Discovering local order parameters in liquid water using machine learning

NASA Astrophysics Data System (ADS)

Soto, Adrian; Lu, Deyu; Yoo, Shinjae; Fernandez-Serra, Marivi

The local arrangement of water molecules in liquid phase is still being discussed and questioned. The prevailing view is that water is composed of a mixture of two structurally different liquids. One of the main challenges has been to find order parameters that are able to discriminate the complex structures of these distinct molecular environments. Several local order parameters have been proposed and studied in all sorts of atomistic simulations of liquid water but, to date, none has been able to capture the predicted dual character. This presents an ideal problem to treat with methods capable of unveiling information from complex data. In this talk we will discuss how local order parameters can be constructed from molecular dynamics trajectories by using machine learning and other related techniques. Work was partially supported by DOE Award No. DE-FG02-09ER16052, by DOE Early Career Award No. DE-SC0003871, by BNL LDRD 16-039 project and BNL Contract No. DE-SC0012704.

Molecular dynamics investigation of dynamical heterogeneity and local structure in the supercooled liquid and glass states of Al

NASA Astrophysics Data System (ADS)

Li, Maozhi; Wang, Cai-Zhuang; Mendelev, Mikhail I.; Ho, Kai-Ming

2008-05-01

Molecular dynamics simulations are performed to study the structure and dynamical heterogeneity in the liquid and glass states of Al using a frequently employed embedded atom potential. While the pair correlation function of the glass and liquid states displays only minor differences, the icosahedral short-range order (ISRO) and the dynamics of the two states are very different. The ISRO is much stronger in the glass than in the liquid. It is also found that both the most mobile and the most immobile atoms in the glass state tend to form clusters, and the clusters formed by the immobile atoms are more compact. In order to investigate the local environment of each atom in the liquid and glass states, a local density is defined to characterize the local atomic packing. There is a strong correlation between the local packing density and the mobility of the atoms. These results indicate that dynamical heterogeneity in glasses is directly correlated to the local structure. We also analyze the diffusion mechanisms of atoms in the liquid and glass states. It is found that for the mobile atoms in the glass state, initially they are confined in the cages formed by their nearest neighbors and vibrating. On the time scale of β relaxation, the mobile atoms try to break up the cage confinement and hop into new cages. In the supercooled liquid states, however, atoms continuously diffuse. Furthermore, it is found that on the time scale of β relaxation, some of the mobile atoms in the glass state cooperatively hop, which is facilitated by the stringlike cluster structures. On the longer time scale, it is found that a certain fraction of atoms can simultaneously hop, although they are not nearest neighbors. Further analysis shows that these hopping atoms form big and more compact clusters than the characterized most mobile atoms. The cooperative rearrangement of these big compact clusters might facilitate the simultaneous hopping of atoms in the glass states on the long time scale.

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

Xiong, L. H.; Wang, X. D.; Yu, Q.

Temperature-dependent atomistic structure evolution of liquid gallium (Ga) has been investigated by using in situ high energy X-ray diffraction experiment and ab initio molecular dynamics simulation. Both experimental and theoretical results reveal the existence of a liquid structural change around 1000 K in liquid Ga. Below and above this temperature the liquid exhibits differences in activation energy for selfdiffusion, temperature-dependent heat capacity, coordination numbers, density, viscosity, electric resistivity and thermoelectric power, which are reflected from structural changes of the bond-orientational order parameter Q6, fraction of covalent dimers, averaged string length and local atomic packing. This finding will trigger more studiesmore » on the liquid-to-liquid crossover in metallic melts.« less

X-ray and simulation studies of water

NASA Astrophysics Data System (ADS)

Nilsson, A.; Schlesinger, D.; G. M. Pettersson, L.

Here we present a picture that combines discussions regarding the thermodynamic anomalies in ambient and supercooled water with recent interpretations of X-ray spectroscopy and scattering data of water. At ambient temperatures most molecules favor a closer packing than tetrahedral, with strongly distorted hydrogen bonds, which allows the quantized librational modes to be excited and contribute to the entropy, but with enthalpically favored tetrahedrally bonded water patches appearing as fluctuations, a competition between entropy and enthalpy. Upon cooling water the amount of molecules participating in tetrahedral structures and the size of the tetrahedral patches increase. The two local structures are connected to the liquid-liquid critical point hypothesis in supercooled water corresponding to high-density liquid (HDL) and low-density liquid (LDL). We demonstrate that the HDL local structure deviates from a tetrahedral coordination not only through a collapse of the 2nd shell but also through severe distortions around the 1st coordination shell.

Si-centered capped trigonal prism ordering in liquid Pd 82Si 18 alloy study by first-principles calculations

DOE PAGES

Dong, F.; Yue, G. Q.; Ames Lab. and Iowa State Univ., Ames, IA; ...

2017-03-24

First-principles molecular dynamic (MD) simulation and X-ray diffraction were employed to study the local structures of Pd–Si liquid at the eutectic composition (Pd 82Si 18). Here, a strong repulsion is found between Si atoms, and Si atoms prefer to be evenly distributed in the liquid. The dominate local structures around Si atoms are found to be with of a trigonal prism capped by three half-octahedra and an archimedean anti-prism. The populations of these clusters increase significantly upon cooling, and may play an important role in the formation of Pd 82Si 18 alloy glass.

Si-centered capped trigonal prism ordering in liquid Pd 82Si 18 alloy study by first-principles calculations

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

Dong, F.; Yue, G. Q.; Ames Lab. and Iowa State Univ., Ames, IA

First-principles molecular dynamic (MD) simulation and X-ray diffraction were employed to study the local structures of Pd–Si liquid at the eutectic composition (Pd 82Si 18). Here, a strong repulsion is found between Si atoms, and Si atoms prefer to be evenly distributed in the liquid. The dominate local structures around Si atoms are found to be with of a trigonal prism capped by three half-octahedra and an archimedean anti-prism. The populations of these clusters increase significantly upon cooling, and may play an important role in the formation of Pd 82Si 18 alloy glass.

Long range stress correlations in the inherent structures of liquids at rest

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

Chowdhury, Sadrul; Abraham, Sneha; Hudson, Toby

2016-03-28

Simulation studies of the atomic shear stress in the local potential energy minima (inherent structures) are reported for binary liquid mixtures in 2D and 3D. These inherent structure stresses are fundamental to slow stress relaxation and high viscosity in supercooled liquids. We find that the atomic shear stress in the inherent structures (IS’s) of both liquids at rest exhibits slowly decaying anisotropic correlations. We show that the stress correlations contribute significantly to the variance of the total shear stress of the IS configurations and consider the origins of the anisotropy and spatial extent of the stress correlations.

Pressure-induced structural change in liquid GeI₄.

PubMed

Fuchizaki, Kazuhiro; Nishimura, Hironori; Hase, Takaki; Saitoh, Hiroyuki

2017-12-13

The similarity in the shape of the melting curve of GeI₄ to that of SnI₄ suggests that a liquid-liquid transition as observed in liquid SnI₄ is also expected to occur in liquid GeI₄. Because the slope of the melting curve of GeI₄ abruptly changes at around 3 GPa, in situ synchrotron diffraction measurements were conducted to examine closely the structural changes upon compression at around 3 GPa. The reduced radial distribution functions of the high- and low-pressure liquid states of GeI₄ share the same feature inherent in the high-pressure (high-density) and low-pressure (low-density) radial distribution functions of liquid SnI₄. This feature allows us to introduce local order parameters that we may use to observe the transition. Unlike the transition in liquid SnI₄, the transition from the low-pressure to the high-pressure structure seems sluggish. We speculate that the liquid-liquid critical point of GeI₄ is no longer a thermodynamically stable state and is slightly located below the melting curve. As a result, the structural change is said to be a crossover rather than a transition. The behavior of the local-order parameters implies a metastable extension of the liquid-liquid phase boundary with a negative slope. . © 2017 IOP Publishing Ltd.

Fractionalized Fermi liquids and exotic superconductivity in the Kitaev-Kondo lattice

NASA Astrophysics Data System (ADS)

Seifert, Urban F. P.; Meng, Tobias; Vojta, Matthias

2018-02-01

Fractionalized Fermi liquids (FL*) have been introduced as non-Fermi-liquid metallic phases, characterized by coexisting electron-like charge carriers and local moments which form a fractionalized spin liquid. Here we investigate a Kondo lattice model on the honeycomb lattice with Kitaev interactions among the local moments, a concrete model hosting FL* phases based on Kitaev's Z2 spin liquid. We characterize the FL* phases via perturbation theory, and we employ a Majorana-fermion mean-field theory to map out the full phase diagram. Most remarkably we find nematic triplet superconducting phases which mask the quantum phase transition between fractionalized and conventional Fermi liquid phases. Their pairing structure is inherited from the Kitaev spin liquid; i.e., superconductivity is driven by Majorana glue.

Temperature dependent structural and vibrational properties of liquid indium

NASA Astrophysics Data System (ADS)

Patel, A. B.; Bhatt, N. K.

2018-05-01

The influence of the temperature effect on both the structure factor and the phonon dispersion relation of liquid indium have been investigated by means of pseudopotential theory. The Percus-Yevick Hard Sphere reference system is applied to describe the structural calculation. The effective electron-ion interaction is explained by using modified empty core potential due to Hasegawa et al. along with a local field correction function due to Ichimaru-Utsumi (IU). The temperature dependence of pair potential needed at higher temperatures was achieved by multiplying the damping factor exp(- π/kBT2k F r ) in the pair potential. Very close agreement of static structure factor, particularly, at elevated temperatures confirms the validity of the local potential. A positive dispersion is found in low-q region and the correct trend of phonon dispersion branches like the experimental; shows all broad features of collective excitations in liquid metals.

Reflection Spectra of Distorted Cholesteric Liquid Crystal Structures in Cells with Interdigitated Electrodes (Postprint)

DTIC Science & Technology

2014-07-01

adjusting the magnitude of the electric field. 15. SUBJECT TERMS liquid crystals , liquid- crystal devices, Bragg reflectors, optical properties, chiral ...160.3710) Liquid crystals ; (230.3720) Liquid- crystal devices; (230.1480) Bragg reflectors; (160.4760) Optical properties; (160.1585) Chiral media...White, and T. J. Bunning, “Local optical spectra and texture for chiral nematic liquid crystals in cells with interdigitated electrodes,” Mol

Chromatic patchy particles: Effects of specific interactions on liquid structure

DOE PAGES

Vasilyev, Oleg A.; Tkachenko, Alexei V.; Klumov, Boris A.

2015-07-13

We study the structural and thermodynamic properties of patchy particle liquids, with a special focus on the role of “color,” i.e., specific interactions between individual patches. A possible experimental realization of such “chromatic” interactions is by decorating the particle patches with single-stranded DNA linkers. The complementarity of the linkers can promote selective bond formation between predetermined pairs of patches. By using MD simulations, we compare the local connectivity, the bond orientation order, and other structural properties of the aggregates formed by the “colored” and “colorless” systems. The analysis is done for spherical particles with two different patch arrangements (tetrahedral andmore » cubic). It is found that the aggregated (liquid) phase of the “colorless” patchy particles is better connected, denser and typically has stronger local order than the corresponding “colored” one. This, in turn, makes the colored liquid less stable thermodynamically. Specifically, we predict that in a typical case the chromatic interactions should increase the relative stability of the crystalline phase with respect to the disordered liquid, thus expanding its region in the phase diagram.« less

Structural ordering at solid-liquid interfaces in Al-Sm system: A molecular-dynamics study

DOE PAGES

Sun, Yang; Zhang, Feng; Ye, Zhuo; ...

