture course, and then progressing through more advanced material up to the level of modern research in the field. The present Part 1 consists of four chapters. Chapter 1 begins with a discussion of Continuum Hypothesis, which is followed by an introduction to macroscopic functions, the velocity vector, pressure, density, and enthalpy. We then analyse the forces acting inside a fluid, and deduce the Navier-Stokes equations for incompressible and compressible fluids in Cartesian and curvilinear coordinates. In Chapter 2 we study the properties of a number of flows that are presented by the so-called exact solutions of the Navier-Stokes equations, including the Couette flow between two parallel plates, Hagen-Poiseuille flow through a pipe, and Karman flow above an infinite rotating disk. Chapter 3 is d...
Grégoire, David; Malheiro, Carine; Miqueu, Christelle
2018-03-01
This study aims at characterising the adsorption-induced pore pressure and confinement in nanoscopic pores by molecular non-local density functional theory (DFT). Considering its important potential industrial applications, the adsorption of methane in graphitic slit pores has been selected as the test case. While retaining the accuracy of molecular simulations at pore scale, DFT has a very low computational cost that allows obtaining highly resolved pore pressure maps as a function of both pore width and thermodynamic conditions. The dependency of pore pressure on these parameters (pore width, pressure and temperature) is carefully analysed in order to highlight the effect of each parameter on the confined fluid properties that impact the solid matrix.
Molecular and phenotypic adaptation in social insect reproductive fluids
DEFF Research Database (Denmark)
Liberti, Joanito
of sperm competition. The seminal fluid of ants and bees with multiply mated queens are known to have evolved proteins that are able to kill the sperm of rival males, but the identity of the proteins involved has remained poorly understood. I sequenced the seminal fluid proteomes of four fungus-growing ant...... species that span the evolutionary transition from single to multiple queen-mating in the fungus-growing ant phylogeny. I then reconstructed the evolutionary histories of these proteins and identified a number of their functions related to energy production, control of oxidative stress, and proteolysis...
Stirling engine with air working fluid
Corey, John A.
1985-01-01
A Stirling engine capable of utilizing air as a working fluid which includes a compact heat exchange module which includes heating tube units, regenerator and cooler positioned about the combustion chamber. This arrangement has the purpose and effect of allowing the construction of an efficient, high-speed, high power-density engine without the use of difficult to seal light gases as working fluids.
Dark energy from cosmological fluids obeying a Shan-Chen non-ideal equation of state
Bini, Donato; Geralico, Andrea; Gregoris, Daniele; Succi, Sauro
2014-01-01
We consider a Friedmann-Robertson-Walker universe with a fluid source obeying a nonideal equation of state with ‘‘asymptotic freedom,’’ namely ideal gas behavior (pressure changes directly proportional to density changes) both at low and high density regimes, following a fluid dynamical model due to Shan and Chen. It is shown that, starting from an ordinary energy density component, such fluids naturally evolve towards a universe with a substantial ‘‘dark energy’’ component at the present tim...
Molecular analysis of pancreatic cyst fluid changes clinical management.
Arner, David M; Corning, Brooke E; Ahmed, Ali M; Ho, Henry C; Weinbaum, Bradley J; Siddiqui, Uzma; Aslanian, Harry; Adams, Reid B; Bauer, Todd W; Wang, Andrew Y; Shami, Vanessa M; Sauer, Bryan G
2018-01-01
DNA molecular analysis has been suggested as a tool to evaluate pancreatic cysts. This study assesses whether the addition of DNA molecular analysis alters clinical management. This is a retrospective review of 46 consecutive patients who underwent EUS-FNA of pancreatic cysts with DNA molecular analysis at two major academic institutions. Cases were presented to two pancreaticobiliary surgeons first without and then with DNA molecular analysis data. The primary outcome was the frequency with which clinical management was altered with the addition of DNA molecular analysis. Forty-six patients with a mean age of 62.0 (±13.4) years and mean cyst size of 3.2 (±2.3) cm were included in the study. Cyst carcinoembryonic antigen (CEA) was available in 30 patients and ranged from 0.4 to 15,927 ng/mL. DNA molecular analysis was described as benign in 23 (50%), statistically indolent in 13 (28%), statistically higher risk in 9 (20%), and indeterminate in 1 (2%). Surgeon #1 changed the management in 13/46 cases (28%) and surgeon #2 changed the management in 12/46 cases (26%) with the addition of DNA molecular analysis. When organized by CEA concentration, those with an intermediate CEA (45-800 ng/mL) or without a CEA concentration had a management changed more frequently (40%) compared to all others (P molecular analysis alters the clinical management of pancreatic cystic lesions most often when CEA levels are intermediate (45-800 ng/mL) or when no CEA concentration is available. Use of DNA molecular analysis can be considered in this cohort. Further study of molecular markers in pancreatic cystic lesions is recommended.
Directory of Open Access Journals (Sweden)
América eVera
2015-05-01
Full Text Available During early stages of development, encephalic vesicles are composed by a layer of neuroepithelial cells surrounding a central cavity filled with embryonic cerebrospinal fluid (eCSF. This fluid contains several morphogens that regulate proliferation and differentiation of neuroepithelial cells. One of these neurogenic factors is SCO-spondin, a giant protein secreted to the eCSF from early stages of development. Inhibition of this protein in vivo or in vitro drastically decreases the neurodifferentiation process. Other important neurogenic factors of the eCSF are low density lipoproteins (LDL, the depletion of which generates a 60% decrease in mesencephalic explant neurodifferentiation. The presence of several LDL receptor class A (LDLrA domains (responsible for LDL binding in other proteins in the SCO-spondin sequence suggests a possible interaction between both molecules. This possibility was analyzed using three different experimental approaches: 1 Bioinformatics analyses of the SCO-spondin region, that contains eight LDLrA domains in tandem, and of comparisons with the LDL receptor consensus sequence; 2 Analysis of the physical interactions of both molecules through immunohistochemical colocalization in embryonic chick brains and through the immunoprecipitation of LDL with anti-SCO-spondin antibodies; and 3 Analysis of functional interactions during the neurodifferentiation process when these molecules were added to a culture medium of mesencephalic explants. The results revealed that LDL and SCO-spondin interact to form a complex that diminishes the neurogenic capacities that both molecules have separately. Our work suggests that the embryonic cerebrospinal fluid is an active signaling center with a complex regulation system that allows for correct brain development.
Energy Technology Data Exchange (ETDEWEB)
Balastre, M.
1999-11-10
Instabilities of concentrated colloidal suspensions are a source of many industrial problems, as in drilling fluid formulations where aggregation and severe settling phenomena can occur. Low molecular weight polyelectrolyte dispersants are used to solve these problems, but their optimal use requires a better understanding of the phenomena that are involved. After materials characterization, adsorption mechanisms of two anionic polyelectrolytes (PANa, PSSNa) on a soluble substrate model, barium sulfate powder are studied. Barium sulfate is the principal additive used to adapt the density of drilling fluids. A simple model allows us to propose a distribution of the microscopic species at the interface. Presence of divalent ions induces the formation of a strong complex with the polyelectrolyte. Adsorption and electro-kinetic data are presented and exchange equilibrium are examined in relation with the surface uptake. The binding mechanism and the surface speciation of the polymer groups are deduced from the ion exchange analysis. The macroscopic behavior of suspensions on different conditions (volume fraction, ionic strength, dispersant concentration) is studied by settling and rheological measurements. The macroscopic properties are connected to structural aspects, and we show that dispersing effects are mostly related to electro-steric repulsion. The dispersion state depends on two principal factors adsorbed amounts and adsorbed layer properties, especially the excess charge, and the molecules conformation. (author)
Choe, Hyonmin; Deirmengian, Carl A.; Hickok, Noreen J.; Morrison, Tiffany N.; Tuan, Rocky S.
2015-01-01
Orthopaedic infections are complex conditions that require immediate diagnosis and accurate identification of the causative organisms to facilitate appropriate management. Conventional methodologies for diagnosis of these infections sometimes lack accuracy or sufficient rapidity. Current molecular diagnostics are an emerging area of bench-to-bedside research in orthopaedic infections. Examples of promising molecular diagnostics include measurement of a specific biomarker in the synovial fluid...
Duran-Olivencia, Miguel A.; Goddard, Ben; Kalliadasis, Serafim
2015-11-01
Over the last few decades the classical density-functional theory (DFT) and its dynamic extensions (DDFTs) have become a remarkably powerful tool in the study of colloidal fluids. Recently there has been extensive research to generalise all previous DDFTs finally yielding a general DDFT equation (for spherical particles) which takes into account both inertia and hydrodynamic interactions (HI) which strongly influence non-equilibrium properties. The present work will be devoted to a further generalisation of such a framework to systems of anisotropic particles. To this end, the kinetic equation for the Brownian particle distribution function is derived starting from the Liouville equation and making use of Zwanzig's projection-operator techniques. By averaging over all but one particle, a DDFT equation is finally obtained with some similarities to that for spherical colloids. However, there is now an inevitable translational-rotational coupling which affects the diffusivity of asymmetric particles. Lastly, in the overdamped (high friction) limit the theory is notably simplified leading to a DDFT equation which agrees with previous derivations. We acknowledge financial support from European Research Council via Advanced Grant No. 247031.
Kioupis, Loukas I.
2000-07-01
With the increased power of modern computers, molecular modeling has been used widely and proven to be a valuable tool for elucidating the physical processes important in many industrial and engineering problems. Of particular interest to us is the rheology and physical chemistry of complex fluids, such as hydrocarbon lubricants and polymers. The goal is to provide qualitative and quantitative molecular-level explanations for the behavior of such fluids, and provide guidance in the development of new improved materials. For example, during the production of poly-α-olefin (PAO) synthetic lubricants, the number of the isomer skeletal structures that can be obtained is staggering. Which of the countless PAO isomers produce a lubricant with superior performance properties? How does it behave under different operational conditions of temperature, pressure, and shear rate? A fundamental understanding of the effect that molecular structure has on the oil's rheological and lubricant performance is first needed, in order to answer these questions. To serve this purpose, we have developed efficient molecular dynamics (MD) simulation programs, which utilize multiple time step algorithms and parallel computational techniques. This enables us to conduct simulations of typical PAO isomers and compute the viscosity, as well as several other dynamic and static properties, as a function of temperature, pressure, and shear rate. The key molecular mechanisms that determine important macroscopic properties, such as viscosity index, viscosity-pressure coefficient, traction coefficient, and shear thinning behavior are discussed. Based on this analysis, lubricant and traction fluid structures that have a high likelihood of having desirable properties are proposed. In addition, studies on simple alkane mixtures are presented, in an attempt to understand the more complex polydisperse lubricant fluids, their blends, and their interaction with additives.
Contact angle dependence on the fluid-wall dispersive energy
Horsch, M.; Heitzig, M.; Dan, C.M.; Harting, J.D.R.; Hasse, H.; Vrabec, J.
2010-01-01
Menisci of the truncated and shifted Lennard-Jones fluid between parallel planar walls are investigated by molecular dynamics simulation. Thereby, the characteristic energy of the unlike dispersive interaction between fluid molecules and wall atoms is systematically varied to determine its influence
Density profiles of granular gases studied by molecular dynamics and Brownian bridges
Peñuñuri, F.; Montoya, J. A.; Carvente, O.
2018-02-01
Despite the inherent frictional forces and dissipative collisions, confined granular matter can be regarded as a system in a stationary state if we inject energy continuously. Under these conditions, both the density and the granular temperature are, in general, non-monotonic variables along the height of the container. In consequence, an analytical description of a granular system is hard to conceive. Here, by using molecular dynamics simulations, we measure the packing fraction profiles for a vertically vibrating three-dimensional granular system in several gaseous-like stationary states. We show that by using the Brownian bridge concept, the determined packing fraction profiles can be reproduced accurately and give a complete description of the distribution of the particles inside the simulation box.
New phenomena in variable-density Rayleigh-Taylor turbulence
Energy Technology Data Exchange (ETDEWEB)
Livescu, D; Ristorcelli, J R; Petersen, M R; Gore, R A, E-mail: livescu@lanl.gov [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)
2010-12-15
This paper presents several issues related to mixing and turbulence structure in buoyancy-driven turbulence at low to moderate Atwood numbers, A, found from direct numerical simulations in two configurations: classical Rayleigh-Taylor instability and an idealized triply periodic Rayleigh-Taylor flow. Simulations at A up to 0.5 are used to examine the turbulence characteristics and contrast them with those obtained close to the Boussinesq approximation. The data sets used represent the largest simulations to date in each configuration. One of the more remarkable issues explored, first reported in (Livescu and Ristorcelli 2008 J. Fluid Mech. 605 145-80), is the marked difference in mixing between different density fluids as opposed to the mixing that occurs between fluids of commensurate densities, corresponding to the Boussinesq approximation. Thus, in the triply periodic configuration and the non-Boussinesq case, an initially symmetric density probability density function becomes skewed, showing that the mixing is asymmetric, with pure heavy fluid mixing more slowly than pure light fluid. A mechanism producing the mixing asymmetry is proposed and the consequences for the classical Rayleigh-Taylor configuration are discussed. In addition, it is shown that anomalous small-scale anisotropy found in the homogeneous configuration (Livescu and Ristorcelli 2008 J. Fluid Mech. 605 145-80) and Rayleigh-Taylor turbulence at A=0.5 (Livescu et al 2008 J. Turbul. 10 1-32) also occurs near the Boussinesq limit. Results pertaining to the moment closure modelling of Rayleigh-Taylor turbulence are also presented. Although the Rayleigh-Taylor mixing layer width reaches self-similar growth relatively fast, the lower-order terms in the self-similar expressions for turbulence moments have long-lasting effects and derived quantities, such as the turbulent Reynolds number, are slow to follow the self-similar predictions. Since eddy diffusivity in the popular gradient transport hypothesis
Resolution of through tubing fluid flow and behind casing fluid flow in multiple completion wells
International Nuclear Information System (INIS)
Arnold, D.M.
1977-01-01
A method is provided for resolving undesired fluid flow in cement channels behind casing in one producing zone of a multi zone completion well operating on gas lift from the fluid flow from lower producing zones in the same well which is contained in production tubing passing through the producing zone being investigated. Gamma rays which are characteristic of the decay of the unstable isotope nitrogen 16 produced by activation of elemental oxygen nuclei comprising the molecular structure of both the tubing fluid flow and the undesired fluid flow are detected in at least two energy bonds at two longitudinally spaced detectors in a well borehole. By appropriately combining the four count rate signals so producing according to predetermined relationships the two fluid flow components in the same direction may be uniquely distinguished on the basis of their differing distances from the gamma ray detectors. 9 claims, 17 figures
Accurate fluid force measurement based on control surface integration
Lentink, David
2018-01-01
Nonintrusive 3D fluid force measurements are still challenging to conduct accurately for freely moving animals, vehicles, and deforming objects. Two techniques, 3D particle image velocimetry (PIV) and a new technique, the aerodynamic force platform (AFP), address this. Both rely on the control volume integral for momentum; whereas PIV requires numerical integration of flow fields, the AFP performs the integration mechanically based on rigid walls that form the control surface. The accuracy of both PIV and AFP measurements based on the control surface integration is thought to hinge on determining the unsteady body force associated with the acceleration of the volume of displaced fluid. Here, I introduce a set of non-dimensional error ratios to show which fluid and body parameters make the error negligible. The unsteady body force is insignificant in all conditions where the average density of the body is much greater than the density of the fluid, e.g., in gas. Whenever a strongly deforming body experiences significant buoyancy and acceleration, the error is significant. Remarkably, this error can be entirely corrected for with an exact factor provided that the body has a sufficiently homogenous density or acceleration distribution, which is common in liquids. The correction factor for omitting the unsteady body force, {{{ {ρ f}} {1 - {ρ f} ( {{ρ b}+{ρ f}} )}.{( {{{{ρ }}b}+{ρ f}} )}}} , depends only on the fluid, {ρ f}, and body, {{ρ }}b, density. Whereas these straightforward solutions work even at the liquid-gas interface in a significant number of cases, they do not work for generalized bodies undergoing buoyancy in combination with appreciable body density inhomogeneity, volume change (PIV), or volume rate-of-change (PIV and AFP). In these less common cases, the 3D body shape needs to be measured and resolved in time and space to estimate the unsteady body force. The analysis shows that accounting for the unsteady body force is straightforward to non
Depolarization of neutron spin echo by magnetic fluid
International Nuclear Information System (INIS)
Achiwa, N.; Sirozu, G.; Nishioka, T.; Ebisawa, T.; Hino, M.; Tasaki, S.; Kawai, T.; Yamazaki, D.
2001-01-01
A new method to study the fluctuations of magnetization in magnetic fluids by measuring relations between the phase shift of Larmor precession and the visibility of the neutron spin echo caused by the change of flight path length is studied. Magnetic fluid in which fine particles of magnetite of about 10 nm diameters coated with oleic acid and suspended in water was used. Thickness of the sample was 2 mm. In the dynamics of magnetic fluids, Brownian motions of colloids and the thermal fluctuations of magnetization known as the superparamagnetism are dominant. Isolated ferromagnetic particles of the present size are superparamagnetic but they aggregate to form clusters in a weak magnetic field in the sample of 40% weight density. When neutrons pass the sample, spins process in the magnetic flux density of the clusters fluctuating in time and space. Consequently the Larmor precession phases become distributed and the quantization axes are fluctuated. The result is observed as a decrease of the visibility of the spin echo signals. The change of magnetic flux density in the magnetic fluid is measured from the change of echo visibility of the neutrons, vice versa. In the present experiment, echo was measured at q=0. It is observed that the phase shift changes as a quadratic function of the sample angle reflecting the change of the path length through the sample. Since the number of Larmor precession is proportional to the product of the magnetic field and the length of the flight path, mean flux density in the magnetic fluid is calculated from the phase shift. On the other hand, the decrease of the spin echo amplitude as the function of the sample angle reflects the time and space fluctuations of the flux density in the sample. If the direction of the magnetic flux density vector (quantization axis) changes slowly enough compared to the Larmor precession period while a neutron passes one magnetic domain, the neutron spin rotation in the domain is given by the spin
Xiao, Li; Luo, Ray
2017-12-07
We explored a multi-scale algorithm for the Poisson-Boltzmann continuum solvent model for more robust simulations of biomolecules. In this method, the continuum solvent/solute interface is explicitly simulated with a numerical fluid dynamics procedure, which is tightly coupled to the solute molecular dynamics simulation. There are multiple benefits to adopt such a strategy as presented below. At this stage of the development, only nonelectrostatic interactions, i.e., van der Waals and hydrophobic interactions, are included in the algorithm to assess the quality of the solvent-solute interface generated by the new method. Nevertheless, numerical challenges exist in accurately interpolating the highly nonlinear van der Waals term when solving the finite-difference fluid dynamics equations. We were able to bypass the challenge rigorously by merging the van der Waals potential and pressure together when solving the fluid dynamics equations and by considering its contribution in the free-boundary condition analytically. The multi-scale simulation method was first validated by reproducing the solute-solvent interface of a single atom with analytical solution. Next, we performed the relaxation simulation of a restrained symmetrical monomer and observed a symmetrical solvent interface at equilibrium with detailed surface features resembling those found on the solvent excluded surface. Four typical small molecular complexes were then tested, both volume and force balancing analyses showing that these simple complexes can reach equilibrium within the simulation time window. Finally, we studied the quality of the multi-scale solute-solvent interfaces for the four tested dimer complexes and found that they agree well with the boundaries as sampled in the explicit water simulations.
Fluid-induced vibration of composite natural gas pipelines
Energy Technology Data Exchange (ETDEWEB)
Zou, G.P.; Cheraghi, N.; Taheri, F. [Dalhousie Univ., Dept. of Civil Engineering, Halifax, NS (Canada)
2005-02-01
Advancements in materials bonding techniques have led to the use of reinforced composite pipelines. The use of steel pipe with a fiber-reinforced composite over-wrap together has produced an exceptionally strong pipe with positive advantages in weight and corrosion resistivity. Understanding the dynamic characteristics of this kind of sub-sea composite pipelines, which often accommodate axial flow of gas, and prediction of their response is of great interest. This paper presents a state-variable model developed for the analysis of fluid-induced vibration of composite pipeline systems. Simply supported, clamped and clamped-simply supported pipelines are investigated. The influence of fluid's Poisson ratio, the ratio of pipe radius to pipe-wall thickness, laminate layup, the ratio of liquid mass density to pipe-wall mass density, the fluid velocity, initial tension and fluid pressure are all considered. The results of our proposed methodology are compared with those of finite element analysis, using ANSYS ssoftware. (Author)
Structural relaxation in dense hard-sphere fluids
International Nuclear Information System (INIS)
Ladd, A.J.C.; Edward Alley, W.; Alder, B.J.
1987-01-01
The long-time decay of the shear-stress autocorrelation function is shown to be quantitatively related to the decay of correlations between the orientation of ''bonds'' connecting colliding pairs of particles. Within computational uncertainties, we find that orientational correlations in high-density fluids decay as a ''stretched'' exponential in time, with an exponent that is independent of density. However, at low densities the decay is exponential. In two-dimensional systems the decay is exponential, even at high density
Generating perfect fluid spheres in general relativity
International Nuclear Information System (INIS)
Boonserm, Petarpa; Visser, Matt; Weinfurtner, Silke
2005-01-01
Ever since Karl Schwarzschild's 1916 discovery of the spacetime geometry describing the interior of a particular idealized general relativistic star--a static spherically symmetric blob of fluid with position-independent density--the general relativity community has continued to devote considerable time and energy to understanding the general-relativistic static perfect fluid sphere. Over the last 90 years a tangle of specific perfect fluid spheres has been discovered, with most of these specific examples seemingly independent from each other. To bring some order to this collection, in this article we develop several new transformation theorems that map perfect fluid spheres into perfect fluid spheres. These transformation theorems sometimes lead to unexpected connections between previously known perfect fluid spheres, sometimes lead to new previously unknown perfect fluid spheres, and in general can be used to develop a systematic way of classifying the set of all perfect fluid spheres
Density and impurity profile behaviours in HL-2A tokamak with different gas fuelling methods
International Nuclear Information System (INIS)
Zheng-Ying, Cui; Yan, Zhou; Wei, Li; Bei-Bin, Feng; Ping, Sun; Chun-Feng, Dong; Yi, Liu; Wen-Yu, Hong; Qing-Wei, Yang; Xuan-Tong, Ding; Xu-Ru, Duan
2009-01-01
The electron density profile peaking and the impurity accumulation in the HL-2A tokamak plasma are observed when three kinds of fuelling methods are separately used at different fuelling particle locations. The density profile becomes more peaked when the line-averaged electron density approaches the Greenwald density limit n G and, consequently, impurity accumulation is often observed. A linear increase regime in the density range n e G and a saturation regime in n e > 0.6n G are obtained. There is no significant difference in achieved density peaking factor f ne between the supersonic molecular beam injection (SMBI) and gas puffing into the plasma main chamber. However, the achieved f ne is relatively low, in particular, in the case of density below 0.7n G , when the working gas is puffed into the divertor chamber. A discharge with a density as high as 1.2n G , i.e. n e = 1.2n G , can be achieved by SMBI just after siliconization as a wall conditioning. The metallic impurities, such as iron and chromium, also increase remarkably when the impurity accumulation happens. The mechanism behind the density peaking and impurity accumulation is studied by investigating both the density peaking factor versus the effective collisionality and the radiation peaking versus density peaking. (fluids, plasmas and electric discharges)
Analyticity of the density of electronic wavefunctions
DEFF Research Database (Denmark)
Fournais, Søren; Hoffmann-Ostenhof, Maria; Hoffmann-Ostenhof, Thomas
2004-01-01
We prove that the electronic densities of atomic and molecular eigenfunctions are real analytic in R^3 away from the nuclei.......We prove that the electronic densities of atomic and molecular eigenfunctions are real analytic in R^3 away from the nuclei....
Itabe, Hiroyuki; Kato, Rina; Sasabe, Naoko; Obama, Takashi; Yamamoto, Matsuo
2018-03-06
Oxidatively modified low-density lipoprotein (oxLDL) is known to be involved in various diseases, including cardiovascular diseases. The presence of oxLDL in the human circulatory system and in atherosclerotic lesions has been demonstrated using monoclonal antibodies. Studies have shown the significance of circulating oxLDL in various systemic diseases, including acute myocardial infarction and diabetic mellitus. Several different enzyme-linked immunosorbent assay (ELISA) procedures to measure oxLDL were utilized. Evidence has been accumulating that reveals changes in oxLDL levels under certain pathological conditions. Since oxLDL concentration tends to correlate with low-density lipoprotein (LDL)-cholesterol, the ratio of oxLDL and LDL rather than oxLDL concentration alone has been focused attention. In addition to circulating plasma, LDL and oxLDL are found in gingival crevicular fluid (GCF), where the ratio of oxLDL to LDL in GCF is much higher than in plasma. LDL and oxLDL levels in GCF show an increase in diabetic patients and periodontal patients, suggesting that GCF might be useful in examining systemic conditions. GCF oxLDL increased when the teeth were affected by periodontitis. It is likely that oxLDL levels in plasma and GCF could reflect oxidative stress and transfer efficacy in circulatory system. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.
Hirano, Toshiyuki; Sato, Fumitoshi
2014-07-28
We used grid-free modified Cholesky decomposition (CD) to develop a density-functional-theory (DFT)-based method for calculating the canonical molecular orbitals (CMOs) of large molecules. Our method can be used to calculate standard CMOs, analytically compute exchange-correlation terms, and maximise the capacity of next-generation supercomputers. Cholesky vectors were first analytically downscaled using low-rank pivoted CD and CD with adaptive metric (CDAM). The obtained Cholesky vectors were distributed and stored on each computer node in a parallel computer, and the Coulomb, Fock exchange, and pure exchange-correlation terms were calculated by multiplying the Cholesky vectors without evaluating molecular integrals in self-consistent field iterations. Our method enables DFT and massively distributed memory parallel computers to be used in order to very efficiently calculate the CMOs of large molecules.