2016-07-12

The structural ordering at solid-liquid interfaces far from equilibrium is studied with molecular dynamics simulations for the Al-Sm system. Using the van-Hove self-correlation function as the criterion to identify attachment/detachment events that occur at the interface, we are able to determine the time-dependent interface position, and characterize the detailed interfacial structure ordering surrounding the attached atoms. For the interface between an undercooled Al90Sm10 liquid and a metastable cubic structure, the solid induces the crystalline order of the cubic phase in the liquid layers, promoting the continuous growth of the crystal phase. When the same liquid is put in contact withmore » f.c.c. Al, Sm from the liquid can still attach to the solid interface despite its insolubility in the Al lattice. Non-f.c.c. order is revealed surrounding the attached Sm atoms. Lastly, we show that the local structure ordering at interface is highly correlated to solid packing and liquid ordering.« less

Bond-orientational order in liquid Si

NASA Technical Reports Server (NTRS)

Wang, Z. Q.; Stroud, D.

1991-01-01

Bond-orientational order in liquid Si via Monte Carlo simulation in conjuncation with empirical two- and three-body potentials of the form proposed by Stillinger and Weber are studied. Bond-orientational order (BOO) is described in terms of combinations of spherical harmonic functions. Liquid Si is found to have pronounced short-range BOO corresponding to l = 3, as expected for a structure with local tetrahedral order. No long-range BOO is found either in the equilibrium or the supercooled liquid. When the three-body potential is artificially removed, the tetrahedral bond-orientation order disappears and the liquid assumes a close-packed structure.

Characterizing the correlations between local phase fractions of gas-liquid two-phase flow with wire-mesh sensor.

PubMed

Tan, C; Liu, W L; Dong, F

2016-06-28

Understanding of flow patterns and their transitions is significant to uncover the flow mechanics of two-phase flow. The local phase distribution and its fluctuations contain rich information regarding the flow structures. A wire-mesh sensor (WMS) was used to study the local phase fluctuations of horizontal gas-liquid two-phase flow, which was verified through comparing the reconstructed three-dimensional flow structure with photographs taken during the experiments. Each crossing point of the WMS is treated as a node, so the measurement on each node is the phase fraction in this local area. An undirected and unweighted flow pattern network was established based on connections that are formed by cross-correlating the time series of each node under different flow patterns. The structure of the flow pattern network reveals the relationship of the phase fluctuations at each node during flow pattern transition, which is then quantified by introducing the topological index of the complex network. The proposed analysis method using the WMS not only provides three-dimensional visualizations of the gas-liquid two-phase flow, but is also a thorough analysis for the structure of flow patterns and the characteristics of flow pattern transition. This article is part of the themed issue 'Supersensing through industrial process tomography'. © 2016 The Author(s).

Characterizing the correlations between local phase fractions of gas–liquid two-phase flow with wire-mesh sensor

PubMed Central

Liu, W. L.; Dong, F.

2016-01-01

Understanding of flow patterns and their transitions is significant to uncover the flow mechanics of two-phase flow. The local phase distribution and its fluctuations contain rich information regarding the flow structures. A wire-mesh sensor (WMS) was used to study the local phase fluctuations of horizontal gas–liquid two-phase flow, which was verified through comparing the reconstructed three-dimensional flow structure with photographs taken during the experiments. Each crossing point of the WMS is treated as a node, so the measurement on each node is the phase fraction in this local area. An undirected and unweighted flow pattern network was established based on connections that are formed by cross-correlating the time series of each node under different flow patterns. The structure of the flow pattern network reveals the relationship of the phase fluctuations at each node during flow pattern transition, which is then quantified by introducing the topological index of the complex network. The proposed analysis method using the WMS not only provides three-dimensional visualizations of the gas–liquid two-phase flow, but is also a thorough analysis for the structure of flow patterns and the characteristics of flow pattern transition. This article is part of the themed issue ‘Supersensing through industrial process tomography’. PMID:27185959

Odd–even structural sensitivity on dynamics in network-forming ionic liquids

DOE PAGES

Yang, Ke; Cai, Zhikun; Tyagi, Madhusudan; ...

2016-04-13

Understanding structural sensitivity on properties of materials is an important step toward the rational design of materials. As a compelling case of sensitive structure-property relationship, an odd-even effect refers to the alternating trend of physical or chemical properties on odd/even number of repeating structural units. In crystalline or semi-crystalline materials, such odd-even variations of macroscopic properties emerge as manifestations of differences in the periodic packing patterns of molecules. Therefore, due to the lack of long-range order, such odd-even phenomenon is not expected in liquids. Herein, we report the discovery of a remarkable odd-even effect of the dynamical properties in themore » liquid phase, which challenges the traditional periodic packing explanations. In a class of network-forming ionic liquid (NIL), using incoherent quasi-elastic neutron scattering measurements, we measured the dynamical properties including the diffusion coefficient and the rotational relaxation time. These dynamical properties showed pronounced alternating trends with increased number of methylene (–CH 2– ) groups in the backbone. Meanwhile, the structure factor S(Q) showed no long-range periodic packing of molecules, while the pair distribution function g(r) revealed subtle differences in the local molecular morphology. As a result, the observed dynamical odd-even phenomenon in liquids showed that profound dynamical changes originate from subtle local structural differences.« less

Transport properties and Stokes-Einstein relation in Al-rich liquid alloys

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

Jakse, N.; Pasturel, A.

We use ab initio molecular dynamics simulations to study the transport properties and the validity of the Stokes-Einstein relation in Al-rich liquid alloys with Ni, Cu, and Zn as alloying elements. First, we show that the composition and temperature dependence of their transport properties present different behaviors, which can be related to their local structural ordering. Then, we evidence that the competition between the local icosahedral ordering and the local chemical ordering may cause the breakdown of the Stokes–Einstein relation even in the liquid phase. We demonstrate that this breakdown can be captured by entropy-scaling relationships developed by Rosenfeld andmore » using the two-body excess entropy. Our findings provide a unique framework to study the relation between structure, thermodynamics, and dynamics in metallic melts and pave the way towards the explanation of various complex transport properties in metallic melts.« less

Transport properties and Stokes-Einstein relation in Al-rich liquid alloys

NASA Astrophysics Data System (ADS)

Jakse, N.; Pasturel, A.

2016-06-01

We use ab initio molecular dynamics simulations to study the transport properties and the validity of the Stokes-Einstein relation in Al-rich liquid alloys with Ni, Cu, and Zn as alloying elements. First, we show that the composition and temperature dependence of their transport properties present different behaviors, which can be related to their local structural ordering. Then, we evidence that the competition between the local icosahedral ordering and the local chemical ordering may cause the breakdown of the Stokes-Einstein relation even in the liquid phase. We demonstrate that this breakdown can be captured by entropy-scaling relationships developed by Rosenfeld and using the two-body excess entropy. Our findings provide a unique framework to study the relation between structure, thermodynamics, and dynamics in metallic melts and pave the way towards the explanation of various complex transport properties in metallic melts.

Self-consistent treatment of the local dielectric permittivity and electrostatic potential in solution for polarizable macromolecular force fields.

PubMed

Hassan, Sergio A

2012-08-21

A self-consistent method is presented for the calculation of the local dielectric permittivity and electrostatic potential generated by a solute of arbitrary shape and charge distribution in a polar and polarizable liquid. The structure and dynamics behavior of the liquid at the solute/liquid interface determine the spatial variations of the density and the dielectric response. Emphasis here is on the treatment of the interface. The method is an extension of conventional methods used in continuum protein electrostatics, and can be used to estimate changes in the static dielectric response of the liquid as it adapts to charge redistribution within the solute. This is most relevant in the context of polarizable force fields, during electron structure optimization in quantum chemical calculations, or upon charge transfer. The method is computationally efficient and well suited for code parallelization, and can be used for on-the-fly calculations of the local permittivity in dynamics simulations of systems with large and heterogeneous charge distributions, such as proteins, nucleic acids, and polyelectrolytes. Numerical calculation of the system free energy is discussed for the general case of a liquid with field-dependent dielectric response.

Self-consistent treatment of the local dielectric permittivity and electrostatic potential in solution for polarizable macromolecular force fields

NASA Astrophysics Data System (ADS)

Hassan, Sergio A.

2012-08-01

A self-consistent method is presented for the calculation of the local dielectric permittivity and electrostatic potential generated by a solute of arbitrary shape and charge distribution in a polar and polarizable liquid. The structure and dynamics behavior of the liquid at the solute/liquid interface determine the spatial variations of the density and the dielectric response. Emphasis here is on the treatment of the interface. The method is an extension of conventional methods used in continuum protein electrostatics, and can be used to estimate changes in the static dielectric response of the liquid as it adapts to charge redistribution within the solute. This is most relevant in the context of polarizable force fields, during electron structure optimization in quantum chemical calculations, or upon charge transfer. The method is computationally efficient and well suited for code parallelization, and can be used for on-the-fly calculations of the local permittivity in dynamics simulations of systems with large and heterogeneous charge distributions, such as proteins, nucleic acids, and polyelectrolytes. Numerical calculation of the system free energy is discussed for the general case of a liquid with field-dependent dielectric response.

Self-consistent treatment of the local dielectric permittivity and electrostatic potential in solution for polarizable macromolecular force fields

PubMed Central

Hassan, Sergio A.

2012-01-01

A self-consistent method is presented for the calculation of the local dielectric permittivity and electrostatic potential generated by a solute of arbitrary shape and charge distribution in a polar and polarizable liquid. The structure and dynamics behavior of the liquid at the solute/liquid interface determine the spatial variations of the density and the dielectric response. Emphasis here is on the treatment of the interface. The method is an extension of conventional methods used in continuum protein electrostatics, and can be used to estimate changes in the static dielectric response of the liquid as it adapts to charge redistribution within the solute. This is most relevant in the context of polarizable force fields, during electron structure optimization in quantum chemical calculations, or upon charge transfer. The method is computationally efficient and well suited for code parallelization, and can be used for on-the-fly calculations of the local permittivity in dynamics simulations of systems with large and heterogeneous charge distributions, such as proteins, nucleic acids, and polyelectrolytes. Numerical calculation of the system free energy is discussed for the general case of a liquid with field-dependent dielectric response. PMID:22920098

Analysis of capacitive force acting on a cantilever tip at solid/liquid interfaces

NASA Astrophysics Data System (ADS)

Umeda, Ken-ichi; Kobayashi, Kei; Oyabu, Noriaki; Hirata, Yoshiki; Matsushige, Kazumi; Yamada, Hirofumi

2013-04-01

Dielectric properties of biomolecules or biomembranes are directly related to their structures and biological activities. Capacitance force microscopy based on the cantilever deflection detection is a useful scanning probe technique that can map local dielectric constant. Here we report measurements and analysis of the capacitive force acting on a cantilever tip at solid/liquid interfaces induced by application of an alternating voltage to explore the feasibility of the measurements of local dielectric constant by the voltage modulation technique in aqueous solutions. The results presented here suggest that the local dielectric constant measurements by the conventional voltage modulation technique are basically possible even in polar liquid media. However, the cantilever deflection is not only induced by the electrostatic force, but also by the surface stress, which does not include the local dielectric information. Moreover, since the voltage applied between the tip and sample are divided by the electric double layer and the bulk polar liquid, the capacitive force acting on the apex of the tip are strongly attenuated. For these reasons, the lateral resolution in the local dielectric constant measurements is expected to be deteriorated in polar liquid media depending on the magnitude of dielectric response. Finally, we present the criteria for local dielectric constant measurements with a high lateral resolution in polar liquid media.

The role of disclinations on the organization and conductivity in liquid crystal nanocomposites

NASA Astrophysics Data System (ADS)

Martinez-Miranda, Luz J.; Romero-Hasler, P.; Meneses-Franco, A.; Soto-Bustamante, E. A.

The structure of TiO2 nanoparticles in a liquid crystal nanocomposite was found to be an oblique structure due to the alignment of the TiO2 with respect to the liquid crystals. This order is anisotropic due to the ordering of the liquid crystals. The particles are highly localized in the nanocomposite, which has consequences in the electrical percolation. We want to obtain an understanding of how the nanoparticles organize in this highly localized fashion. The nanoparticles and the liquid crystals phase separate, with the nanoparticles accumulating in the defects exhibited by the liquid crystal even after being sonicated initially. The liquid crystal is polymerized by the process of electropolymerization that takes place in the isotropic phase of the monomers. The nanoparticles are free to move away from the defects where they phase separate since the defects disappear in the isotropic. We believe the polymerization imposes a limitation in the movement of the nanoparticles. The combination of the accumulation in the disclinations, the polymerization in the isotropic and the formation of the liquid crystal unit side chains can affect the conductivity of the nanocomposite. NSF-OISE-1157589; Fondecyt Project 1130187; CONICYT scholarships 21130413 and 21090713.

Micro-structure and motion of two-dimensional dense short spherocylinder liquids

NASA Astrophysics Data System (ADS)

Wang, Wen; Lin, Jyun-Ting; Su, Yen-Shuo; I, Lin

2018-03-01

We numerically investigate the micro-structure and motion of 2D liquids composed of dense short spherocylinders, by reducing the shape aspect ratio from 3. It is found that reducing shape aspect ratio from 3 causes a smooth transition from heterogeneous structures composed of crystalline ordered domains with good tetratic alignment order to those with good hexagonal bond-orientational order at an aspect ratio equaling 1.35. In the intermediate regime, both structural orders are strongly deteriorated, and the translational hopping rate reaches a maximum due to the poor particle interlocking of the disordered structure. Shortening rod length allows easier rotation, induces monotonic increase of rotational hopping rates, and resumes the separation of rotational and translational hopping time scales at the small aspect ratio end, after the crossover of their rates in the intermediate regime. At the large shape aspect ratio end, the poor local tetratic order has the same positive effects on facilitating local rotational and translational hopping. In contrast, at the small shape aspect ratio end, the poor local bond orientational order has the opposite effects on facilitating local rotational and translational hopping.

Incorporation of metal nanoparticles into wood substrate and methods

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

Rector, Kirk D; Lucas, Marcel

Metal nanoparticles were incorporated into wood. Ionic liquids were used to expand the wood cell wall structure for nanoparticle incorporation into the cell wall structure. Nanoparticles of elemental gold or silver were found to be effective surface enhanced Raman spectroscopy (SERS) imaging contrast or sensing agents. Nanoparticles of elemental iron were found to be efficient microwave absorbers and caused localized heating for disrupting the integrity of the lignocellulosic matrix. Controls suggest that the localized heating around the iron nanoparticles reduces losses of cellulose in the form of water, volatiles and CO.sub.2. The ionic liquid is needed during the incorporation processmore » at room temperature. The use of small amounts of ionic liquid combined with the absence of an ionic liquid purification step and a lower energy and water use are expected to reduce costs in an up-scaled pretreatment process.« less

Structural analysis of zwitterionic liquids vs. homologous ionic liquids

NASA Astrophysics Data System (ADS)

Wu, Boning; Kuroda, Kosuke; Takahashi, Kenji; Castner, Edward W.

2018-05-01

Zwitterionic liquids (Zw-ILs) have been developed that are homologous to monovalent ionic liquids (ILs) and show great promise for controlled dissolution of cellulosic biomass. Using both high energy X-ray scattering and atomistic molecular simulations, this article compares the bulk liquid structural properties for novel Zw-ILs with their homologous ILs. It is shown that the significant localization of the charges on Zw-ILs leads to charge ordering similar to that observed for conventional ionic liquids with monovalent anions and cations. A low-intensity first sharp diffraction peak in the liquid structure factor S(q) is observed for both the Zw-IL and the IL. This is unexpected since both the Zw-IL and IL have a 2-(2-methoxyethoxy)ethyl (diether) functional group on the cationic imidazolium ring and ether functional groups are known to suppress this peak. Detailed analyses show that this intermediate range order in the liquid structure arises for slightly different reasons in the Zw-IL vs. the IL. For the Zw-IL, the ether tails in the liquid are shown to aggregate into nanoscale domains.

Impact of medium-range order on the glass transition in liquid Ni-Si alloys

NASA Astrophysics Data System (ADS)

Lü, Y. J.; Entel, P.

2011-09-01

We study the thermophysical properties and structure of liquid Ni-Si alloys using molecular dynamics simulations. The liquid Ni-5% and 10%Si alloys crystallize to form the face-centered cubic (Ni) at 900 and 850 K, respectively, and the glass transitions take place in Ni-20% and 25%Si alloys at about 700 K. The temperature-dependent self-diffusion coefficients and viscosities exhibit more pronounced non-Arrhenius behavior with the increase of Si content before phase transitions, indicating the enhanced glass-forming ability. These appearances of thermodynamic properties and phase transitions are found to closely relate to the medium-range order clusters with the defective face-centered cubic structure characterized by both local translational and orientational order. This locally ordered structure tends to be destroyed by the addition of more Si atoms, resulting in a delay of nucleation and even glass transition instead.

The Connection Between Local Icosahedral Order in Metallic Liquids and the Nucleation Behavior of Ordered Phases

NASA Technical Reports Server (NTRS)

Kelton, K. F.; Gangopadhyay, A. K.; Lee, G. W.; Hyers, R. W.; Rathz, T. J.; Rogers, J. R.; Robinson, M. B.; Schenk, T.; Simonet, V.

2003-01-01

Over fifty years ago, David Turnbull showed that the temperature of many metallic liquids could be decreased far below their equilibrium melting temperature before crystallization occurred. To explain those surprising results, Charles Frank hypothesized that the local structures of undercooled metallic liquids are different from those of crystal phases, containing a significant degree of icosahedral order that is incompatible with extended periodicity. Such structural differences must create a barrier to the formation crystal phases, explaining the observed undercooling behavior. If true, the nucleation from the liquid of phases with extended icosahedral order should be easier. Icosahedral order is often favored in small clusters, as observed recently in liquid-like clusters of pure Pb on the (111) surface of Si[3], for example. However, it has never been shown that an increasing preference for icosahedral phase formation can be directly linked with the development of icosahedral order in the undercooled liquid. Owing to the combination of very recent advances in levitation techniques and the availability of synchrotron x-ray and high flux neutron facilities, this is shown here.

The Connection Between Local Icosahedral Order in Metallic Liquids and the Nucleation of Ordered Phases

NASA Technical Reports Server (NTRS)

Curreri, Peter A. (Technical Monitor); Kelton, K. F.; Gangopadhyay, A.; Lee, G. W.; Hyers, R. W.; Rathz, R. J.; Rogers, J.; Schenk, T.; Simonet, V.; Holland-Moritz, D.

2003-01-01

Over fifty years ago, David Turnbull showed that the temperature of many metallic liquids could be decreased far below their equilibrium melting temperature before crystallization occurred. To explain those surprising results, Charles Frank hypothesized that the local structures of undercooled metallic liquids are different from those of crystal phases, containing a significant degree of icosahedral order that is incompatible with extended periodicity. Such structural differences must create a barrier to the formation crystal phases, explaining the observed undercooling behavior. If true, the nucleation from the liquid of phases with extended icosahedral order should be easier. Icosahedral order is often favored in small clusters, as observed recently in liquid-like clusters of pure Pb on the (111) surface of Si, for example. However, it has never been shown that an increasing preference for icosahedral phase formation can be directly linked with the development of icosahedral order in the undercooled liquid. Owing to the combination of very recent advances in levitation techniques and the availability of synchrotron x-ray and high flux neutron facilities, this is shown here.

The Connection Between Local Icosahedral Order in Metallic Liquids and the Nucleation of Ordered Phases

NASA Technical Reports Server (NTRS)

Kelton, K. F.; Gangopadhyay, A. K.; Lee, G. W.; Hyers, R. W.; Rathz, T. J.; Rogers, J. R.; Robinson, M. B.; Schenk, T.; Simonet, V.; Holland-Moritz, D.;

A cost-effective quasi-distributed liquid leakage sensor based on the polymer optical fiber and flexible lamp belt with LEDs.

PubMed

Zhang, Yingzi; Hou, Yulong; Zhang, Yanjun; Hu, Yanjun; Zhang, Liang; Gao, Xiaolong; Zhang, Huixin; Liu, Wenyi

2018-04-16

A quasi-distributed liquid leakage (QDLL) sensor in local area is proposed and experimentally demonstrated, providing a real-time yet low-cost method than the existing local QDLL sensor. The sensor mainly consists of a flexible lamp belt (FLB) with light-emitting diodes (LEDs) and a polymer optical fiber (POF) processed with side-coupling structures. The side-coupling structures are illuminated by the LEDs one by one, forming a series of sensing probes. The lights are side-coupled into the POF through the side-coupling structure and pulse sequences are obtained from the power meters connected to the both ends of the POF. Each pulse represents a sensing probe, and the intensity of them increase when the coupling medium changes from air to liquid. The location of the leakage incident can be got by the position of each pulse in its output sequence. The influence of different side-coupling structures on side-coupling ratio are investigated. The experiment results validate the detection and localization abilities of the QDLL sensor along a 1 m-long POF with a spatial resolution of 0.1 m, which can be improved by adjusting the side-coupling structure. Furthermore, the temperature dependence is studied and can be compensated.

Electron Doping a Kagome Spin Liquid

NASA Astrophysics Data System (ADS)

Kelly, Zachary; Gallagher, Miranda; McQueen, Tyrel

In 1987, Anderson proposed that charge doping a material with the resonating valance bond (RVB) state would yield a superconducting state. Ever since, there has been a search for these RVB containing spin liquid materials and their charge doped counterparts. Studies on the most promising spin liquid candidate, Herbertsmithite, ZnCu3(OH)6Cl2, a two dimensional kagomé lattice, show evidence of fractionalized excitations and a gapped ground state. In this work, we report the synthesis and characterization of a newly synthesized electron doped spin liquid, ZnLixCu3(OH)6Cl2 from x = 0 to x = 1.8 (3 / 5 th per Cu2+). Despite heavy doping, the series remains insulating and the magnetism is systematically suppressed. We have done extensive structural studies of the doped series to determine the effect of the intercalated atoms on the structure, and whether these structural differences induce strong localization effects that suppress the metallic and superconducting states. Other doped spin liquid candidates are also being explored to understand if this localization is system dependent or systemic to all doped spin liquid systems. NSF, Division of Materials Research (DMR), Solid State Chemistry (SSMC), CAREER Grant under Award No. DMR- 1253562, Institute for Quantum Matter under Grant No.DE-FG02- 08ER46544, and the David and Lucile Packard Foundation.

Thermodynamic and kinetic considerations of nucleation and stabilization of acoustic cavitation bubbles in water.

PubMed

Bapat, Pratap S; Pandit, Aniruddha B

2008-01-01

Qualitative explanation for a homogeneous nucleation of acoustic cavitation bubbles in the incompressible liquid water with simple phenomenological approach has been provided via the concept of the desorbtion of the dissolved gas and the vaporization of local liquid molecules. The liquid medium has been viewed as an ensemble of lattice structures. Validity of the lattice structure approach against the Brownian motion of molecules in the liquid state has been discussed. Criterion based on probability for nucleus formation has been defined for the vaporization of local liquid molecules. Energy need for the enthalpy of vaporization has been considered as an energy criterion for the formation of a vaporous nucleus. Sound energy, thermal energy of the liquid bulk (Joule-Thomson effect) and free energy of activation, which is associated with water molecules in the liquid state (Brownian motion) as per the modified Eyring's kinetic theory of liquid are considered as possible sources for the enthalpy of vaporization of water molecules forming a single unit lattice. The classical nucleation theory has then been considered for expressing further growth of the vaporous nucleus against the surface energy barrier. Effect of liquid property (temperature), and effect of an acoustic parameter (frequency) on an acoustic cavitation threshold pressure have been discussed. Kinetics of nucleation has been considered.

Electrical resistivity of liquid lanthanides using charge hard sphere system

NASA Astrophysics Data System (ADS)

Sonvane, Y. A.; Thakor, P. B.; Jani, A. R.

2013-06-01

In the present paper, we have studied electrical resistivity (ρ) of liquid lanthanides. To describe the structural information, the structure factor S(q) due to the charged hard sphere (CHS) reference systems is used along with our newly constructed model potential. To see the influence of exchange and correlation effect on the electrical resistivity (ρ) have used different local field correction functions like Hartree (H), Sarkar et al (S) and Taylor (T). Lastly we conclude that the proper choice of the model potential along with local field correction function plays a vital role to the study of the electrical resistivity (ρ).