Magnetic fluids stabilized by polypropylene glycol
Energy Technology Data Exchange (ETDEWEB)
Lebedev, A.V., E-mail: lav@icmm.r [Institute of Continuous Media Mechanics, UB RAS, Academic Korolev Str. 1, Perm 614013 (Russian Federation); Lysenko, S.N. [Institute of Technical Chemistry, UB RAS, Academic Korolev Str. 3, Perm 614013 (Russian Federation)
2011-05-15
A series of samples of magnetic fluids stabilized with low-molecular weight polypropylene glycol (PPG) of different molecular masses were synthesized. The use of PPG allowed the maximum extension of the carrier fluid range to include ethyl- and butyl-acetate, ethanol, butanol, acetone, carbon tetrachloride, toluene, kerosene and PPG itself. Magnetic and rheological properties of the samples were investigated. Based on the results of investigation it has been concluded that magnetic nanoparticles are covered by a monolayer of surfactant molecules. At low temperatures the propanol-based sample preserves fluidity up to -115 {sup o}C. Measurement of critical temperatures of other base fluids showed that alcohols are the best carrier medium. Coagulation stability of the ethanol-based ferrocolloid with respect to water and kerosene was explored. It has been found that kerosene, whose fraction by weight exceeds 22.5%, does not mix with the colloid. This effect can be used to produce magneto-controllable extractors of ethyl alcohol. Under the action of water the colloid coagulates, which allows one to substitute the carrier fluid and to separate the colloid into fractions. - Research highlights: PPG stabilizes the magnetic particles in the polar and non-polar media. The minimum operating temperature reaches -115 {sup o}C. Alcohols are the best environment for PPG-stabilized particles. PPG magnetic fluids can be used as magnetic extractors of alcohol. PPG MF can be divided into fractions by partial coagulation with water.
International Nuclear Information System (INIS)
Holmstroem, E.; Kuronen, A.; Nordlund, K.
2008-01-01
We studied threshold displacement energies for creating stable Frenkel pairs in silicon using density functional theory molecular dynamics simulations. The average threshold energy over all lattice directions was found to be 36±2 STAT ±2 SYST eV, and thresholds in the directions and were found to be 20±2 SYST eV and 12.5±1.5 SYST eV, respectively. Moreover, we found that in most studied lattice directions, a bond defect complex is formed with a lower threshold than a Frenkel pair. The average threshold energy for producing either a bond defect or a Frenkel pair was found to be 24±1 STAT ±2 SYST eV
International Nuclear Information System (INIS)
Vogelsang, R.; Hoheisel, C.
1987-01-01
For a large region of dense fluid states of a Lennard-Jones system, they have calculated the friction coefficient by the force autocorrelation function of a Brownian-type particle by molecular dynamics (MD). The time integral over the force autocorrelation function showed an interesting behavior and the expected plateau value when the mass of the Brownian particle was chosen to be about a factor of 100 larger than the mass of the fluid particle. Sufficient agreement was found for the friction coefficient calculated by this way and that obtained by calculations of the self-diffusion coefficient using the common relation between these coefficients. Furthermore, a modified friction coefficient was determined by integration of the force autocorrelation function up to the first maximum. This coefficient can successfully be used to derive a reasonable soft part of the friction coefficient necessary for the Rice-Allnatt approximation for the shear velocity and simple liquids
A study of highly correlated classical and quantum fluids
International Nuclear Information System (INIS)
Clements, B.E.
1988-01-01
We have determined, by molecular dynamics simulation, the l = 0, 2, 4, and 6 Legendre coefficients of the static pair-pair correlation function Q(r,r'), the dynamic pair-pair correlation function Q(r,r';t) and the dynamic four point correlation function S 4 (k, -k,q, -q;t). The interaction potential was taken to be Lennard-Jones. The simulation was carried out at two different values of density and temperature; one coinciding with that of liquid argon near its triple point and the other coinciding with high density argon at room temperature. We argue that an important contribution to the pair-pair correlation function comes from the thee-body correlations. We find that the Legendre coefficients of Q(r,r') provide strong evidence that, upon freezing, the resulting crystalline structure will be a close-packed structure. A study of dynamical fluctuations characterized by Legendre coefficients of the dynamic pair-pair correlation function support this assertion. Finally, we provide a discussion on a decoupling scheme, used in the literature, to approximate the static and dynamic four point correlation function. A variational calculation with the Penrose-Reatto-Chester-Jastrow density matrix is used to study the finite temperature properties of Bose quantum fluids. This analysis provides a systematic method for adding correction terms to the density matrix approach of Campbell, Ristig, Kurten and Senger. We find that the excitation spectrum for the elementary excitations has the proper temperature dependence in contrast to earlier calculations
Directory of Open Access Journals (Sweden)
Masoud Ahmadi
2017-12-01
Full Text Available Nowadays, atomic-force microscopy plays a significant role in nanoscience and nanotechnology, and is widely used for direct measurement at atomic scale and scanning the sample surfaces. In tapping mode, the microcantilever of atomic-force microscope is excited at resonance frequency. Therefore, it is important to study its resonance. Moreover, atomic-force microscopes can be operated in fluid environments such as their applications in chemical and biological sensors. Additionally, piezoelectric microcantilevers are used to enhance atomic-force microscope scanning. Motivated by these considerations, presented herein is a finite element investigation into the nonlinear vibration behavior of piezoelectric microcantilever of atomic-force microscopes in fluid environment. For this purpose, a 3D finite element model coupled with a computational fluid dynamics model is introduced based upon a fluid-solid interaction analysis. First, the reliability of present fluid-solid interaction analysis is revealed by comparison with experimental data available in the literature. Then, numerical results are presented to study the influences of fluid dynamic viscosity and density on the resonance frequency, resonance amplitude and time response of piezoelectric microcantilever. It was shown that increasing the fluid density and dynamic viscosity results in the decrease of resonance frequency. For example, for density equal to 1000 kg/m3 , increasing the viscosity of fluid environment from 0.1 to 1, 10 and 20 mPa.s leads to decrease of resonance frequency about 3%, 29% and 42%, respectively. Also, the resonance amplitude of microcantilever increases as the density increases, while increasing dynamic viscosity has a decreasing effect on the resonance amplitude.
Adsorption of hairy particles with mobile ligands: Molecular dynamics and density functional study
Borówko, M.; Sokołowski, S.; Staszewski, T.; Pizio, O.
2018-01-01
We study models of hairy nanoparticles in contact with a hard wall. Each particle is built of a spherical core with a number of ligands attached to it and each ligand is composed of several spherical, tangentially jointed segments. The number of segments is the same for all ligands. Particular models differ by the numbers of ligands and of segments per ligand, but the total number of segments is constant. Moreover, our model assumes that the ligands are tethered to the core in such a manner that they can "slide" over the core surface. Using molecular dynamics simulations we investigate the differences in the structure of a system close to the wall. In order to characterize the distribution of the ligands around the core, we have calculated the end-to-end distances of the ligands and the lengths and orientation of the mass dipoles. Additionally, we also employed a density functional approach to obtain the density profiles. We have found that if the number of ligands is not too high, the proposed version of the theory is capable to predict the structure of the system with a reasonable accuracy.
Critical phenomena and their effect on thermal energy storage in supercritical fluids
International Nuclear Information System (INIS)
Hobold, Gustavo M.; Da Silva, Alexandre K.
2017-01-01
Highlights: •High power thermal energy storage using supercritical fluids. •Influence of property variation on energy and power density. •Multi-fluid analysis and generalization for several storage temperatures. •Cost, heat transfer and energy density evaluation for high temperature storage. -- Abstract: Large-scale implementation of concentrated solar power plants requires energy storage systems if fossil sources are to be fully replaced. While several candidates have appeared, most still face major issues such as cost, limited energy density and material compatibility. The present paper explores the influence of property variation in the proximity of the critical point on thermal energy storage using supercritical fluids (sTES) from thermodynamic and heat transfer standpoints. Influence of thermodynamic operational parameters on energy density of isobaric and isochoric sTES and their optima is discussed, showing that the energy density results from a competition between average specific heat and loaded density. Moreover, sTES is shown to be applicable to virtually any storage temperature, depending only on the fluid’s critical point. Finally, a heat transfer and energy density comparison to other existing storage mechanisms is presented and supercritical water is shown to be competitive for high temperature thermal energy storage.
RISM theory distribution functions for Lennard--Jones interaction site fluids
International Nuclear Information System (INIS)
Johnson, E.; Hazoume, R.P.
1978-01-01
Reference interaction site model (RISM) theory distribution functions for Lennard-Jones interaction site fluids are discussed. The comparison with computer simulation results suggests that these distribution functions are as accurate as RISM distribution functions for fused hard sphere molecular fluids
Fluid analog model for boundary effects in field theory
International Nuclear Information System (INIS)
Ford, L. H.; Svaiter, N. F.
2009-01-01
Quantum fluctuations in the density of a fluid with a linear phonon dispersion relation are studied. In particular, we treat the changes in these fluctuations due to nonclassical states of phonons and to the presence of boundaries. These effects are analogous to similar effects in relativistic quantum field theory, and we argue that the case of the fluid is a useful analog model for effects in field theory. We further argue that the changes in the mean squared density are, in principle, observable by light scattering experiments.
On the efficiency of a fluid-fluid centrifugal separation
International Nuclear Information System (INIS)
Apazidis, N.
1984-05-01
Efficiency of a separation process of two immiscible incompressible fluids of different densities occuring under the influence of a combined centrifugal and gravitational force field is investigated. The analysis is based on the set of equations for a rotating two-phase flow of a mixture as presented by Greenspan (1983). The geometry of the separation process is considered and the total flow of the separated phases evaluated. (author)
Low-frequency fluid waves in fractures and pipes
Energy Technology Data Exchange (ETDEWEB)
Korneev, Valeri
2010-09-01
Low-frequency analytical solutions have been obtained for phase velocities of symmetrical fluid waves within both an infinite fracture and a pipe filled with a viscous fluid. Three different fluid wave regimes can exist in such objects, depending on the various combinations of parameters, such as fluid density, fluid viscosity, walls shear modulus, channel thickness, and frequency. Equations for velocities of all these regimes have explicit forms and are verified by comparisons with the exact solutions. The dominant role of fractures in rock permeability at field scales and the strong amplitude and frequency effects of Stoneley guided waves suggest the importance of including these wave effects into poroelastic theories.
Molecular aspect ratio and anchoring strength effects in a confined Gay-Berne liquid crystal
Cañeda-Guzmán, E.; Moreno-Razo, J. A.; Díaz-Herrera, E.; Sambriski, E. J.
2014-04-01
Phase diagrams for Gay-Berne (GB) fluids were obtained from molecular dynamics simulations for GB(2, 5, 1, 2) (i.e. short mesogens) and GB(3, 5, 1, 2) (i.e. long mesogens), which yield isotropic, nematic, and smectic-B phases. The long-mesogen fluid also yields the smectic-A phase. Ordered phases of the long-mesogen fluid form at higher temperatures and lower densities when compared to those of the short-mesogen fluid. The effect of confinement under weak and strong substrate couplings in slab geometry was investigated. Compared to the bulk, the isotropic-nematic transition does not shift in temprature significantly for the weakly coupled substrate in either mesogen fluid. However, the strongly coupled substrate shifts the transition to lower temperature. Confinement induces marked stratification in the short-mesogen fluid. This effect diminishes with distance from the substrate, yielding bulk-like behaviour in the slab central region. Fluid stratification is very weak for the long-mesogen fluid, but the strongly coupled substrate induces 'smectisation', an ordering effect that decays with distance. Orientation of the fluid on the substrate depends on the mesogen. There is no preferred orientation in a plane parallel to the substrate for the weakly coupled case. In the strongly coupled case, the mesogen orientation mimics that of adjacent fluid layers. Planar anchoring is observed with a broad distribution of orientations in the weakly coupled case. In the strongly coupled case, the distribution leans toward planar orientations for the short-mesogen fluid, while a marginal preference for tilting persists in the long-mesogen fluid.
International Nuclear Information System (INIS)
Ng, T Y; Yeak, S H; Liew, K M
2008-01-01
A multiscale technique is developed that couples empirical molecular dynamics (MD) and ab initio density functional theory (DFT). An overlap handshaking region between the empirical MD and ab initio DFT regions is formulated and the interaction forces between the carbon atoms are calculated based on the second-generation reactive empirical bond order potential, the long-range Lennard-Jones potential as well as the quantum-mechanical DFT derived forces. A density of point algorithm is also developed to track all interatomic distances in the system, and to activate and establish the DFT and handshaking regions. Through parallel computing, this multiscale method is used here to study the dynamic behavior of single-walled carbon nanotubes (SWCNTs) under asymmetrical axial compression. The detection of sideways buckling due to the asymmetrical axial compression is reported and discussed. It is noted from this study on SWCNTs that the MD results may be stiffer compared to those with electron density considerations, i.e. first-principle ab initio methods
International Nuclear Information System (INIS)
Zheng, Xingwei; Li, Jiangang; Hu, Jiansheng; Li, Jiahong; Ding, Rui; Cao, Bin; Wu, Jinhua
2013-01-01
To achieve desirable plasma density control, a supersonic molecular beam injection (SMBI) feedback control system has been developed recently for the EAST tokamak. The performance of the SMBI and gas puffing (GP) feedback systems were used and compared. The performance of pulse width mode is better than that of pulse amplitude mode when GP was used for density feedback control. During one-day experiments, the variation of gas input and wall retention can be clarified into two stages. In the first stage the retention ratio is as high as 80–90%, and the gas input is about an order of 10 22 D 2 . However, in the second stage, the retention ratio is at a range of 50–70%. The gas input of a single discharge is small and the net wall retention grows slowly. The results of the SMBI feedback control experiment was analyzed. The shorter delay time of SMBI makes it faster at feeding back control the plasma density. The result showed that, compared with GP, the gas input of SMBI was decreased ∼30% and the wall retention was reduced ∼40%. This shows SMBI's advantage for the long pulse high density discharges in EAST. (paper)
Golub, M.; Lehofer, B.; Martinez, N.; Ollivier, J.; Kohlbrecher, J.; Prassl, R.; Peters, J.
2017-04-01
Lipid composition of human low-density lipoprotein (LDL) and its physicochemical characteristics are relevant for proper functioning of lipid transport in the blood circulation. To explore dynamical and structural features of LDL particles with either a normal or a triglyceride-rich lipid composition we combined coherent and incoherent neutron scattering methods. The investigations were carried out under high hydrostatic pressure (HHP), which is a versatile tool to study the physicochemical behavior of biomolecules in solution at a molecular level. Within both neutron techniques we applied HHP to probe the shape and degree of freedom of the possible motions (within the time windows of 15 and 100 ps) and consequently the flexibility of LDL particles. We found that HHP does not change the types of motion in LDL, but influences the portion of motions participating. Contrary to our assumption that lipoprotein particles, like membranes, are highly sensitive to pressure we determined that LDL copes surprisingly well with high pressure conditions, although the lipid composition, particularly the triglyceride content of the particles, impacts the molecular dynamics and shape arrangement of LDL under pressure.
Dynamics of viscoelastic fluid filaments in microfluidic devices
Steinhaus, Benjamin; Shen, Amy Q.; Sureshkumar, Radhakrishna
2007-07-01
The effects of fluid elasticity and channel dimension on polymeric droplet formation in the presence of a flowing continuous Newtonian phase are investigated systematically by using different molecular weight (MW) poly(ethylene oxide) (PEO) solutions and varying microchannel dimensions with constant orifice width (w) to depth (h) ratio (w/h=1/2) and w =25μm, 50μm, 100μm, and 1mm. The flow rate is varied so that the mean shear rate is practically identical for all cases considered. Relevant times scales include inertia-capillary Rayleigh time τR=(Rmax3ρ/σ)1/2, viscocapillary Tomotika time τT=η0Rmax/σ, and the polymer relaxation time λ, where ρ is the fluid density of the dispersed phase, σ is the interfacial tension, η0 is the zero shear viscosity of the dispersed polymer phase, and Rmax is the maximum filament radius. Dimensionless numbers include the elasticity number E =λν/Rmax2, elastocapillary number Ec=λ/τT, and Deborah number, De =λ/τR, where ν =η0/ρ is the kinematic shear viscosity of the fluids. Experiments show that higher MW Boger fluids possessing longer relaxation times and larger extensional viscosities exhibit longer thread lengths and longer pinch-off times (tp). The polymer filament dynamics are controlled primarily by an elastocapillary mechanism with increasing elasticity effect at smaller length scales (larger E and Ec). However, with weaker elastic effects (i.e., larger w and lower MW), pinch-off is initiated by inertia-capillary mechanisms, followed by an elastocapillary regime. A high degree of correlation exists between the dimensionless pinch-off times and the elasticity numbers. We also observe that higher elasticity number E yields smaller effective λ. Based on the estimates of polymer scission probabilities predicted by Brownian dynamics simulations for uniaxial extensional flows, polymer chain scission is likely to occur for ultrasmall orifices and high MW fluids, yielding smaller λ. Finally, the inhibition of
Vieira, Sheila Lopes; de Arruda, Antonio Celso Fonseca
In the majority of published articles on the topic, ER fluids have been studied as if they were viscous liquids. In this work, electrorheological fluids were characterized as solids and their mechanical properties were determined. The results infer that ER materials are controllably resistant to compression, tensile and shear stress, in this order of magnitude. More precisely, fluids made of starch have elasticity modulus similar to that of rubber, they have tensile strength 103 to 5×104 times lower than that of low density polyethylene (LDPE), static yield stress 4×104 to 8×105 times lower than that of acrylonitrile-butadiene-styrene terpolymer (ABS) and fatigue life similar to some polymers like polyethylene(PE) and polypropylene (PP).
Exact analytical density profiles and surface tension
Indian Academy of Sciences (India)
journal of. May 2005 physics pp. 785–801. Classical charged fluids at equilibrium near ... is provided by the excess surface tension for an air–water interface, which is determined ... the potential drop created by the electric layer which appears as soon as the fluid has ...... radii, by symmetry, the charge density profile is flat,.
Mortazavi, Majid; Brandenburg, Jan Gerit; Maurer, Reinhard J; Tkatchenko, Alexandre
2018-01-18
Accurate prediction of structure and stability of molecular crystals is crucial in materials science and requires reliable modeling of long-range dispersion interactions. Semiempirical electronic structure methods are computationally more efficient than their ab initio counterparts, allowing structure sampling with significant speedups. We combine the Tkatchenko-Scheffler van der Waals method (TS) and the many-body dispersion method (MBD) with third-order density functional tight-binding (DFTB3) via a charge population-based method. We find an overall good performance for the X23 benchmark database of molecular crystals, despite an underestimation of crystal volume that can be traced to the DFTB parametrization. We achieve accurate lattice energy predictions with DFT+MBD energetics on top of vdW-inclusive DFTB3 structures, resulting in a speedup of up to 3000 times compared with a full DFT treatment. This suggests that vdW-inclusive DFTB3 can serve as a viable structural prescreening tool in crystal structure prediction.
Chaos analysis of viscoelastic chaotic flows of polymeric fluids in a micro-channel
Energy Technology Data Exchange (ETDEWEB)
Lim, C. P.; Lam, Y. C., E-mail: myclam@ntu.edu.sg [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 639798 (Singapore); BioSystems and Micromechanics (BioSyM) IRG, Singapore-MIT Alliance for Research and Technology (SMART) Centre, 138602 (Singapore); Han, J. [BioSystems and Micromechanics (BioSyM) IRG, Singapore-MIT Alliance for Research and Technology (SMART) Centre, 138602 (Singapore); Department of Electrical Engineering and Computer Science, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Department of Biological Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States)
2015-07-15
Many fluids, including biological fluids such as mucus and blood, are viscoelastic. Through the introduction of chaotic flows in a micro-channel and the construction of maps of characteristic chaos parameters, differences in viscoelastic properties of these fluids can be measured. This is demonstrated by creating viscoelastic chaotic flows induced in an H-shaped micro-channel through the steady infusion of a polymeric fluid of polyethylene oxide (PEO) and another immiscible fluid (silicone oil). A protocol for chaos analysis was established and demonstrated for the analysis of the chaotic flows generated by two polymeric fluids of different molecular weight but with similar relaxation times. The flows were shown to be chaotic through the computation of their correlation dimension (D{sub 2}) and the largest Lyapunov exponent (λ{sub 1}), with D{sub 2} being fractional and λ{sub 1} being positive. Contour maps of D{sub 2} and λ{sub 1} of the respective fluids in the operating space, which is defined by the combination of polymeric fluids and silicone oil flow rates, were constructed to represent the characteristic of the chaotic flows generated. It was observed that, albeit being similar, the fluids have generally distinct characteristic maps with some similar trends. The differences in the D{sub 2} and λ{sub 1} maps are indicative of the difference in the molecular weight of the polymers in the fluids because the driving force of the viscoelastic chaotic flows is of molecular origin. This approach in constructing the characteristic maps of chaos parameters can be employed as a diagnostic tool for biological fluids and, more generally, chaotic signals.
Low defect densities in molecular beam epitaxial GaAs achieved by isoelectronic In doping
Bhattacharya, P. K.; Dhar, S.; Berger, P.; Juang, F.-Y.
1986-01-01
A study has been made of the effects of adding small amounts of In (0.2-1.2 pct) to GaAs grown by molecular beam epitaxy. The density of four electron traps decreases in concentration by an order of magnitude, and the peak intensities of prominent emissions in the excitonic spectra are reduced with increase in In content. Based on the higher surface migration rate of In, compared to Ga, at the growth temperatures it is apparent that the traps and the excitonic transitions are related to point defects. This agrees with earlier observations by Briones and Collins (1982) and Skromme et al. (1985).
Self-regulation in self-propelled nematic fluids.
Baskaran, A; Marchetti, M C
2012-09-01
We consider the hydrodynamic theory of an active fluid of self-propelled particles with nematic aligning interactions. This class of materials has polar symmetry at the microscopic level, but forms macrostates of nematic symmetry. We highlight three key features of the dynamics. First, as in polar active fluids, the control parameter for the order-disorder transition, namely the density, is dynamically convected by the order parameter via active currents. The resulting dynamical self-regulation of the order parameter is a generic property of active fluids and destabilizes the uniform nematic state near the mean-field transition. Secondly, curvature-driven currents render the system unstable deep in the nematic state, as found previously. Finally, and unique to self-propelled nematics, nematic order induces local polar order that in turn leads to the growth of density fluctuations. We propose this as a possible mechanism for the smectic order of polar clusters seen in numerical simulations.
Molecular dynamics studies of transport properties and equation of state of supercritical fluids
Nwobi, Obika C.
Many chemical propulsion systems operate with one or more of the reactants above the critical point in order to enhance their performance. Most of the computational fluid dynamics (CFD) methods used to predict these flows require accurate information on the transport properties and equation of state at these supercritical conditions. This work involves the determination of transport coefficients and equation of state of supercritical fluids by equilibrium molecular dynamics (MD) simulations on parallel computers using the Green-Kubo formulae and the virial equation of state, respectively. MD involves the solution of equations of motion of a system of molecules that interact with each other through an intermolecular potential. Provided that an accurate potential can be found for the system of interest, MD can be used regardless of the phase and thermodynamic conditions of the substances involved. The MD program uses the effective Lennard-Jones potential, with system sizes of 1000-1200 molecules and, simulations of 2,000,000 time-steps for computing transport coefficients and 200,000 time-steps for pressures. The computer code also uses linked cell lists for efficient sorting of molecules, periodic boundary conditions, and a modified velocity Verlet algorithm for particle displacement. Particle decomposition is used for distributing the molecules to different processors of a parallel computer. Simulations have been carried out on pure argon, nitrogen, oxygen and ethylene at various supercritical conditions, with self-diffusion coefficients, shear viscosity coefficients, thermal conductivity coefficients and pressures computed for most of the conditions. Results compare well with experimental and the National Institute of Standards and Technology (NIST) values. The results show that the number of molecules and the potential cut-off radius have no significant effect on the computed coefficients, while long-time integration is necessary for accurate determination of the
Laser induced ablatively driven interfacial nonlinear fluid instabilities in multilayer targets
International Nuclear Information System (INIS)
Manoranjan Khan; Gupta, M.R.; Mandal, L.K.; Roy, S.; Banerjee, R.
2010-01-01
Complete text of publication follows. High power laser driven shock waves in condensed matter have important application for studying equation of state (EOS) and high pressure physics. This is an important phenomenon in fuel compression for Inertial Confinement Fusion (ICF) experiments where multilayer targets of differing shock impedance are interacted by laser induced shocks. The interface between the two fluid becomes unstable when driven by the impulsive force (Richtmyer-Meshkov) due to such a shock wave or a continuously acting force e.g., gravity (Rayleigh-Taylor). In the nonlinear stage, the fluid interface is found to develop structures having finger-like shapes. The structures resemble a bubble (spike) accordingly as a lighter (heavier) fluid pushes in a heavier (lighter) fluid. These effects need to be mitigated for efficient compression in ICF experiment. We have studied the effect of density variation on R-T and R-M instability on the temporal development of nonlinear two fluid interfacial structures like bubble and spike. It is shown that the velocity of bubble or spike decreases leading to stabilization if the density of the fluids leads to lowering of the Atwood number. The Atwood number A = ρ a -ρ b / ρ a +ρ b changes to A* = ρ a *ρ b */ ρ a *ρ b * where ρ* m = ρ m (1-1/γ m ), m = [a,b], assuming ρ a > ρ b . It has been seen that the stabilization or destabilization (depending on the algebraic sign of the gradient) will be proportional to the pressure p 0 at the interface. The set of equation describing the dynamics of the bubbles and spikes in presence of fluid density variation are not analytically integrable in closed form. All the results are derived by numerical methods and are represented and interpreted. Analytical calculations are performed (not presented here) to modify the dynamical boundary condition between the two fluids and we have finally arrived at the following expression for the asymptotic bubble velocity ν b 2 = 2(r
Advances in fluid modeling and turbulence measurements
International Nuclear Information System (INIS)
Wada, Akira; Ninokata, Hisashi; Tanaka, Nobukazu
2002-01-01
The context of this book consists of four fields: Environmental Fluid Mechanics; Industrial Fluid Mechanics; Fundamentals of Fluid Mechanics; and Turbulence Measurements. Environmental Fluid Mechanics includes free surface flows in channels, rivers, seas, and estuaries. It also discusses wind engineering issues, ocean circulation model and dispersion problems in atmospheric, water and ground water environments. In Industrial Fluid Mechanics, fluid phenomena in energy exchanges, modeling of turbulent two- or multi-phase flows, swirling flows, flows in combustors, variable density flows and reacting flows, flows in turbo-machines, pumps and piping systems, and fluid-structure interaction are discussed. In Fundamentals of Fluid Mechanics, progress in modeling turbulent flows and heat/mass transfers, computational fluid dynamics/numerical techniques, parallel computing algorithms, applications of chaos/fractal theory in turbulence are reported. In Turbulence Measurements, experimental studies of turbulent flows, experimental and post-processing techniques, quantitative and qualitative flow visualization techniques are discussed. Separate abstracts were presented for 15 of the papers in this issue. The remaining 89 were considered outside the subject scope of INIS. (J.P.N.)