Static heterogeneities in liquid water

NASA Astrophysics Data System (ADS)

Stanley, H. Eugene; Buldyrev, Sergey V.; Giovambattista, Nicolas

2004-10-01

The thermodynamic behavior of water seems to be closely related to static heterogeneities. These static heterogeneities are related to the local structure of water molecules, and when properly characterized, may offer an economical explanation of thermodynamic data. The key feature of liquid water is not so much that the existence of hydrogen bonds, first pointed out by Linus Pauling, but rather the local geometry of the liquid molecules is not spherical or oblong but tetrahedral. In the consideration of static heterogeneities, this local geometry is critical. Recent experiments suggested more than one phase of amorphous solid water, while simulations suggest that one of these phases is metastable with respect to another, so that in fact there are only two stable phases.

Optical isotropy and iridescence in a smectic 'blue phase'.

PubMed

Yamamoto, Jun; Nishiyama, Isa; Inoue, Miyoshi; Yokoyama, Hiroshi

2005-09-22

When liquid crystal molecules are chiral, the twisted structure competes with spatially uniform liquid crystalline orders, resulting in a variety of modulated liquid crystal phases, such as the cholesteric blue phase, twist grain boundary and smectic blue phases. Here we report a liquid crystal smectic blue phase (SmBP(iso)), formed from a two-component mixture containing a chiral monomer and a 'twin' containing two repeat units of the first molecule connected by a linear hydrocarbon spacer. The phase exhibits the simultaneous presence of finite local-order parameters of helices and smectic layers, without any discontinuity on a mesoscopic length scale. The anomalous softening of elasticity due to a strong reduction in entropy caused by mixing the monomer and the twin permits the seamless coexistence of these two competing liquid crystal orders. The new phase spontaneously exhibits an optically isotropic but uniformly iridescent colour and automatically acquires spherical symmetry, so that the associated photonic band gap maintains the same symmetry despite the local liquid crystalline order. We expect a range of unusual optical transmission properties based on this three-dimensional isotropic structure, and complete tunability due to the intrinsic softness and responsiveness of the liquid crystalline order against external fields.

Dynamical, structural and chemical heterogeneities in a binary metallic glass-forming liquid

NASA Astrophysics Data System (ADS)

Puosi, F.; Jakse, N.; Pasturel, A.

2018-04-01

As it approaches the glass transition, particle motion in liquids becomes highly heterogeneous and regions with virtually no mobility coexist with liquid-like domains. This complex dynamic is believed to be responsible for different phenomena including non-exponential relaxation and the breakdown of the Stokes-Einstein relation. Understanding the relationships between dynamical heterogeneities and local structure in metallic liquids and glasses is a major scientific challenge. Here we use classical molecular dynamics simulations to study the atomic dynamics and microscopic structure of Cu50Zr50 alloy in the supercooling regime. Dynamical heterogeneities are identified via an isoconfigurational analysis. We demonstrate the transition from isolated to clustering low mobility with decreasing temperature. These slow clusters, whose sizes grow upon cooling, are also associated with concentration fluctuations, characterized by a Zr-enriched phase, with a composition CuZr2 . In addition, a structural analysis of slow clusters based on Voronoi tessellation evidences an increase with respect of the bulk system of the fraction of Cu atoms having a local icosahedral order. These results are in agreement with the consolidated scenario of the relevant role played by icosahedral order in the dynamic slowing-down in supercooled metal alloys.

In-situ High-energy X-ray Diffraction Study of the Local Structure of Supercooled Liquid Si

NASA Technical Reports Server (NTRS)

Lee, G. W.; Kim, T. H.; Sieve, B.; Gangopadhyay, A. K.; Hyers, R. W.; Rathz, T. J.; Rogers, J. R.; Robinson, D. S.; Kelton, K. F.; Goldman, A. I.

2005-01-01

While changes in the coordination number for liquid silicon upon supercooling, signaling an underlying liquid-liquid phase transition, have been predicted, x-ray and neutron measurements have produced conflicting reports. In particular some studies have found an increase in the first shell coordination as temperature decreases in the supercooled regime, while others have reported increases in the coordination number with decreasing temperature. Employing the technique of electrostatic levitation coupled with high energy x-ray diffraction (125 keV), and rapid data acquisition (100ms collection times) using an area detector, we have obtained high quality structural data more deeply into the supercooled regime than has been possible before. No change in coordination number is observed in this temperature region, calling into question previous experimental claims of structural evidence for the existence of a liquid-liquid phase transition.

Nucleophosmin integrates within the nucleolus via multi-modal interactions with proteins displaying R-rich linear motifs and rRNA.

PubMed

Mitrea, Diana M; Cika, Jaclyn A; Guy, Clifford S; Ban, David; Banerjee, Priya R; Stanley, Christopher B; Nourse, Amanda; Deniz, Ashok A; Kriwacki, Richard W

2016-02-02

The nucleolus is a membrane-less organelle formed through liquid-liquid phase separation of its components from the surrounding nucleoplasm. Here, we show that nucleophosmin (NPM1) integrates within the nucleolus via a multi-modal mechanism involving multivalent interactions with proteins containing arginine-rich linear motifs (R-motifs) and ribosomal RNA (rRNA). Importantly, these R-motifs are found in canonical nucleolar localization signals. Based on a novel combination of biophysical approaches, we propose a model for the molecular organization within liquid-like droplets formed by the N-terminal domain of NPM1 and R-motif peptides, thus providing insights into the structural organization of the nucleolus. We identify multivalency of acidic tracts and folded nucleic acid binding domains, mediated by N-terminal domain oligomerization, as structural features required for phase separation of NPM1 with other nucleolar components in vitro and for localization within mammalian nucleoli. We propose that one mechanism of nucleolar localization involves phase separation of proteins within the nucleolus.

Ultrafast vibrational spectroscopy (2D-IR) of CO{sub 2} in ionic liquids: Carbon capture from carbon dioxide’s point of view

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

Brinzer, Thomas; Berquist, Eric J.; Ren, Zhe

2015-06-07

The CO{sub 2}ν{sub 3} asymmetric stretching mode is established as a vibrational chromophore for ultrafast two-dimensional infrared (2D-IR) spectroscopic studies of local structure and dynamics in ionic liquids, which are of interest for carbon capture applications. CO{sub 2} is dissolved in a series of 1-butyl-3-methylimidazolium-based ionic liquids ([C{sub 4}C{sub 1}im][X], where [X]{sup −} is the anion from the series hexafluorophosphate (PF{sub 6}{sup −}), tetrafluoroborate (BF{sub 4}{sup −}), bis-(trifluoromethyl)sulfonylimide (Tf{sub 2}N{sup −}), triflate (TfO{sup −}), trifluoroacetate (TFA{sup −}), dicyanamide (DCA{sup −}), and thiocyanate (SCN{sup −})). In the ionic liquids studied, the ν{sub 3} center frequency is sensitive to the local solvationmore » environment and reports on the timescales for local structural relaxation. Density functional theory calculations predict charge transfer from the anion to the CO{sub 2} and from CO{sub 2} to the cation. The charge transfer drives geometrical distortion of CO{sub 2}, which in turn changes the ν{sub 3} frequency. The observed structural relaxation timescales vary by up to an order of magnitude between ionic liquids. Shoulders in the 2D-IR spectra arise from anharmonic coupling of the ν{sub 2} and ν{sub 3} normal modes of CO{sub 2}. Thermal fluctuations in the ν{sub 2} population stochastically modulate the ν{sub 3} frequency and generate dynamic cross-peaks. These timescales are attributed to the breakup of ion cages that create a well-defined local environment for CO{sub 2}. The results suggest that the picosecond dynamics of CO{sub 2} are gated by local diffusion of anions and cations.« less

Localized modes in optics of photonic liquid crystals with local anisotropy of absorption

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

Belyakov, V. A., E-mail: bel1937@mail.ru, E-mail: bel@landau.ac.ru; Semenov, S. V.

2016-05-15

The localized optical modes in spiral photonic liquid crystals are theoretically studied for the certainty at the example of chiral liquid crystals (CLCs) for the case of CLC with an anisotropic local absorption. The model adopted here (absence of dielectric interfaces in the structures under investigation) makes it possible to get rid of mixing of polarizations on the surfaces of the CLC layer and of the defect structure and to reduce the corresponding equations to only the equations for light with polarization diffracting in the CLC. The dispersion equations determining connection of the edge mode (EM) and defect mode (DM)more » frequencies with the CLC layer parameters (anisotropy of local absorption, CLC order parameter) and other parameters of the DMS are obtained. Analytic expressions for the transmission and reflection coefficients of CLC layer and DMS for the case of CLC with an anisotropic local absorption are presented and analyzed. It is shown that the CLC layers with locally anisotropic absorption reduce the EM and DM lifetimes (and increase the lasing threshold) in the way different from the case of CLC with an isotropic local absorption. Due to the Borrmann effect revealing of which is different at the opposite stop-band edges in the case of CLC layers with an anisotropic local absorption the EM life-times for the EM frequencies at the opposite stop-bands edges may be significantly different. The options of experimental observations of the theoretically revealed phenomena are briefly discussed.« less

Localized modes in optics of photonic liquid crystals with local anisotropy of absorption

NASA Astrophysics Data System (ADS)

Belyakov, V. A.; Semenov, S. V.

2016-05-01

The localized optical modes in spiral photonic liquid crystals are theoretically studied for the certainty at the example of chiral liquid crystals (CLCs) for the case of CLC with an anisotropic local absorption. The model adopted here (absence of dielectric interfaces in the structures under investigation) makes it possible to get rid of mixing of polarizations on the surfaces of the CLC layer and of the defect structure and to reduce the corresponding equations to only the equations for light with polarization diffracting in the CLC. The dispersion equations determining connection of the edge mode (EM) and defect mode (DM) frequencies with the CLC layer parameters (anisotropy of local absorption, CLC order parameter) and other parameters of the DMS are obtained. Analytic expressions for the transmission and reflection coefficients of CLC layer and DMS for the case of CLC with an anisotropic local absorption are presented and analyzed. It is shown that the CLC layers with locally anisotropic absorption reduce the EM and DM lifetimes (and increase the lasing threshold) in the way different from the case of CLC with an isotropic local absorption. Due to the Borrmann effect revealing of which is different at the opposite stop-band edges in the case of CLC layers with an anisotropic local absorption the EM life-times for the EM frequencies at the opposite stop-bands edges may be significantly different. The options of experimental observations of the theoretically revealed phenomena are briefly discussed.

Water polygons in high-resolution protein crystal structures.

PubMed

Lee, Jonas; Kim, Sung-Hou

2009-07-01

We have analyzed the interstitial water (ISW) structures in 1500 protein crystal structures deposited in the Protein Data Bank that have greater than 1.5 A resolution with less than 90% sequence similarity with each other. We observed varieties of polygonal water structures composed of three to eight water molecules. These polygons may represent the time- and space-averaged structures of "stable" water oligomers present in liquid water, and their presence as well as relative population may be relevant in understanding physical properties of liquid water at a given temperature. On an average, 13% of ISWs are localized enough to be visible by X-ray diffraction. Of those, averages of 78% are water molecules in the first water layer on the protein surface. Of the localized ISWs beyond the first layer, almost half of them form water polygons such as trigons, tetragons, as well as expected pentagons, hexagons, higher polygons, partial dodecahedrons, and disordered networks. Most of the octagons and nanogons are formed by fusion of smaller polygons. The trigons are most commonly observed. We suggest that our observation provides an experimental basis for including these water polygon structures in correlating and predicting various water properties in liquid state.