Frei, Maxi; Erben, Johannes; Martin, Julian; Zengerle, Roland; Kerzenmacher, Sven
2017-09-01
The poisoning of platinum anodes by body-fluid constituents such as amino acids is currently the main hurdle preventing the application of abiotic glucose fuel cells as battery-independent power supply for medical implants. We present a novel anode material that enables continuous operation of glucose oxidation anodes in horse serum for at least 30 days at a current density of (7.2 ± 1.9) μA cm-2. The fabrication process is based on the electro-deposition of highly porous platinum onto a 3-dimensional carbon nanofiber support, leading to approximately 2-fold increased electrode roughness factors (up to 16500 ± 2300). The material's superior performance is not only related to its high specific surface area, but also to an improved catalytic activity and/or poisoning resistance. Presumably, this results from the micro- and nanostructure of the platinum deposits. This represents a major step forward in the development of implantable glucose fuel cells based on long-term stable platinum electrodes.
Nonequilibrium molecular dynamics theory, algorithms and applications
Todd, Billy D
2017-01-01
Written by two specialists with over twenty-five years of experience in the field, this valuable text presents a wide range of topics within the growing field of nonequilibrium molecular dynamics (NEMD). It introduces theories which are fundamental to the field - namely, nonequilibrium statistical mechanics and nonequilibrium thermodynamics - and provides state-of-the-art algorithms and advice for designing reliable NEMD code, as well as examining applications for both atomic and molecular fluids. It discusses homogenous and inhomogenous flows and pays considerable attention to highly confined fluids, such as nanofluidics. In addition to statistical mechanics and thermodynamics, the book covers the themes of temperature and thermodynamic fluxes and their computation, the theory and algorithms for homogenous shear and elongational flows, response theory and its applications, heat and mass transport algorithms, applications in molecular rheology, highly confined fluids (nanofluidics), the phenomenon of slip and...
Molecular Electronic Angular Motion Transducer Broad Band Self-Noise
Zaitsev, Dmitry; Agafonov, Vadim; Egorov, Egor; Antonov, Alexander; Shabalina, Anna
2015-01-01
Modern molecular electronic transfer (MET) angular motion sensors combine high technical characteristics with low cost. Self-noise is one of the key characteristics which determine applications for MET sensors. However, until the present there has not been a model describing the sensor noise in the complete operating frequency range. The present work reports the results of an experimental study of the self-noise level of such sensors in the frequency range of 0.01–200 Hz. Based on the experimental data, a theoretical model is developed. According to the model, self-noise is conditioned by thermal hydrodynamic fluctuations of the operating fluid flow in the frequency range of 0.01–2 Hz. At the frequency range of 2–100 Hz, the noise power spectral density has a specific inversely proportional dependence of the power spectral density on the frequency that could be attributed to convective processes. In the high frequency range of 100–200 Hz, the noise is conditioned by the voltage noise of the electronics module input stage operational amplifiers and is heavily reliant to the sensor electrical impedance. The presented results allow a deeper understanding of the molecular electronic sensor noise nature to suggest the ways to reduce it. PMID:26610502
Directory of Open Access Journals (Sweden)
Markus Schmid
2016-01-01
Full Text Available The effect of the amount of hydrolyzed WPI (h-WPI in WPI-based films on the technofunctional properties and structure of the films has not hitherto been systematically researched. The main objective of this study was therefore to explore the quantitative and qualitative molecular interactions and structures of these films. Different buffer systems were used for the solubility studies to obtain information about the qualitative molecular interactions. Swelling studies were performed to provide qualitative statements about the WPI network. In addition, the cross-linking density (CLD of the WPI-based films was derived from the swelling tests. The measurements showed that increasing the h-WPI content decreases the CLD significantly. The CLD values of films with 0% and 50% h-WPI content were 1.61·10-4 mol·cm−3 and 0.25·10-4 mol·cm−3. The study indicates that noncovalent interactions have more influence on barrier properties than the cross-linking density through disulphide bonds. In general, the results of the swelling tests correlated with the solubility studies.
Research of mechanism of density lock
International Nuclear Information System (INIS)
Wang Shengfei; Yan Changqi; Gu Haifeng
2010-01-01
Mechanism of density lock was analyzed according to the work conditions of density lock. The results showed that: the stratification with no disturbance satisfied the work conditions of density lock; fluids between the stratification were not mixed at the condition of connected to each other; the density lock can be open automatically by controlled the pressure balance at the stratification. When disturbance existed, the stratification might be broken and mass would be transferred by convection. The stability of stratification can be enhanced by put the special structure in density lock to ensure the normal work of density lock. At last, the minimum of heat loss in density lock was also analyzed. (authors)
Zhang, Kai; Wang, Feng-hui; Lu, Yong-jun
2018-01-01
It is necessary to understand and predict the behavior of continuous nanoflow, especially inside the nanochannel with uneven wettability. Because the properties of fluid confined in the nanochannel are different from the macroscopic fluid, molecular level understanding is critical for future applications. In this work, a series of molecular dynamics simulations were executed to investigate the effect of the wettability gradient on the continuous nanofluid. In the simulations, different osmotic pressures were applied to make the water transport through different nanochannels. Simulation data was analyzed to obtain water flow rate, shear viscosity, capillary force, density distributions along the height directions of channel and apparent friction factor. Results show that the uneven wettability has a significant effect on the transportation of confined water only under the proper applied osmotic pressure and the height of channel. Under the appropriate conditions, the uneven wettability has a promotion on the transportation of water when it is at the exit of channel. When the uneven wettability locates in the entrance and middle of the channel, the uneven wettability will hinder the transportation of water. Especially, it is worth mentioning that there is a special phenomenon when the height of the nanochannel becomes 0.8 nm. Depending on the applied osmotic pressure, the uneven wettability has a double-sided effect on the confined fluid inside the channel with H = 0.8 nm. Our work may contribute to the design of nanochannels.
Molecular dynamics simulation of heat transfer through a water layer between two platinum slabs
International Nuclear Information System (INIS)
Iype, E; Arlemark, E J; Nedea, S V; Rindt, C C M; Zondag, H A
2012-01-01
Heat transfer through micro channels is being investigated due to its importance in micro channel cooling applications. Molecular dynamics simulation is regarded as a potential tool for studying such microscopic phenomena in detail. However, the applicability of molecular dynamics method is limited due to scarcely known inter atomic interactions involved in complex fluids. In this study we use an empirical force field (ReaxFF), which is parameterized using accurate quantum chemical simulation results for water, to simulate heat transfer phenomena through a layer of water confined between two platinum slabs. The model for water seems to reproduce the macroscopic properties such as density, radial distribution function and diffusivity quite well. The heat transfer phenomena through a channel filled with water, which is confined by two platinum (100) surfaces are studied using ReaxFF. The model accurately predicts the formation of surface mono-layer. The heat transfer analysis shows temperature jumps near the walls which are creating significant heat transfer resistances. A low bulk density in the channel creates a multi-phase region with vapor transport in the region.
Sheela, N R; Muthu, S; Sampathkrishnan, S; Al-Saadi, Abdulaziz A
2015-03-15
The spectroscopic techniques and semi-empirical molecular calculations have been utilized to analyze the drug Tizanidine (5CDIBTA). The solid phase Fourier Transform Infrared (FTIR) and Fourier Transform Raman (FTR) spectral analysis of 5CDIBTA is carried out along with density functional theory (DFT) calculations (B3LYP) with the 6-311++G(d,p) basis set. Detailed interpretation of the vibrational spectra of the compound has been made on the basis of the calculated potential energy distribution (PED). The individual atomic charges by NPA using B3LYP method is studied. A study on the Mulliken atomic charges, frontier molecular orbitals (HOMO-LUMO), molecular electrostatic potential (MEP) and thermodynamic properties were performed. The electric dipole moment (μ) and the first hyperpolarizability (α) values of the investigated molecule were also computed. Copyright © 2014 Elsevier B.V. All rights reserved.
Schnyder, Simon K.; Horbach, Jürgen
2018-02-01
Molecular dynamics simulations of interacting soft disks confined in a heterogeneous quenched matrix of soft obstacles show dynamics which is fundamentally different from that of hard disks. The interactions between the disks can enhance transport when their density is increased, as disks cooperatively help each other over the finite energy barriers in the matrix. The system exhibits a transition from a diffusive to a localized state, but the transition is strongly rounded. Effective exponents in the mean-squared displacement can be observed over three decades in time but depend on the density of the disks and do not correspond to asymptotic behavior in the vicinity of a critical point, thus, showing that it is incorrect to relate them to the critical exponents in the Lorentz model scenario. The soft interactions are, therefore, responsible for a breakdown of the universality of the dynamics.
Closed-cycle gas turbine working fluids
International Nuclear Information System (INIS)
Lee, J.C.; Campbell, J. Jr.; Wright, D.E.
1981-01-01
Characteristic requirements of a closed-cycle gas turbine (CCGT) working fluid were identified and the effects of their thermodynamic and transport properties on the CCGT cycle performance, required heat exchanger surface area and metal operating temperature, cycle operating pressure levels, and the turbomachinery design were investigated. Material compatibility, thermal and chemical stability, safety, cost, and availability of the working fluid were also considered in the study. This paper also discusses CCGT working fluids utilizing mixtures of two or more pure gases. Some mixtures of gases exhibit pronounced synergetic effects on their characteristic properties including viscosity, thermal conductivity and Prandtl number, resulting in desirable heat transfer properties and high molecular weights. 21 refs
The Voronoi volume and molecular representation of molar volume: equilibrium simple fluids.
Hunjan, Jagtar Singh; Eu, Byung Chan
2010-04-07
The Voronoi volume of simple fluids was previously made use of in connection with volume transport phenomena in nonequilibrium simple fluids. To investigate volume transport phenomena, it is important to develop a method to compute the Voronoi volume of fluids in nonequilibrium. In this work, as a first step to this goal, we investigate the equilibrium limit of the nonequilibrium Voronoi volume together with its attendant related molar (molal) and specific volumes. It is proved that the equilibrium Voronoi volume is equivalent to the molar (molal) volume. The latter, in turn, is proved equivalent to the specific volume. This chain of equivalences provides an alternative procedure of computing the equilibrium Voronoi volume from the molar volume/specific volume. We also show approximate methods of computing the Voronoi and molar volumes from the information on the pair correlation function. These methods may be employed for their quick estimation, but also provide some aspects of the fluid structure and its relation to the Voronoi volume. The Voronoi volume obtained from computer simulations is fitted to a function of temperature and pressure in the region above the triple point but below the critical point. Since the fitting function is given in terms of reduced variables for the Lennard-Jones (LJ) model and the kindred volumes (i.e., specific and molar volumes) are in essence equivalent to the equation of state, the formula obtained is a reduced equation state for simple fluids obeying the LJ model potential in the range of temperature and pressure examined and hence can be used for other simple fluids.
Hamiltonian structure of reduced fluid models for plasmas obtained from a kinetic description
International Nuclear Information System (INIS)
Guillebon, L. de; Chandre, C.
2012-01-01
We consider the Hamiltonian structure of reduced fluid models obtained from a kinetic description of collisionless plasmas by Vlasov–Maxwell equations. We investigate the possibility of finding Poisson subalgebras associated with fluid models starting from the Vlasov–Maxwell Poisson algebra. In this way, we show that the only possible Poisson subalgebra involves the moments of zeroth and first order of the Vlasov distribution, meaning the fluid density and the fluid velocity. We find that the bracket derived in [B.A. Shadwick, G.M. Tarkenton, E.H. Esarey, Phys. Rev. Lett. 93 (2004) 175002] which involves moments of order 2 is not a Poisson bracket since it does not satisfy the Jacobi identity. -- Highlights: ► We investigate fluid reductions from the Vlasov–Maxwell Poisson bracket. ► The only Poisson subalgebra involves fluid density and fluid velocity. ► The bracket derived in [B.A. Shadwick, G.M. Tarkenton, E.H. Esarey, Phys. Rev. Lett. 93 (2004) 175002] is not Hamiltonian.
Senet, P; Aparicio, F
2007-04-14
By using the exact density functional theory, one demonstrates that the value of the local electronic softness of a molecular fragment is directly related to the polarization charge (Coulomb hole) induced by a test electron removed (or added) from (at) the fragment. Our finding generalizes to a chemical group a formal relation between these molecular descriptors recently obtained for an atom in a molecule using an approximate atomistic model [P. Senet and M. Yang, J. Chem. Sci. 117, 411 (2005)]. In addition, a practical ab initio computational scheme of the Coulomb hole and related local descriptors of reactivity of a molecular family having in common a similar fragment is presented. As a blind test, the method is applied to the lateral chains of the 20 isolated amino acids. One demonstrates that the local softness of the lateral chain is a quantitative measure of the similarity of the amino acids. It predicts the separation of amino acids in different biochemical groups (aliphatic, basic, acidic, sulfur contained, and aromatic). The present approach may find applications in quantitative structure activity relationship methodology.
Molecular Model for HNBR with Tunable Cross-Link Density.
Molinari, N; Khawaja, M; Sutton, A P; Mostofi, A A
2016-12-15
We introduce a chemically inspired, all-atom model of hydrogenated nitrile butadiene rubber (HNBR) and assess its performance by computing the mass density and glass-transition temperature as a function of cross-link density in the structure. Our HNBR structures are created by a procedure that mimics the real process used to produce HNBR, that is, saturation of the carbon-carbon double bonds in NBR, either by hydrogenation or by cross-linking. The atomic interactions are described by the all-atom "Optimized Potentials for Liquid Simulations" (OPLS-AA). In this paper, first, we assess the use of OPLS-AA in our models, especially using NBR bulk properties, and second, we evaluate the validity of the proposed model for HNBR by investigating mass density and glass transition as a function of the tunable cross-link density. Experimental densities are reproduced within 3% for both elastomers, and qualitatively correct trends in the glass-transition temperature as a function of monomer composition and cross-link density are obtained.
Clustering the Orion B giant molecular cloud based on its molecular emission.
Bron, Emeric; Daudon, Chloé; Pety, Jérôme; Levrier, François; Gerin, Maryvonne; Gratier, Pierre; Orkisz, Jan H; Guzman, Viviana; Bardeau, Sébastien; Goicoechea, Javier R; Liszt, Harvey; Öberg, Karin; Peretto, Nicolas; Sievers, Albrecht; Tremblin, Pascal
2018-02-01
Previous attempts at segmenting molecular line maps of molecular clouds have focused on using position-position-velocity data cubes of a single molecular line to separate the spatial components of the cloud. In contrast, wide field spectral imaging over a large spectral bandwidth in the (sub)mm domain now allows one to combine multiple molecular tracers to understand the different physical and chemical phases that constitute giant molecular clouds (GMCs). We aim at using multiple tracers (sensitive to different physical processes and conditions) to segment a molecular cloud into physically/chemically similar regions (rather than spatially connected components), thus disentangling the different physical/chemical phases present in the cloud. We use a machine learning clustering method, namely the Meanshift algorithm, to cluster pixels with similar molecular emission, ignoring spatial information. Clusters are defined around each maximum of the multidimensional Probability Density Function (PDF) of the line integrated intensities. Simple radiative transfer models were used to interpret the astrophysical information uncovered by the clustering analysis. A clustering analysis based only on the J = 1 - 0 lines of three isotopologues of CO proves suffcient to reveal distinct density/column density regimes ( n H ~ 100 cm -3 , ~ 500 cm -3 , and > 1000 cm -3 ), closely related to the usual definitions of diffuse, translucent and high-column-density regions. Adding two UV-sensitive tracers, the J = 1 - 0 line of HCO + and the N = 1 - 0 line of CN, allows us to distinguish two clearly distinct chemical regimes, characteristic of UV-illuminated and UV-shielded gas. The UV-illuminated regime shows overbright HCO + and CN emission, which we relate to a photochemical enrichment effect. We also find a tail of high CN/HCO + intensity ratio in UV-illuminated regions. Finer distinctions in density classes ( n H ~ 7 × 10 3 cm -3 ~ 4 × 10 4 cm -3 ) for the densest regions are also
Crystal density predictions for nitramines based on quantum chemistry
International Nuclear Information System (INIS)
Qiu Ling; Xiao Heming; Gong Xuedong; Ju Xuehai; Zhu Weihua
2007-01-01
An efficient and convenient method for predicting the crystalline densities of energetic materials was established based on the quantum chemical computations. Density functional theory (DFT) with four different basis sets (6-31G**, 6-311G**, 6-31+G**, and 6-311++G**) and various semiempirical molecular orbital (MO) methods have been employed to predict the molecular volumes and densities of a series of energetic nitramines including acyclic, monocyclic, and polycyclic/cage molecules. The relationships between the calculated values and experimental data were discussed in detail, and linear correlations were suggested and compared at different levels. The calculation shows that if the selected basis set is larger, it will expend more CPU (central processing unit) time, larger molecular volume and smaller density will be obtained. And the densities predicted by the semiempirical MO methods are all systematically larger than the experimental data. In comparison with other methods, B3LYP/6-31G** is most accurate and economical to predict the solid-state densities of energetic nitramines. This may be instructive to the molecular designing and screening novel HEDMs
Lennard-Jones fluids in two-dimensional nano-pores. Multi-phase coexistence and fluid structure
Yatsyshin, Petr; Savva, Nikos; Kalliadasis, Serafim
2014-03-01
We present a number of fundamental findings on the wetting behaviour of nano-pores. A popular model for fluid confinement is a one-dimensional (1D) slit pore formed by two parallel planar walls and it exhibits capillary condensation (CC): a first-order phase transition from vapour to capillary-liquid (Kelvin shift). Capping such a pore at one end by a third orthogonal wall forms a prototypical two-dimensional (2D) pore. We show that 2D pores possess a wetting temperature such that below this temperature CC remains of first order, above it becomes a continuous phase transition manifested by a slab of capillary-liquid filling the pore from the capping wall. Continuous CC exhibits hysteresis and can be preceded by a first-order capillary prewetting transition. Additionally, liquid drops can form in the corners of the 2D pore (remnant of 2D wedge prewetting). The three fluid phases, vapour, capillary-liquid slab and corner drops, can coexist at the pore triple point. Our model is based on the statistical mechanics of fluids in the density functional formulation. The fluid-fluid and fluid-substrate interactions are dispersive. We analyze in detail the microscopic fluid structure, isotherms and full phase diagrams. Our findings also suggest novel ways to control wetting of nano-pores. We are grateful to the European Research Council via Advanced Grant No. 247031 for support.
Directory of Open Access Journals (Sweden)
Narimatsu C.P.
2001-01-01
Full Text Available In this work, the effects of particle size and density on the fluid dynamic behavior of vertical gas-solid transport of Group D particles in a 53.4 mm diameter transport tube were studied. For the conditions tested, the experimental curves of pressure gradient versus air velocity presented a minimum pressure gradient point, which is associated with a change in the flow regime from dense to dilute phase. The increases in particle size from 1.00 to 3.68 mm and in density from 935 to 2500 kg/m³ caused an increase in pressure gradient for the dense-phase transport region, but were not relevant in dilute transport. The transition velocity between dense and dilute flow (Umin also increased with increasing particle density and diameter. An empirical equation was fitted for predicting transition air velocity for the transport of glass spheres. Additional experiments, covering a wider range of conditions and particles properties, are still needed to allow the fitting of a generalized equation for prediction of Umin.
Energy Technology Data Exchange (ETDEWEB)
Kriaa, Wassim; Mhiri, Hatem; Le Palec, Georges E-mail: lepalec@unimeca.univ-mrs.fr; Bournot, Philippe
2003-07-01
In this work, we intend to solve the equations governing two laminar isothermal or non-isothermal coaxial plane jets with variable density in an ambient fluid at rest in order to study the initial conditions influence (i.e. the nozzles ejection conditions) on the jet characteristic parameters. A finite difference method is developed to solve the dimensionless Navier-Stokes and energy equations resulting from some assumptions. The discussion about the results relates primarily to the concentration core length according to the nozzles thicknesses ratios. The influences of the gas velocity and temperature resulting from the external nozzle are also examined. This made it possible to deduce correlations of practical use between these parameters in order to apply them in engineering processes.
Hydrodynamic cavitation in Stokes flow of anisotropic fluids
Stieger, Tillmann; Agha, Hakam; Schoen, Martin; Mazza, Marco G.; Sengupta, Anupam
2017-01-01
Cavitation, the nucleation of vapour in liquids, is ubiquitous in fluid dynamics, and is often implicated in a myriad of industrial and biomedical applications. Although extensively studied in isotropic liquids, corresponding investigations in anisotropic liquids are largely lacking. Here, by combining liquid crystal microfluidic experiments, nonequilibrium molecular dynamics simulations and theoretical arguments, we report flow-induced cavitation in an anisotropic fluid. The cavitation domai...
Free surface modelling with two-fluid model and reduced numerical diffusion of the interface
International Nuclear Information System (INIS)
Strubelj, Luka; Tiselj, Izrok
2008-01-01
Full text of publication follows: The free surface flows are successfully modelled with one of existing free surface models, such as: level set method, volume of fluid method (with/without surface reconstruction), front tracking, two-fluid model (two momentum equations) with modified interphase force and others. The main disadvantage of two-fluid model used for simulations of free surface flows is numerical diffusion of the interface, which can be significantly reduced using the method presented in this paper. Several techniques for reduction of numerical diffusion of the interface have been implemented in the volume of fluid model and are based on modified numerical schemes for advection of volume fraction near the interface. The same approach could be used also for two-fluid method, but according to our experience more successful reduction of numerical diffusion of the interface can be achieved with conservative level set method. Within the conservative level set method, continuity equation for volume fraction is solved and after that the numerical diffusion of the interface is reduced in such a way that the thickness of the interface is kept constant during the simulation. Reduction of the interface diffusion can be also called interface sharpening. In present paper the two-fluid model with interface sharpening is validated on Rayleigh-Taylor instability. Under assumptions of isothermal and incompressible flow of two immiscible fluids, we simulated a system with the fluid of higher density located above the fluid of smaller density in two dimensions. Due to gravity in the system, fluid with higher density moves below the fluid with smaller density. Initial condition is not a flat interface between the fluids, but a sine wave with small amplitude, which develops into a mushroom-like structure. Mushroom-like structure in simulation of Rayleigh-Taylor instability later develops to small droplets as result of numerical dispersion of interface (interface sharpening
Experiments and MPS analysis of stratification behavior of two immiscible fluids
Energy Technology Data Exchange (ETDEWEB)
Li, Gen, E-mail: ligen@fuji.waseda.jp [Cooperative Major in Nuclear Energy, Waseda University, 3-4-1, Okubo, Shinjuku-ku, Tokyo 169-8555 (Japan); Oka, Yoshiaki [Cooperative Major in Nuclear Energy, Waseda University, 3-4-1, Okubo, Shinjuku-ku, Tokyo 169-8555 (Japan); Furuya, Masahiro; Kondo, Masahiro [Nuclear Technology Research Laboratory, Central Research Institute of Electric Power Industry (CRIEPI), 2-11-1 Iwado-kita, Komae, Tokyo 201-8511 (Japan)
2013-12-15
Highlights: • Improving numerical stability of MPS method. • Implicitly calculating viscous term in momentum equation for highly viscous fluids. • Validation of the enhanced MPS method by analyzing dam break problem. • Various stratification behavior analysis by experiments and simulations. • Sensitivity analysis of the effects of the fluid viscosity and density difference. - Abstract: Stratification behavior is of great significance in the late in-vessel stage of core melt severe accident of a nuclear reactor. Conventional numerical methods have difficulties in analyzing stratification process accompanying with free surface without depending on empirical correlations. The Moving Particle Semi-implicit (MPS) method, which calculates free surface and multiphase flow without empirical equations, is applicable for analyzing the stratification behavior of fluids. In the present study, the original MPS method was improved to simulate the stratification behavior of two immiscible fluids. The improved MPS method was validated through simulating classical dam break problem. Then, the stratification processes of two fluid columns and injected fluid were investigated through experiments and simulations, using silicone oil and salt water as the simulant materials. The effects of fluid viscosity and density difference on stratification behavior were also sensitively investigated by simulations. Typical fluid configurations at various parametric and geometrical conditions were observed and well predicted by improved MPS method.
Vitale, Valerio; Dziedzic, Jacek; Albaugh, Alex; Niklasson, Anders M N; Head-Gordon, Teresa; Skylaris, Chris-Kriton
2017-03-28
Iterative energy minimization with the aim of achieving self-consistency is a common feature of Born-Oppenheimer molecular dynamics (BOMD) and classical molecular dynamics with polarizable force fields. In the former, the electronic degrees of freedom are optimized, while the latter often involves an iterative determination of induced point dipoles. The computational effort of the self-consistency procedure can be reduced by re-using converged solutions from previous time steps. However, this must be done carefully, as not to break time-reversal symmetry, which negatively impacts energy conservation. Self-consistent schemes based on the extended Lagrangian formalism, where the initial guesses for the optimized quantities are treated as auxiliary degrees of freedom, constitute one elegant solution. We report on the performance of two integration schemes with the same underlying extended Lagrangian structure, which we both employ in two radically distinct regimes-in classical molecular dynamics simulations with the AMOEBA polarizable force field and in BOMD simulations with the Onetep linear-scaling density functional theory (LS-DFT) approach. Both integration schemes are found to offer significant improvements over the standard (unpropagated) molecular dynamics formulation in both the classical and LS-DFT regimes.