Water polygons in high-resolution protein crystal structures

PubMed Central

Lee, Jonas; Kim, Sung-Hou

2009-01-01

We have analyzed the interstitial water (ISW) structures in 1500 protein crystal structures deposited in the Protein Data Bank that have greater than 1.5 Å resolution with less than 90% sequence similarity with each other. We observed varieties of polygonal water structures composed of three to eight water molecules. These polygons may represent the time- and space-averaged structures of “stable” water oligomers present in liquid water, and their presence as well as relative population may be relevant in understanding physical properties of liquid water at a given temperature. On an average, 13% of ISWs are localized enough to be visible by X-ray diffraction. Of those, averages of 78% are water molecules in the first water layer on the protein surface. Of the localized ISWs beyond the first layer, almost half of them form water polygons such as trigons, tetragons, as well as expected pentagons, hexagons, higher polygons, partial dodecahedrons, and disordered networks. Most of the octagons and nanogons are formed by fusion of smaller polygons. The trigons are most commonly observed. We suggest that our observation provides an experimental basis for including these water polygon structures in correlating and predicting various water properties in liquid state. PMID:19551896

Atomic-scale structural signature of dynamic heterogeneities in metallic liquids

NASA Astrophysics Data System (ADS)

Pasturel, Alain; Jakse, Noel

2017-08-01

With sufficiently high cooling rates, liquids will cross their equilibrium melting temperatures and can be maintained in a metastable undercooled state before solidifying. Studies of undercooled liquids reveal several intriguing dynamic phenomena and because explicit connections between liquid structure and liquids dynamics are difficult to identify, it remains a major challenge to capture the underlying structural link to these phenomena. Ab initio molecular dynamics (AIMD) simulations are yet especially powerful in providing atomic-scale details otherwise not accessible in experiments. Through the AIMD-based study of Cr additions in Al-based liquids, we evidence for the first time a close relationship between the decoupling of component diffusion and the emergence of dynamic heterogeneities in the undercooling regime. In addition, we demonstrate that the origin of both phenomena is related to a structural heterogeneity caused by a strong interplay between chemical short-range order (CSRO) and local fivefold topology (ISRO) at the short-range scale in the liquid phase that develops into an icosahedral-based medium-range order (IMRO) upon undercooling. Finally, our findings reveal that this structural signature is also captured in the temperature dependence of partial pair-distribution functions which opens up the route to more elaborated experimental studies.

Dynamics of topological solitons, knotted streamlines, and transport of cargo in liquid crystals

NASA Astrophysics Data System (ADS)

Sohn, Hayley R. O.; Ackerman, Paul J.; Boyle, Timothy J.; Sheetah, Ghadah H.; Fornberg, Bengt; Smalyukh, Ivan I.

2018-05-01

Active colloids and liquid crystals are capable of locally converting the macroscopically supplied energy into directional motion and promise a host of new applications, ranging from drug delivery to cargo transport at the mesoscale. Here we uncover how topological solitons in liquid crystals can locally transform electric energy to translational motion and allow for the transport of cargo along directions dependent on frequency of the applied electric field. By combining polarized optical video microscopy and numerical modeling that reproduces both the equilibrium structures of solitons and their temporal evolution in applied fields, we uncover the physical underpinnings behind this reconfigurable motion and study how it depends on the structure and topology of solitons. We show that, unexpectedly, the directional motion of solitons with and without the cargo arises mainly from the asymmetry in rotational dynamics of molecular ordering in liquid crystal rather than from the asymmetry of fluid flows, as in conventional active soft matter systems.

Understanding cage effects in imidazolium ionic liquids by 129Xe NMR: MD simulations and relativistic DFT calculations.

PubMed

Saielli, Giacomo; Bagno, Alessandro; Castiglione, Franca; Simonutti, Roberto; Mauri, Michele; Mele, Andrea

2014-12-04

(129)Xe NMR has been recently employed to probe the local structure of ionic liquids (ILs). However, no theoretical investigation has been yet reported addressing the problem of the dependence of the chemical shift of xenon on the cage structure of the IL. Therefore, we present here a study of the chemical shift of (129)Xe in two ionic liquids, [bmim][Cl] and [bmim][PF6], by a combination of classical MD simulations and relativistic DFT calculations of the xenon shielding constant. The bulk structure of the two ILs is investigated by means of the radial distribution functions, paying special attention to the local structure, volume, and charge distribution of the cage surrounding the xenon atom. Relativistic DFT calculations, based on the ZORA formalism, on clusters extracted from the trajectory files of the two systems, yield an average relative chemical shift in good agreement with the experimental data. Our results demonstrate the importance of the cage volume and the average charge surrounding the xenon nucleus in the IL cage as the factors determining the effective shielding.

Nonlinear periodic wavetrains in thin liquid films falling on a uniformly heated horizontal plate

NASA Astrophysics Data System (ADS)

Issokolo, Remi J. Noumana; Dikandé, Alain M.

2018-05-01

A thin liquid film falling on a uniformly heated horizontal plate spreads into fingering ripples that can display a complex dynamics ranging from continuous waves, nonlinear spatially localized periodic wave patterns (i.e., rivulet structures) to modulated nonlinear wavetrain structures. Some of these structures have been observed experimentally; however, conditions under which they form are still not well understood. In this work, we examine profiles of nonlinear wave patterns formed by a thin liquid film falling on a uniformly heated horizontal plate. For this purpose, the Benney model is considered assuming a uniform temperature distribution along the film propagation on the horizontal surface. It is shown that for strong surface tension but a relatively small Biot number, spatially localized periodic-wave structures can be analytically obtained by solving the governing equation under appropriate conditions. In the regime of weak nonlinearity, a multiple-scale expansion combined with the reductive perturbation method leads to a complex Ginzburg-Landau equation: the solutions of which are modulated periodic pulse trains which amplitude and width and period are expressed in terms of characteristic parameters of the model.

Statistical Fine Structure in Inhomogeneously Broadened Absorption Lines in Solids.

DTIC Science & Technology

1987-12-22

the inhomogeneously broadened zero-phonon SijSo (0-0) absorption of pentacene molecules in crystals of p-terphenyl at liquid helium temperatures. SFS...structure (SFS) in the inhomogeneously broadened zero-phonon S, +- So (0-0) absorption of pentacene molecules in crystals of p-terphenyl at liquid helium...tile large multiplicity of local environments. Inhomogeneously broadened absorption lines are usually treated as smooth, Gaussian profiles. In recent

Temperature dependent structural and dynamical properties of liquid Cu80Si20 binary alloy

NASA Astrophysics Data System (ADS)

Suthar, P. H.; Shah, A. K.; Gajjar, P. N.

2018-05-01

Ashcroft and Langreth binary structure factor have been used to study for pair correlation function and the study of dynamical variable: velocity auto correlation functions, power spectrum and mean square displacement calculated based on the static harmonic well approximation in liquid Cu80Si20 binary alloy at wide temperature range (1140K, 1175K, 1210K, 1250K, 1373K, 1473K.). The effective interaction for the binary alloy is computed by our well established local pseudopotential along with the exchange and correction functions Sarkar et al(S). The negative dip in velocity auto correlation decreases as the various temperature is increases. For power spectrum as temperature increases, the peak of power spectrum shifts toward lower ω. Good agreement with the experiment is observed for the pair correlation functions. Velocity auto correlation showing the transferability of the local pseudopotential used for metallic liquid environment in the case of copper based binary alloys.

Impact of water dilution and cation tail length on ionic liquid characteristics: Interplay between polar and non-polar interactions

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

Hegde, Govind A.; Bharadwaj, Vivek S.; Kinsinger, Corey L.

2016-08-14

The recalcitrance of lignocellulosic biomass poses a major challenge that hinders the economical utilization of biomass for the production of biofuel, plastics, and chemicals. Ionic liquids have become a promising solvent that addresses many issues in both the pretreatment process and the hydrolysis of the glycosidic bond for the deconstruction of cellulosic materials. However, to make the use of ionic liquids economically viable, either the cost of ionic liquids must be reduced, or a less expensive solvent (e.g., water) may be added to reduce the overall amount of ionic liquid used in addition to reducing the viscosity of the binarymore » liquid mixture. In this work, we employ atomistic molecular dynamics simulations to investigate the impact of water dilution on the overall liquid structure and properties of three imidazolium based ionic liquids. It is found that ionic liquid-water mixtures exhibit characteristics that can be grouped into two distinct regions, which are a function of the ionic liquid concentration. The trends observed in each region are found to correlate with the ordering in the local structure of the ionic liquid that arises from the dynamic interactions between the ion pairs. Simulation results suggest that there is a high level of local ordering in the molecular structure at high concentrations of ionic liquids that is driven by the aggregation of the cationic tails and the anion-water interactions. It is found that as the concentration of ionic liquids in the binary mixture is decreased, there is a point at which the competing self and cross interaction energies between the ionic liquid and water shifts away from a cation-anion dominated regime, which results in a significant change in the mixture properties. This break point, which occurs around 75% w/w ionic liquids, corresponds to the point at which water molecules percolate into the ionic liquid network disrupting the ionic liquids’ nanostructure. It is observed that as the cationic alkyl tail length increases, the changes in the binary mixtures’ properties become more pronounced.« less

Nucleophosmin integrates within the nucleolus via multi-modal interactions with proteins displaying R-rich linear motifs and rRNA

PubMed Central

Mitrea, Diana M; Cika, Jaclyn A; Guy, Clifford S; Ban, David; Banerjee, Priya R; Stanley, Christopher B; Nourse, Amanda; Deniz, Ashok A; Kriwacki, Richard W

2016-01-01

The nucleolus is a membrane-less organelle formed through liquid-liquid phase separation of its components from the surrounding nucleoplasm. Here, we show that nucleophosmin (NPM1) integrates within the nucleolus via a multi-modal mechanism involving multivalent interactions with proteins containing arginine-rich linear motifs (R-motifs) and ribosomal RNA (rRNA). Importantly, these R-motifs are found in canonical nucleolar localization signals. Based on a novel combination of biophysical approaches, we propose a model for the molecular organization within liquid-like droplets formed by the N-terminal domain of NPM1 and R-motif peptides, thus providing insights into the structural organization of the nucleolus. We identify multivalency of acidic tracts and folded nucleic acid binding domains, mediated by N-terminal domain oligomerization, as structural features required for phase separation of NPM1 with other nucleolar components in vitro and for localization within mammalian nucleoli. We propose that one mechanism of nucleolar localization involves phase separation of proteins within the nucleolus. DOI: http://dx.doi.org/10.7554/eLife.13571.001 PMID:26836305

Nucleophosmin integrates within the nucleolus via multi-modal interactions with proteins displaying R-rich linear motifs and rRNA

DOE PAGES

Mitrea, Diana M.; Cika, Jaclyn A.; Guy, Clifford S.; ...

2016-02-02

In this study, the nucleolus is a membrane-less organelle formed through liquid-liquid phase separation of its components from the surrounding nucleoplasm. Here, we show that nucleophosmin (NPM1) integrates within the nucleolus via a multi-modal mechanism involving multivalent interactions with proteins containing arginine-rich linear motifs (R-motifs) and ribosomal RNA (rRNA). Importantly, these R-motifs are found in canonical nucleolar localization signals. Based on a novel combination of biophysical approaches, we propose a model for the molecular organization within liquid-like droplets formed by the N-terminal domain of NPM1 and R-motif peptides, thus providing insights into the structural organization of the nucleolus. We identifymore » multivalency of acidic tracts and folded nucleic acid binding domains, mediated by N-terminal domain oligomerization, as structural features required for phase separation of NPM1 with other nucleolar components in vitro and for localization within mammalian nucleoli. We propose that one mechanism of nucleolar localization involves phase separation of proteins within the nucleolus.« less

Role of string-like collective atomic motion on diffusion and structural relaxation in glass forming Cu-Zr alloys

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

Zhang, Hao; Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 2V4; Zhong, Cheng

2015-04-28

We investigate Cu-Zr liquid alloys using molecular dynamics simulation and well-accepted embedded atom method potentials over a wide range of chemical composition and temperature as model metallic glass-forming (GF) liquids. As with other types of GF materials, the dynamics of these complex liquids are characterized by “dynamic heterogeneity” in the form of transient polymeric clusters of highly mobile atoms that are composed in turn of atomic clusters exhibiting string-like cooperative motion. In accordance with the string model of relaxation, an extension of the Adam-Gibbs (AG) model, changes in the activation free energy ΔG{sub a} with temperature of both the Cumore » and Zr diffusion coefficients D, and the alpha structural relaxation time τ{sub α} can be described to a good approximation by changes in the average string length, L. In particular, we confirm that the strings are a concrete realization of the abstract “cooperatively rearranging regions” of AG. We also find coexisting clusters of relatively “immobile” atoms that exhibit predominantly icosahedral local packing rather than the low symmetry packing of “mobile” atoms. These two distinct types of dynamic heterogeneity are then associated with different fluid structural states. Glass-forming liquids are thus analogous to polycrystalline materials where the icosahedrally packed regions correspond to crystal grains, and the strings reside in the relatively disordered grain boundary-like regions exterior to these locally well-ordered regions. A dynamic equilibrium between localized (“immobile”) and wandering (“mobile”) particles exists in the liquid so that the dynamic heterogeneity can be considered to be type of self-assembly process. We also characterize changes in the local atomic free volume in the course of string-like atomic motion to better understand the initiation and propagation of these fluid excitations.« less

Local structural ordering in surface-confined liquid crystals

NASA Astrophysics Data System (ADS)

Śliwa, I.; Jeżewski, W.; Zakharov, A. V.