The descent into glass formation in polymer fluids.
Freed, Karl F
2011-03-15
Glassy materials have been fundamental to technology since the dawn of civilization and remain so to this day: novel glassy systems are currently being developed for applications in energy storage, electronics, food, drugs, and more. Glass-forming fluids exhibit a universal set of transitions beginning at temperatures often in excess of twice the glass transition temperature T(g) and extending down to T(g), below which relaxation becomes so slow that systems no longer equilibrate on experimental time scales. Despite the technological importance of glasses, no prior theory explains this universal behavior nor describes the huge variations in the properties of glass-forming fluids that result from differences in molecular structure. Not surprisingly, the glass transition is currently regarded by many as the deepest unsolved problem in solid state theory. In this Account, we describe our recently developed theory of glass formation in polymer fluids. Our theory explains the origin of four universal characteristic temperatures of glass formation and their dependence on monomer-monomer van der Waals energies, conformational energies, and pressure and, perhaps most importantly, on molecular details, such as monomer structure, molecular weight, size of side groups, and so forth. The theory also provides a molecular explanation for fragility, a parameter that quantifies the rate of change with temperature of the viscosity and other dynamic mechanical properties at T(g). The fragility reflects the fluid's thermal sensitivity and determines the manner in which glass-formers can be processed, such as by extrusion, casting, or inkjet spotting. Specifically, the theory describes the change in thermodynamic properties and fragility of polymer glasses with variations in the monomer structure, the rigidity of the backbone and side groups, the cohesive energy, and so forth. The dependence of the structural relaxation time at lower temperatures emerges from the theory as the Vogel
Fast plane wave density functional theory molecular dynamics calculations on multi-GPU machines
International Nuclear Information System (INIS)
Jia, Weile; Fu, Jiyun; Cao, Zongyan; Wang, Long; Chi, Xuebin; Gao, Weiguo; Wang, Lin-Wang
2013-01-01
Plane wave pseudopotential (PWP) density functional theory (DFT) calculation is the most widely used method for material simulations, but its absolute speed stagnated due to the inability to use large scale CPU based computers. By a drastic redesign of the algorithm, and moving all the major computation parts into GPU, we have reached a speed of 12 s per molecular dynamics (MD) step for a 512 atom system using 256 GPU cards. This is about 20 times faster than the CPU version of the code regardless of the number of CPU cores used. Our tests and analysis on different GPU platforms and configurations shed lights on the optimal GPU deployments for PWP-DFT calculations. An 1800 step MD simulation is used to study the liquid phase properties of GaInP
Walker, Martin; Basáñez, María-Gloria; Ouédraogo, André Lin; Hermsen, Cornelus; Bousema, Teun; Churcher, Thomas S
2015-01-16
Quantitative molecular methods (QMMs) such as quantitative real-time polymerase chain reaction (q-PCR), reverse-transcriptase PCR (qRT-PCR) and quantitative nucleic acid sequence-based amplification (QT-NASBA) are increasingly used to estimate pathogen density in a variety of clinical and epidemiological contexts. These methods are often classified as semi-quantitative, yet estimates of reliability or sensitivity are seldom reported. Here, a statistical framework is developed for assessing the reliability (uncertainty) of pathogen densities estimated using QMMs and the associated diagnostic sensitivity. The method is illustrated with quantification of Plasmodium falciparum gametocytaemia by QT-NASBA. The reliability of pathogen (e.g. gametocyte) densities, and the accompanying diagnostic sensitivity, estimated by two contrasting statistical calibration techniques, are compared; a traditional method and a mixed model Bayesian approach. The latter accounts for statistical dependence of QMM assays run under identical laboratory protocols and permits structural modelling of experimental measurements, allowing precision to vary with pathogen density. Traditional calibration cannot account for inter-assay variability arising from imperfect QMMs and generates estimates of pathogen density that have poor reliability, are variable among assays and inaccurately reflect diagnostic sensitivity. The Bayesian mixed model approach assimilates information from replica QMM assays, improving reliability and inter-assay homogeneity, providing an accurate appraisal of quantitative and diagnostic performance. Bayesian mixed model statistical calibration supersedes traditional techniques in the context of QMM-derived estimates of pathogen density, offering the potential to improve substantially the depth and quality of clinical and epidemiological inference for a wide variety of pathogens.
Supercritical fluid analytical methods
International Nuclear Information System (INIS)
Smith, R.D.; Kalinoski, H.T.; Wright, B.W.; Udseth, H.R.
1988-01-01
Supercritical fluids are providing the basis for new and improved methods across a range of analytical technologies. New methods are being developed to allow the detection and measurement of compounds that are incompatible with conventional analytical methodologies. Characterization of process and effluent streams for synfuel plants requires instruments capable of detecting and measuring high-molecular-weight compounds, polar compounds, or other materials that are generally difficult to analyze. The purpose of this program is to develop and apply new supercritical fluid techniques for extraction, separation, and analysis. These new technologies will be applied to previously intractable synfuel process materials and to complex mixtures resulting from their interaction with environmental and biological systems
Bertram, Erik; Glover, Simon C. O.; Clark, Paul C.; Ragan, Sarah E.; Klessen, Ralf S.
2016-02-01
We run numerical simulations of molecular clouds, adopting properties similar to those found in the central molecular zone (CMZ) of the Milky Way. For this, we employ the moving mesh code AREPO and perform simulations which account for a simplified treatment of time-dependent chemistry and the non-isothermal nature of gas and dust. We perform simulations using an initial density of n0 = 103 cm-3 and a mass of 1.3 × 105 M⊙. Furthermore, we vary the virial parameter, defined as the ratio of kinetic and potential energy, α = Ekin/|Epot|, by adjusting the velocity dispersion. We set it to α = 0.5, 2.0 and 8.0, in order to analyse the impact of the kinetic energy on our results. We account for the extreme conditions in the CMZ and increase both the interstellar radiation field (ISRF) and the cosmic ray flux (CRF) by a factor of 1000 compared to the values found in the solar neighbourhood. We use the radiative transfer code RADMC-3D to compute synthetic images in various diagnostic lines. These are [C II] at 158 μm, [O I] (145 μm), [O I] (63 μm), 12CO (J = 1 → 0) and 13CO (J = 1 → 0) at 2600 and 2720 μm, respectively. When α is large, the turbulence disperses much of the gas in the cloud, reducing its mean density and allowing the ISRF to penetrate more deeply into the cloud's interior. This significantly alters the chemical composition of the cloud, leading to the dissociation of a significant amount of the molecular gas. On the other hand, when α is small, the cloud remains compact, allowing more of the molecular gas to survive. We show that in each case the atomic tracers accurately reflect most of the physical properties of both the H2 and the total gas of the cloud and that they provide a useful alternative to molecular lines when studying the interstellar medium in the CMZ.
Benchmarking variable-density flow in saturated and unsaturated porous media
Guevara Morel, Carlos Roberto; Cremer, Clemens; Graf, Thomas
2015-04-01
In natural environments, fluid density and viscosity can be affected by spatial and temporal variations of solute concentration and/or temperature. These variations can occur, for example, due to salt water intrusion in coastal aquifers, leachate infiltration from waste disposal sites and upconing of saline water from deep aquifers. As a consequence, potentially unstable situations may exist in which a dense fluid overlies a less dense fluid. This situation can produce instabilities that manifest as dense plume fingers that move vertically downwards counterbalanced by vertical upwards flow of the less dense fluid. Resulting free convection increases solute transport rates over large distances and times relative to constant-density flow. Therefore, the understanding of free convection is relevant for the protection of freshwater aquifer systems. The results from a laboratory experiment of saturated and unsaturated variable-density flow and solute transport (Simmons et al., Transp. Porous Medium, 2002) are used as the physical basis to define a mathematical benchmark. The HydroGeoSphere code coupled with PEST are used to estimate the optimal parameter set capable of reproducing the physical model. A grid convergency analysis (in space and time) is also undertaken in order to obtain the adequate spatial and temporal discretizations. The new mathematical benchmark is useful for model comparison and testing of variable-density variably saturated flow in porous media.
Two-fluid and parallel compressibility effects in tokamak plasmas
International Nuclear Information System (INIS)
Sugiyama, L.E.; Park, W.
1998-01-01
The MHD, or single fluid, model for a plasma has long been known to provide a surprisingly good description of much of the observed nonlinear dynamics of confined plasmas, considering its simple nature compared to the complexity of the real system. On the other hand, some of the supposed agreement arises from the lack of the detailed measurements that are needed to distinguish MHD from more sophisticated models that incorporate slower time scale processes. At present, a number of factors combine to make models beyond MHD of practical interest. Computational considerations still favor fluid rather than particle models for description of the full plasma, and suggest an approach that starts from a set of fluid-like equations that extends MHD to slower time scales and more accurate parallel dynamics. This paper summarizes a set of two-fluid equations for toroidal (tokamak) geometry that has been developed and tested as the MH3D-T code [1] and some results from the model. The electrons and ions are described as separate fluids. The code and its original MHD version, MH3D [2], are the first numerical, initial value models in toroidal geometry that include the full 3D (fluid) compressibility and electromagnetic effects. Previous nonlinear MHD codes for toroidal geometry have, in practice, neglected the plasma density evolution, on the grounds that MHD plasmas are only weakly compressible and that the background density variation is weaker than the temperature variation. Analytically, the common use of toroidal plasma models based on aspect ratio expansion, such as reduced MHD, has reinforced this impression, since this ordering reduces plasma compressibility effects. For two-fluid plasmas, the density evolution cannot be neglected in principle, since it provides the basic driving energy for the diamagnetic drifts of the electrons and ions perpendicular to the magnetic field. It also strongly influences the parallel dynamics, in combination with the parallel thermal
Molecular dynamics simulations of melting behavior of alkane as phase change materials slurry
International Nuclear Information System (INIS)
Rao Zhonghao; Wang Shuangfeng; Wu Maochun; Zhang Yanlai; Li Fuhuo
2012-01-01
Highlights: ► The melting behavior of phase change materials slurry was investigated by molecular dynamics simulation method. ► Four different PCM slurry systems including pure water and water/n-nonadecane composite were constructed. ► Amorphous structure and periodic boundary conditions were used in the molecular dynamics simulations. ► The simulated melting temperatures are very close to the published experimental values. - Abstract: The alkane based phase change materials slurry, with high latent heat storage capacity, is effective to enhance the heat transfer rate of traditional fluid. In this paper, the melting behavior of composite phase change materials slurry which consists of n-nonadecane and water was investigated by using molecular dynamics simulation. Four different systems including pure water and water/n-nonadecane composite were constructed with amorphous structure and periodic boundary conditions. The results showed that the simulated density and melting temperature were very close to the published experimental values. Mixing the n-nonadecane into water decreased the mobility but increased the energy storage capacity of composite systems. To describe the melting behavior of alkane based phase change materials slurry on molecular or atomic scale, molecular dynamics simulation is an effective method.
Unbiased estimators for spatial distribution functions of classical fluids
Adib, Artur B.; Jarzynski, Christopher
2005-01-01
We use a statistical-mechanical identity closely related to the familiar virial theorem, to derive unbiased estimators for spatial distribution functions of classical fluids. In particular, we obtain estimators for both the fluid density ρ(r) in the vicinity of a fixed solute and the pair correlation g(r) of a homogeneous classical fluid. We illustrate the utility of our estimators with numerical examples, which reveal advantages over traditional histogram-based methods of computing such distributions.
short communication densities and ultrasonic speed of 2-hydroxy-5
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interactions, and can be used for the development of molecular models for ... necessary not only for giving information about molecular features of pure ... understanding of molecular interactions and their organization in the fluid ... high dielectric constant (u = 3.24 Debye and ε = 36.71 at 25 0C) [14]which enables to dissolve.
Structural Transition in a Fluid of Spheroids: A Low-Density Vestige of Jamming.
Cohen, A P; Dorosz, S; Schofield, A B; Schilling, T; Sloutskin, E
2016-03-04
A thermodynamically equilibrated fluid of hard spheroids is a simple model of liquid matter. In this model, the coupling between the rotational degrees of freedom of the constituent particles and their translations may be switched off by a continuous deformation of a spheroid of aspect ratio t into a sphere (t=1). We demonstrate, by experiments, theory, and computer simulations, that dramatic nonanalytic changes in structure and thermodynamics of the fluids take place, as the coupling between rotations and translations is made to vanish. This nonanalyticity, reminiscent of a second-order liquid-liquid phase transition, is not a trivial consequence of the shape of an individual particle. Rather, free volume considerations relate the observed transition to a similar nonanalyticity at t=1 in structural properties of jammed granular ellipsoids. This observation suggests a deep connection to exist between the physics of jamming and the thermodynamics of simple fluids.
Liu, Zhongqiang; Zhang, Xianxi; Zhang, Yuexing; Li, Renjie; Jiang, Jianzhuang
2006-10-01
A theoretical investigation of the fully optimized geometries and electronic structures of the metal-free (TPdPzH(2)), N,N'-dideuterio (TPdPzD(2)), and magnesium (TPdPzMg) tetra-2,3-pyridino-porphyrazine has been conducted based on density functional theory. The optimized geometries at density functional theory level for these compounds are reported here for the first time. A comparison between the different molecules for the geometry, molecular orbital, and atomic charge is made. The substituent effect of the N atoms on the molecular structures of these compounds is discussed. The IR and Raman spectra for these three compounds have also been calculated at density functional B3LYP level using the 6-31G(d) basis set. Detailed assignments of the NH, NM, and pyridine ring vibrational bands in the IR and Raman spectra have been made based on assistance of animated pictures. The simulated IR spectra of TPdPzH(2) are compared with the experimental absorption spectra, and very good consistency has been found. The isotope effect on the IR and Raman spectra is also discussed.