2017-06-01

The effect of the interplay between attractive nonlocal surface interactions and attractive pair long-range intermolecular couplings on molecular structures of liquid crystals confined in thin cells with flat solid surfaces has been studied. Extending the McMillan mean field theory to include finite systems, it has been shown that confining surfaces can induce complex orientational and translational ordering of molecules. Typically, local smectic A, nematic, and isotropic phases have been shown to coexist in certain temperature ranges, provided that confining cells are sufficiently thick, albeit finite. Due to the nonlocality of surface interactions, the spatial arrangement of these local phases can display, in general, an unexpected complexity along the surface normal direction. In particular, molecules located in the vicinity of surfaces can still be organized in smectic layers, even though nematic and/or isotropic order can simultaneously appear in the interior of cells. The resulting surface freezing of smectic layers has been confirmed to occur even for rather weak surface interactions. The surface interactions cannot, however, prevent smectic layers from melting relatively close to system boundaries, even when molecules are still arranged in layers within the central region of the system. The internal interfaces, separating individual liquid-crystal phases, are demonstrated here to form fronts of local finite-size transitions that move across cells under temperature changes. Although the complex molecular ordering in surface confined liquid-crystal systems can essentially be controlled by temperature variations, specific thermal properties of these systems, especially the nature of the local transitions, are argued to be strongly conditioned to the degree of molecular packing.

Aspirin locally disrupts the liquid-ordered phase

NASA Astrophysics Data System (ADS)

Alsop, Richard J.; Himbert, Sebastian; Dhaliwal, Alexander; Schmalzl, Karin; Rheinstädter, Maikel C.

2018-02-01

Local structure and dynamics of lipid membranes play an important role in membrane function. The diffusion of small molecules, the curvature of lipids around a protein and the existence of cholesterol-rich lipid domains (rafts) are examples for the membrane to serve as a functional interface. The collective fluctuations of lipid tails, in particular, are relevant for diffusion of membrane constituents and small molecules in and across membranes, and for structure and formation of membrane domains. We studied the effect of aspirin (acetylsalicylic acid, ASA) on local structure and dynamics of membranes composed of dimyristoylphosphocholine (DMPC) and cholesterol. Aspirin is a common analgesic, but is also used in the treatment of cholesterol. Using coherent inelastic neutron scattering experiments and molecular dynamics (MD) simulations, we present evidence that ASA binds to liquid-ordered, raft-like domains and disturbs domain organization and dampens collective fluctuations. By hydrogen-bonding to lipid molecules, ASA forms `superfluid' complexes with lipid molecules that can organize laterally in superlattices and suppress cholesterol's ordering effect.

Site-Specific Preparation of Intact Solid–Liquid Interfaces by Label-Free In Situ Localization and Cryo-Focused Ion Beam Lift-Out

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

Zachman, Michael J.; Asenath-Smith, Emily; Estroff, Lara A.

Abstract Scanning transmission electron microscopy (STEM) allows atomic scale characterization of solid–solid interfaces, but has seen limited applications to solid–liquid interfaces due to the volatility of liquids in the microscope vacuum. Although cryo-electron microscopy is routinely used to characterize hydrated samples stabilized by rapid freezing, sample thinning is required to access the internal interfaces of thicker specimens. Here, we adapt cryo-focused ion beam (FIB) “lift-out,” a technique recently developed for biological specimens, to prepare intact internal solid–liquid interfaces for high-resolution structural and chemical analysis by cryo-STEM. To guide the milling process we introduce a label-freein situmethod of localizing subsurface structuresmore » in suitable materials by energy dispersive X-ray spectroscopy (EDX). Monte Carlo simulations are performed to evaluate the depth-probing capability of the technique, and show good qualitative agreement with experiment. We also detail procedures to produce homogeneously thin lamellae, which enable nanoscale structural, elemental, and chemical analysis of intact solid–liquid interfaces by analytical cryo-STEM. This work demonstrates the potential of cryo-FIB lift-out and cryo-STEM for understanding physical and chemical processes at solid–liquid interfaces.« less

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

Armstrong, Clare L; Haeussler, Wolfgang; Seydel, Tilo

Lipid dynamics in the cholesterol-rich (40 mol%) liquid-ordered (lo) phase of dimyristoylphosphatidylcholine membranes were studied using neutron spin-echo and neutron backscattering. Recent theoretical and experimental evidence supports the notion of the liquid-ordered phase in phospholipid membranes as a locally structured liquid, with small ordered domains of a highly dynamic nature in equilibrium with a disordered matrix [S. Meinhardt, R. L. C. Vink and F. Schmid, Proc. Natl. Acad. Sci. U. S. A., 2013, 110(12), 4476 4481, C. L. Armstrong et al., PLoS One, 2013, 8(6), e66162]. This local structure was found to have a pronounced impact on the membranes' dynamicalmore » properties. We found that the long-wavelength dynamics in the liquid-ordered phase, associated with the elastic properties of the membranes, were faster by two orders of magnitude as compared to the liquid disordered phase. At the same time, collective nanoscale diffusion was significantly slower. The presence of a soft-mode (a slowing down) in the longwavelength dispersion relationship suggests an upper size limit for the ordered lipid domain of ~220 A. Moreover, from the relaxation rate of the collective lipid diffusion of lipid lipid distances, the lifetime of these domains was estimated to be about 100 nanoseconds.« less

A liquid-liquid transition can exist in monatomic transition metals with a positive melting slope

PubMed Central

Lee, Byeongchan; Lee, Geun Woo

2016-01-01

Liquid-liquid transitions under high pressure are found in many elemental materials, but the transitions are known to be associated with either sp-valent materials or f-valent rare-earth elements, in which the maximum or a negative slope in the melting line is readily suggestive of the transition. Here we find a liquid-liquid transition with a positive melting slope in transition metal Ti from structural, electronic, and thermodynamic studies using ab-initio molecular dynamics calculations, showing diffusion anomaly, but no density anomaly. The origin of the transition in liquid Ti is a pressure-induced increase of local structures containing very short bonds with directionality in electronic configurations. This behavior appears to be characteristic of the early transition metals. In contrast, the late transition metal liquid Ni does not show the L-L transition with pressure. This result suggests that the possibility of the L-L transition decreases from early to late transition metals as electronic structures of late transition metals barely have a Jahn-Teller effect and bond directionality. Our results generalize that a phase transition in disordered materials is found with any valence band regardless of the sign of the melting slope, but related to the symmetry of electronic structures of constituent elements. PMID:27762334

Probing the structural and dynamical properties of liquid water with models including non-local electron correlation

NASA Astrophysics Data System (ADS)

Del Ben, Mauro; Hutter, Jürg; VandeVondele, Joost

2015-08-01

Water is a ubiquitous liquid that displays a wide range of anomalous properties and has a delicate structure that challenges experiment and simulation alike. The various intermolecular interactions that play an important role, such as repulsion, polarization, hydrogen bonding, and van der Waals interactions, are often difficult to reproduce faithfully in atomistic models. Here, electronic structure theories including all these interactions at equal footing, which requires the inclusion of non-local electron correlation, are used to describe structure and dynamics of bulk liquid water. Isobaric-isothermal (NpT) ensemble simulations based on the Random Phase Approximation (RPA) yield excellent density (0.994 g/ml) and fair radial distribution functions, while various other density functional approximations produce scattered results (0.8-1.2 g/ml). Molecular dynamics simulation in the microcanonical (NVE) ensemble based on Møller-Plesset perturbation theory (MP2) yields dynamical properties in the condensed phase, namely, the infrared spectrum and diffusion constant. At the MP2 and RPA levels of theory, ice is correctly predicted to float on water, resolving one of the anomalies as resulting from a delicate balance between van der Waals and hydrogen bonding interactions. For several properties, obtaining quantitative agreement with experiment requires correction for nuclear quantum effects (NQEs), highlighting their importance, for structure, dynamics, and electronic properties. A computed NQE shift of 0.6 eV for the band gap and absorption spectrum illustrates the latter. Giving access to both structure and dynamics of condensed phase systems, non-local electron correlation will increasingly be used to study systems where weak interactions are of paramount importance.

Local structure in anisotropic systems determined by molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Komolkin, Andrei V.; Maliniak, Arnold

In the present communication we describe the investigation of local structure using a new visualization technique. The approach is based on two-dimensional pair correlation functions derived from a molecular dynamics computer simulation. We have used this method to analyse a trajectory produced in a simulation of a nematic liquid crystal of 4-n-pentyl-4'-cyanobiphenyl (5CB) (Komolkin et al., 1994, J. chem. Phys., 101, 4103). The molecule is assumed to have cylindrical symmetry, and the liquid crystalline phase is treated as uniaxial. The pair correlation functions or cylindrical distribution functions (CDFs) are calculated in the molecular (m) and laboratory (l) frames, gm2(z1 2, d1 2) and g12(Z1 2, D1 2). Anisotropic molecular organization in the liquid crystal is reflected in laboratory frame CDFs. The molecular excluded volume is determined and the effect of the fast motion in the alkyl chain is observed. The intramolecular distributions are included in the CDFs and indicate the size of the motional amplitude in the chain. Absence of long range order was confirmed, a feature typical for a nematic liquid crystal.

Whiskers growth and self-healing in Ti-based metallic glasses during ion irradiation

NASA Astrophysics Data System (ADS)

Zhang, Kun; Hu, Zheng; Zhao, Ziqiang; Wei, Bingchen; Li, Yansen; Wei, Yuhang

2018-04-01

Ti-based metallic glasses were subjected to a 20 MeV Cl4+ ion radiation under liquid-nitrogen cooling. Their responses, as well as effects of the electronic excitation and nucleus-nucleus collision were evaluated. The collision cascade during irradiation typically changes the structure by increasing the liquid-like zone/cluster, or the content of the free volume. However, along the ion incident depth, the structure change is inhomogeneous. Numerous whiskers appear and aggregate on the side of the irradiation surface, which are several micrometers away from the edge. This corresponds with the maximum collision depth obtained by the Monte Carlo simulation, where nuclear loss plays a dominant role. Moreover, the liquid-like zone continually forms, which add to the whiskers growth and subsequent self-healing. Results suggest that the irradiation-induced local shear stress combines with the well-localized liquid-like zone results in the observed phenomena. This study demonstrates that metallic glasses have high morphological instability under ion irradiation, which assets can pave new paths for their further applications.

Structure and Liquid Fragility in Sodium Carbonate.