A novel muon detector for borehole density tomography
Bonneville, Alain; Kouzes, Richard T.; Yamaoka, Jared; Rowe, Charlotte; Guardincerri, Elena; Durham, J. Matthew; Morris, Christopher L.; Poulson, Daniel C.; Plaud-Ramos, Kenie; Morley, Deborah J.; Bacon, Jeffrey D.; Bynes, James; Cercillieux, Julien; Ketter, Chris; Le, Khanh; Mostafanezhad, Isar; Varner, Gary; Flygare, Joshua; Lintereur, Azaree T.
2017-04-01
Muons can be used to image the density of materials through which they pass, including geological structures. Subsurface applications of the technology include tracking fluid migration during injection or production, with increasing concern regarding such timely issues as induced seismicity or chemical leakage into aquifers. Current density monitoring options include gravimetric data collection and active or passive seismic surveys. One alternative, or complement, to these methods is the development of a muon detector that is sufficiently compact and robust for deployment in a borehole. Such a muon detector can enable imaging of density structure to monitor small changes in density - a proxy for fluid migration - at depths up to 1500 m. Such a detector has been developed, and Monte Carlo modeling methods applied to simulate the anticipated detector response. Testing and measurements using a prototype detector in the laboratory and shallow underground laboratory demonstrated robust response. A satisfactory comparison with a large drift tube-based muon detector is also presented.
Federrath, Christoph; Salim, Diane M.; Medling, Anne M.; Davies, Rebecca L.; Yuan, Tiantian; Bian, Fuyan; Groves, Brent A.; Ho, I.-Ting; Sharp, Robert; Kewley, Lisa J.; Sweet, Sarah M.; Richards, Samuel N.; Bryant, Julia J.; Brough, Sarah; Croom, Scott; Scott, Nicholas; Lawrence, Jon; Konstantopoulos, Iraklis; Goodwin, Michael
2017-07-01
Stars form in cold molecular clouds. However, molecular gas is difficult to observe because the most abundant molecule (H2) lacks a permanent dipole moment. Rotational transitions of CO are often used as a tracer of H2, but CO is much less abundant and the conversion from CO intensity to H2 mass is often highly uncertain. Here we present a new method for estimating the column density of cold molecular gas (Σgas) using optical spectroscopy. We utilize the spatially resolved Hα maps of flux and velocity dispersion from the Sydney-AAO Multi-object Integral field spectrograph (SAMI) Galaxy Survey. We derive maps of Σgas by inverting the multi-freefall star formation relation, which connects the star formation rate surface density (ΣSFR) with Σgas and the turbulent Mach number (M). Based on the measured range of ΣSFR = 0.005-1.5 {M_{⊙} yr^{-1} kpc^{-2}} and M=18-130, we predict Σgas = 7-200 {M_{⊙} pc^{-2}} in the star-forming regions of our sample of 260 SAMI galaxies. These values are close to previously measured Σgas obtained directly with unresolved CO observations of similar galaxies at low redshift. We classify each galaxy in our sample as 'star-forming' (219) or 'composite/AGN/shock' (41), and find that in 'composite/AGN/shock' galaxies the average ΣSFR, M and Σgas are enhanced by factors of 2.0, 1.6 and 1.3, respectively, compared to star-forming galaxies. We compare our predictions of Σgas with those obtained by inverting the Kennicutt-Schmidt relation and find that our new method is a factor of 2 more accurate in predicting Σgas, with an average deviation of 32 per cent from the actual Σgas.
Some universal trends of the Mie(n,m) fluid thermodynamics
International Nuclear Information System (INIS)
Orea, Pedro; Reyes-Mercado, Yuri; Duda, Yurko
2008-01-01
By using canonical Monte Carlo simulation, the liquid-vapor phase diagram, surface tension, interface width, and pressure for the Mie(n,m) model fluids are calculated for six pairs of parameters m and n. It is shown that after certain re-scaling of fluid density the corresponding states rule can be applied for the calculations of the thermodynamic properties of the Mie model fluids, and for some real substances
Kvaal, Simen; Helgaker, Trygve
2015-11-14
The relationship between the densities of ground-state wave functions (i.e., the minimizers of the Rayleigh-Ritz variation principle) and the ground-state densities in density-functional theory (i.e., the minimizers of the Hohenberg-Kohn variation principle) is studied within the framework of convex conjugation, in a generic setting covering molecular systems, solid-state systems, and more. Having introduced admissible density functionals as functionals that produce the exact ground-state energy for a given external potential by minimizing over densities in the Hohenberg-Kohn variation principle, necessary and sufficient conditions on such functionals are established to ensure that the Rayleigh-Ritz ground-state densities and the Hohenberg-Kohn ground-state densities are identical. We apply the results to molecular systems in the Born-Oppenheimer approximation. For any given potential v ∈ L(3/2)(ℝ(3)) + L(∞)(ℝ(3)), we establish a one-to-one correspondence between the mixed ground-state densities of the Rayleigh-Ritz variation principle and the mixed ground-state densities of the Hohenberg-Kohn variation principle when the Lieb density-matrix constrained-search universal density functional is taken as the admissible functional. A similar one-to-one correspondence is established between the pure ground-state densities of the Rayleigh-Ritz variation principle and the pure ground-state densities obtained using the Hohenberg-Kohn variation principle with the Levy-Lieb pure-state constrained-search functional. In other words, all physical ground-state densities (pure or mixed) are recovered with these functionals and no false densities (i.e., minimizing densities that are not physical) exist. The importance of topology (i.e., choice of Banach space of densities and potentials) is emphasized and illustrated. The relevance of these results for current-density-functional theory is examined.
Spiers Memorial Lecture. Molecular mechanics and molecular electronics.
Beckman, Robert; Beverly, Kris; Boukai, Akram; Bunimovich, Yuri; Choi, Jang Wook; DeIonno, Erica; Green, Johnny; Johnston-Halperin, Ezekiel; Luo, Yi; Sheriff, Bonnie; Stoddart, Fraser; Heath, James R
2006-01-01
We describe our research into building integrated molecular electronics circuitry for a diverse set of functions, and with a focus on the fundamental scientific issues that surround this project. In particular, we discuss experiments aimed at understanding the function of bistable rotaxane molecular electronic switches by correlating the switching kinetics and ground state thermodynamic properties of those switches in various environments, ranging from the solution phase to a Langmuir monolayer of the switching molecules sandwiched between two electrodes. We discuss various devices, low bit-density memory circuits, and ultra-high density memory circuits that utilize the electrochemical switching characteristics of these molecules in conjunction with novel patterning methods. We also discuss interconnect schemes that are capable of bridging the micrometre to submicrometre length scales of conventional patterning approaches to the near-molecular length scales of the ultra-dense memory circuits. Finally, we discuss some of the challenges associated with fabricated ultra-dense molecular electronic integrated circuits.
Plasma volume methodology: Evans blue, hemoglobin-hematocrit, and mass density transformations
Greenleaf, J. E.; Hinghofer-Szalkay, H.
1985-01-01
Methods for measuring absolute levels and changes in plasma volume are presented along with derivations of pertinent equations. Reduction in variability of the Evans blue dye dilution technique using chromatographic column purification suggests that the day-to-day variability in the plasma volume in humans is less than + or - 20 m1. Mass density determination using the mechanical-oscillator technique provides a method for measuring vascular fluid shifts continuously for assessing the density of the filtrate, and for quantifying movements of protein across microvascular walls. Equations for the calculation of volume and density of shifted fluid are presented.
Hydrodynamic cavitation in Stokes flow of anisotropic fluids
Stieger, Tillmann; Agha, Hakam; Schoen, Martin; Mazza, Marco G.; Sengupta, Anupam
2017-05-01
Cavitation, the nucleation of vapour in liquids, is ubiquitous in fluid dynamics, and is often implicated in a myriad of industrial and biomedical applications. Although extensively studied in isotropic liquids, corresponding investigations in anisotropic liquids are largely lacking. Here, by combining liquid crystal microfluidic experiments, nonequilibrium molecular dynamics simulations and theoretical arguments, we report flow-induced cavitation in an anisotropic fluid. The cavitation domain nucleates due to sudden pressure drop upon flow past a cylindrical obstacle within a microchannel. For an anisotropic fluid, the inception and growth of the cavitation domain ensued in the Stokes regime, while no cavitation was observed in isotropic liquids flowing under similar hydrodynamic parameters. Using simulations we identify a critical value of the Reynolds number for cavitation inception that scales inversely with the order parameter of the fluid. Strikingly, the critical Reynolds number for anisotropic fluids can be 50% lower than that of isotropic fluids.
International Nuclear Information System (INIS)
Joong Hun Bae; Jung Yul Yoo; Haecheon Choi
2005-01-01
Full text of publication follows: The influence of variable fluid property on turbulent convective heat transfer is investigated using direct numerical simulations. We consider thermally-developing flows of air and supercritical-pressure CO 2 in a vertical annular channel where the inner wall is heated with a constant heat flux and the outer wall is insulated. Turbulence statistics show that the heat and momentum transport characteristics of variable-property flows are significantly different from those of constant-property flows. The difference is mainly caused by the spatial and temporal variations of fluid density. The non-uniform density distribution causes fluid particles to be accelerated either by expansion or buoyancy force, while the temporal density fluctuations change the heat and momentum transfer via transport of turbulent mass flux, ρ'u' i . Both effects of the spatial and temporal variations of density are shown to be important in the analysis of turbulent convective heat transfer for supercritical-pressure fluids. For variable-property heated air flows, however, the effect of temporal density fluctuations can be neglected at low Mach number, which is in good accordance with the Morkovin's hypothesis. (authors)
Tracking sharp interface of two fluids by the CIP (cubic-interpolated propagation) scheme
International Nuclear Information System (INIS)
Yabe, T.; Xiao, F.
1993-01-01
A method to treat a sharp discontinuity by the density function is proposed. The surface of the density function is described by one grid throughout the calculation even when the surface is largely distorted. This description is made possible by the CIP method combined with variable transformation. This scheme is applied to the linear wave propagation in one- and two-dimensions. In the nonlinear case, the injection of heavier fluid into lighter fluid his calculated and the winding of mushroom structure is successfully treated by the density function. (author)
Momentum density maps for molecules
International Nuclear Information System (INIS)
Cook, J.P.D.; Brion, C.E.
1982-01-01
Momentum-space and position-space molecular orbital density functions computed from LCAO-MO-SCF wavefunctions are used to rationalize the shapes of some momentum distributions measured by binary (e,2e) spectroscopy. A set of simple rules is presented which enable one to sketch the momentum density function and the momentum distribution from a knowledge of the position-space wavefunction and the properties and effects of the Fourier Transform and the spherical average. Selected molecular orbitals of H 2 , N 2 and CO 2 are used to illustrate this work
Molecular dynamics simulations of field emission from a planar nanodiode
Energy Technology Data Exchange (ETDEWEB)
Torfason, Kristinn; Valfells, Agust; Manolescu, Andrei [School of Science and Engineering, Reykjavik University, Menntavegur 1, IS-101 Reykjavik (Iceland)
2015-03-15
High resolution molecular dynamics simulations with full Coulomb interactions of electrons are used to investigate field emission in planar nanodiodes. The effects of space-charge and emitter radius are examined and compared to previous results concerning transition from Fowler-Nordheim to Child-Langmuir current [Y. Y. Lau, Y. Liu, and R. K. Parker, Phys. Plasmas 1, 2082 (1994) and Y. Feng and J. P. Verboncoeur, Phys. Plasmas 13, 073105 (2006)]. The Fowler-Nordheim law is used to determine the current density injected into the system and the Metropolis-Hastings algorithm to find a favourable point of emission on the emitter surface. A simple fluid like model is also developed and its results are in qualitative agreement with the simulations.
Carney, Randy P.; Kim, Jin Young; Qian, Huifeng; Jin, Rongchao; Mehenni, Hakim; Stellacci, Francesco; Bakr, Osman
2011-01-01
Nanoparticles are finding many research and industrial applications, yet their characterization remains a challenge. Their cores are often polydisperse and coated by a stabilizing shell that varies in size and composition. No single technique can characterize both the size distribution and the nature of the shell. Advances in analytical ultracentrifugation allow for the extraction of the sedimentation (s) and diffusion coefficients (D). Here we report an approach to transform the s and D distributions of nanoparticles in solution into precise molecular weight (M), density (?P) and particle diameter (dp) distributions. M for mixtures of discrete nanocrystals is found within 4% of the known quantities. The accuracy and the density information we achieve on nanoparticles are unparalleled. A single experimental run is sufficient for full nanoparticle characterization, without the need for standards or other auxiliary measurements. We believe that our method is of general applicability and we discuss its limitations. 2011 Macmillan Publishers Limited. All rights reserved.