PubMed

Wilson, Mark; Ribeiro, Mauro C C; Wilding, Martin C; Benmore, Chris; Weber, J K R; Alderman, Oliver; Tamalonis, Anthony; Parise, J B

2018-02-01

The relationship between local structure and dynamics is explored for molten sodium carbonate. A flexible fluctuating-charge model, which allows for changes in the shape and charge distribution of the carbonate molecular anion, is developed. The system shows the evolution of highly temperature-dependent complex low-dimensional structures which control the dynamics (and hence the liquid fragility). By varying the molecular anion charge distribution, the key interactions responsible for the formation of these structures can be identified and rationalized. An increase in the mean charge separation within the carbonate ions increases the connectivity of the emerging structures and leads to an increase in the system fragility.

Study of electronic structure of liquid Pb

NASA Astrophysics Data System (ADS)

Vora, A. M.; Gajjar, P. N.

2018-04-01

The Fiolhais et al.'s universal model potential in conjunction with the hard sphere technique of Percus and Yevick has been used for the study of electronic structure, Fermi energy and density of states of liquid Pb. The screening influence of the different forms of the local field correction functions proposed by Hartree (H) and Taylor (T) on the afore said properties is studied, which replicates the changing effects of screening and found suitable for the present study.

Statistical mechanics of monatomic liquids

NASA Astrophysics Data System (ADS)

Wallace, Duane C.

1997-10-01

Two key experimental properties of elemental liquids, together with an analysis of the condensed-system potential-energy surface, lead us logically to the dynamical theory of monatomic liquids. Experimentally, the ion motional specific heat is approximately 3Nk for N ions, implying the normal modes of motion are approximately 3N independent harmonic oscillators. This implies the potential surface contains nearly harmonic valleys. The equilibrium configuration at the bottom of each valley is a ``structure.'' Structures are crystalline or amorphous, and amorphous structures can have a remnant of local crystal symmetry, or can be random. The random structures are by far the most numerous, and hence dominate the statistical mechanics of the liquid state, and their macroscopic properties are uniform over the structure class, for large-N systems. The Hamiltonian for any structural valley is the static structure potential, a sum of harmonic normal modes, and an anharmonic correction. Again from experiment, the constant-density entropy of melting contains a universal disordering contribution of NkΔ, suggesting the random structural valleys are of universal number wN, where lnw=Δ. Our experimental estimate for Δ is 0.80. In quasiharmonic approximation, the liquid theory for entropy agrees with experiment, for all currently analyzable experimental data at elevated temperatures, to within 1-2% of the total entropy. Further testable predictions of the theory are mentioned.

Developing interface localized liquid dielectrophoresis for optical applications

NASA Astrophysics Data System (ADS)

McHale, Glen; Brown, Carl V.; Newton, Michael I.; Wells, Gary G.; Sampara, Naresh

2012-11-01

Electrowetting charges the solid-liquid interface to change the contact area of a droplet of a conducting liquid. It is a powerful technique used to create variable focus liquid lenses, electronic paper and other devices, but it depends upon ions within the liquid. Liquid dielectrophoresis (L-DEP) is a bulk force acting on the dipoles throughout a dielectric liquid and is not normally considered to be a localized effect acting at the interface between the liquid and a solid or other fluid. In this work, we show theoretically how non-uniform electric fields generated by interdigitated electrodes can effectively convert L-DEP into an interface localized form. We show that for droplets of sufficient thickness, the change in the cosine of the contact angle is proportional to the square of the applied voltage and so obeys a similar equation to that for electrowetting - this we call dielectrowetting. However, a major difference to electrowetting is that the strength of the effect is controlled by the electrode spacing and the liquid permittivity rather than the properties of an insulator in a sandwich structure. Experimentally, we show that that this dielectrowetting equation accurately describes the contact angle of a droplet of oil viewed across parallel interdigitated electrodes. Importantly, the induced spreading can be complete, such that contact angle saturation does not occur. We then show that for thin films, L-DEP can shape the liquid-air interface creating a spatially periodic wrinkle and that such a wrinkle can be used to create a voltage programmable phase diffraction grating.

Theoretical Investigation of Phonon Dispersion Relation of 3d Liquid Transition Metals

NASA Astrophysics Data System (ADS)

Thakor, P. B.; Sonvane, Y. A.; Gajjar, P. N.; Jani, A. R.

2011-12-01

The phonon dispersion relations of 3d liquid transition metals have been obtained in the present study. We have used Hubbard and Beeby (HB) method to generate phonon dispersion relation of liquid metals. To describe the structural information, the structure factor S(q) due to the Percus-Yevick hard sphere (PYHS) reference systems is used along with our newly constructed parameter free model potential. The influence of exchange and correlation effect on the phonon dispersion relation of 3d liquid transition metals is examined explicitly, which reflects the varying effects of screening. We have used different local field correction functions like Hartree (H), Taylor (T) and Sarkar et al (S). Present results have found good in agreement with available experimental data.

Slits, plates, and Poisson-Boltzmann theory in a local formulation of nonlocal electrostatics

NASA Astrophysics Data System (ADS)

Paillusson, Fabien; Blossey, Ralf

2010-11-01

Polar liquids like water carry a characteristic nanometric length scale, the correlation length of orientation polarizations. Continuum theories that can capture this feature commonly run under the name of “nonlocal” electrostatics since their dielectric response is characterized by a scale-dependent dielectric function ɛ(q) , where q is the wave vector; the Poisson(-Boltzmann) equation then turns into an integro-differential equation. Recently, “local” formulations have been put forward for these theories and applied to water, solvated ions, and proteins. We review the local formalism and show how it can be applied to a structured liquid in slit and plate geometries, and solve the Poisson-Boltzmann theory for a charged plate in a structured solvent with counterions. Our results establish a coherent picture of the local version of nonlocal electrostatics and show its ease of use when compared to the original formulation.

Transmission X-ray scattering as a probe for complex liquid-surface structures

DOE PAGES

Fukuto, Masafumi; Yang, Lin; Nykypanchuk, Dmytro; ...

2016-01-28

The need for functional materials calls for increasing complexity in self-assembly systems. As a result, the ability to probe both local structure and heterogeneities, such as phase-coexistence and domain morphologies, has become increasingly important to controlling self-assembly processes, including those at liquid surfaces. The traditional X-ray scattering methods for liquid surfaces, such as specular reflectivity and grazing-incidence diffraction, are not well suited to spatially resolving lateral heterogeneities due to large illuminated footprint. A possible alternative approach is to use scanning transmission X-ray scattering to simultaneously probe local intermolecular structures and heterogeneous domain morphologies on liquid surfaces. To test the feasibilitymore » of this approach, transmission small- and wide-angle X-ray scattering (TSAXS/TWAXS) studies of Langmuir films formed on water meniscus against a vertically immersed hydrophilic Si substrate were recently carried out. First-order diffraction rings were observed in TSAXS patterns from a monolayer of hexagonally packed gold nanoparticles and in TWAXS patterns from a monolayer of fluorinated fatty acids, both as a Langmuir monolayer on water meniscus and as a Langmuir–Blodgett monolayer on the substrate. The patterns taken at multiple spots have been analyzed to extract the shape of the meniscus surface and the ordered-monolayer coverage as a function of spot position. These results, together with continual improvement in the brightness and spot size of X-ray beams available at synchrotron facilities, support the possibility of using scanning-probe TSAXS/TWAXS to characterize heterogeneous structures at liquid surfaces.« less

Cation effect on small phosphonium based ionic liquid electrolytes with high concentrations of lithium salt

NASA Astrophysics Data System (ADS)

Chen, Fangfang; Kerr, Robert; Forsyth, Maria

2018-05-01

Ionic liquid electrolytes with high alkali salt concentrations have displayed some excellent electrochemical properties, thus opening up the field for further improvements to liquid electrolytes for lithium or sodium batteries. Fundamental computational investigations into these high concentration systems are required in order to gain a better understanding of these systems, yet they remain lacking. Small phosphonium-based ionic liquids with high concentrations of alkali metal ions have recently shown many promising results in experimental studies, thereby prompting us to conduct further theoretical exploration of these materials. Here, we conducted a molecular dynamics simulation on four small phosphonium-based ionic liquids with 50 mol. % LiFSI salt, focusing on the effect of cation structure on local structuring and ion diffusional and rotational dynamics—which are closely related to the electrochemical properties of these materials.

A liquid-liquid transition in supercooled aqueous solution related to the HDA-LDA transition

NASA Astrophysics Data System (ADS)

Woutersen, Sander; Ensing, Bernd; Hilbers, Michiel; Zhao, Zuofeng; Angell, C. Austen

2018-03-01

Simulations and theory suggest that the thermodynamic anomalies of water may be related to a phase transition between two supercooled liquid states, but so far this phase transition has not been observed experimentally because of preemptive ice crystallization. We used calorimetry, infrared spectroscopy, and molecular dynamics simulations to investigate a water-rich hydrazinium trifluoroacetate solution in which the local hydrogen bond structure surrounding a water molecule resembles that in neat water at elevated pressure, but which does not crystallize upon cooling. Instead, this solution underwent a sharp, reversible phase transition between two homogeneous liquid states. The hydrogen-bond structures of these two states are similar to those established for high- and low-density amorphous (HDA and LDA) water. Such structural similarity supports theories that predict a similar sharp transition in pure water under pressure if ice crystallization could be suppressed.

Dual-plane ultrasound flow measurements in liquid metals

NASA Astrophysics Data System (ADS)

Büttner, Lars; Nauber, Richard; Burger, Markus; Räbiger, Dirk; Franke, Sven; Eckert, Sven; Czarske, Jürgen

2013-05-01

An ultrasound measurement system for dual-plane, two-component flow velocity measurements especially in opaque liquids is presented. Present-day techniques for measuring local flow structures in opaque liquids disclose considerable drawbacks concerning line-wise measurement of single ultrasound probes. For studying time-varying flow patterns, conventional ultrasound techniques are either limited by time-consuming mechanical traversing or by the sequential operation of single probes. The measurement system presented within this paper employs four transducer arrays with a total of 100 single elements which allows for flow mapping without mechanical traversing. A high frame rate of several 10 Hz has been achieved due to an efficient parallelization scheme using time-division multiplexing realized by a microcontroller-based electronic switching matrix. The functionality and capability of the measurement system are demonstrated on a liquid metal flow at room temperature inside a cube driven by a rotating magnetic field (RMF). For the first time, the primary and the secondary flow have been studied in detail and simultaneously using a configuration with two crossed measurement planes. The experimental data confirm predictions made by numeric simulation. After a sudden switching on of the RMF, inertial oscillations of the secondary flow were observed by means of a time-resolved measurement with a frame rate of 3.4 Hz. The experiments demonstrate that the presented measurement system is able to investigate complex and transient flow structures in opaque liquids. Due to its ability to study the temporal evolution of local flow structures, the measurement system could provide considerable progress for fluid dynamics research, in particular for applications in the food industry or liquid metal technologies.

AB INITIO Molecular Dynamics Simulations on Local Structure and Electronic Properties in Liquid Sb from 913 K to 1193 K

NASA Astrophysics Data System (ADS)

Hao, Qing-Hai; Li, Y. D.; Kong, Xiang-Shan; Liu, C. S.

2013-02-01

Ab initio molecular dynamics simulations on liquid Sb have been carried out at five different temperatures from 913 K to 1193 K. We have investigated the temperature dependence of structure properties including structural factor S(Q), pair correlation function g(r), bond-angle distribution function g3(θ), cluster properties and bond order parameter Q4 and Q6. A shoulder was reproduced in the high wave number side of the first peak in the S(Q) implying that the residual structure units of crystalline Sb remain in liquid Sb. There is a noticeable bend at around 1023 K in the temperature dependence of the first-peak height of S(Q), the cluster properties and bond order parameter Q4, respectively, indicating that an abnormal structural change may occur at 973-1023 K.

Atomic study on the ordered structure in Al melts induced by liquid/substrate interface with Ti solute

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

Zhang, H. L.; Han, Y. F., E-mail: yfhan@sjtu.edu.cn, E-mail: bdsun@sjtu.edu.cn; Zhou, W.

2015-01-26

Atomic ordering in Al melts induced by liquid/substrate interface with Ti solute was investigated by ab initio molecular dynamics simulations and in-situ synchrotron X-ray diffraction. It is predicted that deformed nanoscale ordering Al layers with a rhombohedral-centered hexagonal structure (R3{sup ¯}m space group) instead of the intrinsic fcc structure (Fm3{sup ¯}m space group) form on substrate at temperature above Al liquids. With Al atoms stacking away from the interface, the ordering structure reaches a critical thickness, which inhibits the consecutive stacking of Al atoms on substrates. The locally stacking reconstruction induced by Ti atom relieves the accumulated elastic strain energymore » in ordered Al layers, facilitating fully heterogeneous nucleation on substrate beyond the deformed ordering Al layer around the melting point. The roles of liquid/substrate interface with Ti solute in the physical behavior of heterogeneous nucleation on substrate were discussed.« less

Water: a responsive small molecule.

PubMed

Shultz, Mary Jane; Vu, Tuan Hoang; Meyer, Bryce; Bisson, Patrick

2012-01-17

Unique among small molecules, water forms a nearly tetrahedral yet flexible hydrogen-bond network. In addition to its flexibility, this network is dynamic: bonds are formed or broken on a picosecond time scale. These unique features make probing the local structure of water challenging. Despite the challenges, there is intense interest in developing a picture of the local water structure due to water's fundamental importance in many fields of chemistry. Understanding changes in the local network structure of water near solutes likely holds the key to unlock problems from analyzing parameters that determine the three dimensional structure of proteins to modeling the fate of volatile materials released into the atmosphere. Pictures of the local structure of water are heavily influenced by what is known about the structure of ice. In hexagonal I(h) ice, the most stable form of solid water under ordinary conditions, water has an equal number of donor and acceptor bonds; a kind of symmetry. This symmetric tetrahedral coordination is only approximately preserved in the liquid. The most obvious manifestation of this altered tetrahedral bonding is the greater density in the liquid compared with the solid. Formation of an interface or addition of solutes further modifies the local bonding in water. Because the O-H stretching frequency is sensitive to the environment, vibrational spectroscopy provides an excellent probe for the hydrogen-bond structure in water. In this Account, we examine both local interactions between water and small solutes and longer range interactions at the aqueous surface. Locally, the results suggest that water is not a symmetric donor or acceptor, but rather has a propensity to act as an acceptor. In interactions with hydrocarbons, action is centered at the water oxygen. For soluble inorganic salts, interaction is greater with the cation than the anion. The vibrational spectrum of the surface of salt solutions is altered compared with that of neat water. Studies of local salt-water interactions suggest that the picture of the local water structure and the ion distribution at the surface deduced from the surface vibrational spectrum should encompass both ions of the salt.

Calorimetric evidence for two distinct molecular packing arrangements in stable glasses of indomethacin.

PubMed

Kearns, Kenneth L; Swallen, Stephen F; Ediger, M D; Sun, Ye; Yu, Lian

2009-02-12

Indomethacin glasses of varying stabilities were prepared by physical vapor deposition onto substrates at 265 K. Enthalpy relaxation and the mobility onset temperature were assessed with differential scanning calorimetry (DSC). Quasi-isothermal temperature-modulated DSC was used to measure the reversing heat capacity during annealing above the glass transition temperature Tg. At deposition rates near 8 A/s, scanning DSC shows two enthalpy relaxation peaks and quasi-isothermal DSC shows a two-step change in the reversing heat capacity. We attribute these features to two distinct local packing structures in the vapor-deposited glass, and this interpretation is supported by the strong correlation between the two calorimetric signatures of the glass to liquid transformation. At lower deposition rates, a larger fraction of the sample is prepared in the more stable local packing. The transformation of the vapor-deposited glasses into the supercooled liquid above Tg is exceedingly slow, as much as 4500 times slower than the structural relaxation time of the liquid.

Local structure of molten AuGa 2 under pressure: Evidence for coordination change and planetary implications

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

Kalkan, Bora; Godwal, Budhiram; Raju, Selva Vennila

In situ x-ray diffraction measurements and inverse Monte Carlo simulations of pair distribution functions were used to characterize the local structure of molten AuGa 2 up to 16 GPa and 940 K. Our results document systematic changes in liquid structure due to a combination of bond compression and coordination increase. Empirical potential structure refinement shows the first-neighbor coordination of Ga around Au and of Au around Ga to increase from about 8 to 10 and 4 to 5, respectively between 0 and 16 GPa, and the inferred changes in liquid structure can explain the observed melting-point depression of AuGa2 upmore » to 5 GPa. As intermetallic AuGa 2 is an analogue for metallic SiO 2 at much higher pressures, our results imply that structural changes documented for non-metallic silicate melts below 100 GPa are followed by additional coordination changes in the metallic state at pressures in the 0.2–1 TPa range achieved inside large planets.« less

Local structure of molten AuGa 2 under pressure: Evidence for coordination change and planetary implications

DOE PAGES

Kalkan, Bora; Godwal, Budhiram; Raju, Selva Vennila; ...

2018-05-01

In situ x-ray diffraction measurements and inverse Monte Carlo simulations of pair distribution functions were used to characterize the local structure of molten AuGa 2 up to 16 GPa and 940 K. Our results document systematic changes in liquid structure due to a combination of bond compression and coordination increase. Empirical potential structure refinement shows the first-neighbor coordination of Ga around Au and of Au around Ga to increase from about 8 to 10 and 4 to 5, respectively between 0 and 16 GPa, and the inferred changes in liquid structure can explain the observed melting-point depression of AuGa2 upmore » to 5 GPa. As intermetallic AuGa 2 is an analogue for metallic SiO 2 at much higher pressures, our results imply that structural changes documented for non-metallic silicate melts below 100 GPa are followed by additional coordination changes in the metallic state at pressures in the 0.2–1 TPa range achieved inside large planets.« less

Atomistic cluster alignment method for local order mining in liquids and glasses

NASA Astrophysics Data System (ADS)

Fang, X. W.; Wang, C. Z.; Yao, Y. X.; Ding, Z. J.; Ho, K. M.

2010-11-01

An atomistic cluster alignment method is developed to identify and characterize the local atomic structural order in liquids and glasses. With the “order mining” idea for structurally disordered systems, the method can detect the presence of any type of local order in the system and can quantify the structural similarity between a given set of templates and the aligned clusters in a systematic and unbiased manner. Moreover, population analysis can also be carried out for various types of clusters in the system. The advantages of the method in comparison with other previously developed analysis methods are illustrated by performing the structural analysis for four prototype systems (i.e., pure Al, pure Zr, Zr35Cu65 , and Zr36Ni64 ). The results show that the cluster alignment method can identify various types of short-range orders (SROs) in these systems correctly while some of these SROs are difficult to capture by most of the currently available analysis methods (e.g., Voronoi tessellation method). Such a full three-dimensional atomistic analysis method is generic and can be applied to describe the magnitude and nature of noncrystalline ordering in many disordered systems.

MD simulation study of the diffusion and local structure of n-alkanes in liquid and supercritical methanol at infinite dilution.

PubMed

Feng, Huajie; Gao, Wei; Su, Li; Sun, Zhenfan; Chen, Liuping

2017-06-01

The diffusion coefficients of 14 n-alkanes (ranging from methane to n-tetradecane) in liquid and supercritical methanol at infinite dilution (at a pressure of 10.5 MPa and at temperatures of 299 K and 515 K) were deduced via molecular dynamics simulations. Values for the radial distribution function, coordination number, and number of hydrogen bonds were then calculated to explore the local structure of each fluid. The flexibility of the n-alkane (as characterized by the computed dihedral distribution, end-to-end distance, and radius of gyration) was found to be a major influence and hydrogen bonding to be a minor influence on the local structure. Hydrogen bonding reduces the flexibility of the n-alkane, whereas increasing the temperature enhances its flexibility, with temperature having a greater effect than hydrogen bonding on flexibility. Graphical abstract The flexibility of the alkane is a major influence and the hydrogen bonding is a minor influence on the first solvation shell; the coordination numbers of long-chain n-alkanes in the first solvation shell are rather low.

Experimental study on spatio-temporal behavior of a single particle forming a particle accumulation structure (PAS) in half-zone liquid bridge

NASA Astrophysics Data System (ADS)

Oba, Takeru; Ueno, Ichiro; Kaneko, Toshihiro

2017-11-01

We focus on particle behavior due to thermocapillary-driven convection in a half-zone liquid bridge of high-Prandtl number fluid. It has been known that the suspended particles exhibit a unique solid-like structure known as 'particle accumulation structure (PAS)' in a rotating frame of reference with traveling-type hydrothermal wave. It is said that PAS is caused by interaction between particles and the free surface of a half-zone liquid bridge. Such structures arise even under small Stokes number conditions. When observing PAS two-dimensionally, it looks like a closed single string, but the actual movement of particles is different. Therefore we employ three-dimensional particle tracking velocimetry to the half-zone liquid bridge of 2.5 mm in radius and 1.7 mm in height, and detect the particle behaviors close to the free surface. We explain the spatio-temporal correlation between the solid-like global structure of PAS and the local particle motions, and make comparisons with proposed physical models of PAS formation.

Small angle neutron scattering from 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids ([Cnmim][PF6], n=4, 6, and 8)

NASA Astrophysics Data System (ADS)

Hardacre, Christopher; Holbrey, John D.; Mullan, Claire L.; Youngs, Tristan G. A.; Bowron, Daniel T.

2010-08-01

The presence of local anisotropy in the bulk, isotropic, and ionic liquid phases—leading to local mesoscopic inhomogeneity—with nanoscale segregation and expanding nonpolar domains on increasing the length of the cation alkyl-substituents has been proposed on the basis of molecular dynamics (MD) simulations. However, there has been little conclusive experimental evidence for the existence of intermediate mesoscopic structure between the first/second shell correlations shown by neutron scattering on short chain length based materials and the mesophase structure of the long chain length ionic liquid crystals. Herein, small angle neutron scattering measurements have been performed on selectively H/D-isotopically substituted 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids with butyl, hexyl, and octyl substituents. The data show the unambiguous existence of a diffraction peak in the low-Q region for all three liquids which moves to longer distances (lower Q), sharpens, and increases in intensity with increasing length of the alkyl substituent. It is notable, however, that this peak occurs at lower values of Q (longer length scale) than predicted in any of the previously published MD simulations of ionic liquids, and that the magnitude of the scattering from this peak is comparable with that from the remainder of the amorphous ionic liquid. This strongly suggests that the peak arises from the second coordination shells of the ions along the vector of alkyl-chain substituents as a consequence of increasing the anisotropy of the cation, and that there is little or no long-range correlated nanostructure in these ionic liquids.

Relaxation processes of the liquid crystal ME6N in the isotropic phase studied by Raman scattering experiments

NASA Astrophysics Data System (ADS)

Giorgini, Maria Grazia; Arcioni, Alberto; Polizzi, Ciro; Musso, Maurizio; Ottaviani, Paolo

2004-03-01

We have investigated the Raman profiles of the ν(C≡N) and ν(C=O) vibrational modes of the nematic liquid crystal ME6N (4-cyanophenyl-4'-hexylbenzoate) in the isotropic phase at different temperatures and used them as probes of the dynamics and structural organization of this liquid. The vibrational time correlation functions of the ν(C≡N) mode, rather adequately interpreted within the assumption of exponential modulation function (the Kubo-Rothschild theory), indicate that the system experiences an intermediate dynamical regime that gets only slightly faster with increasing temperature. However, this theory fails in predicting the non-exponential behavior that the time correlation functions manifest in the long time range (t>3 ps). For this reason we have additionally approached the interpretation of vibrational correlation functions in terms of the theory formulated by Rothschild and co-workers for locally structured liquids. The application of this theory reveals that the molecular dynamics in this liquid crystal in the isotropic phase is that deriving from a distribution of differently sized clusters, which narrows as the temperature increases. Even at the highest temperature reached in this study (87 °C above the nematic-isotropic transition), the liquid has not yet achieved the structure of the simple liquid and the dynamics has not reached the limit of the single channel process. The vibrational and orientational relaxations occur in very different time scales. The temperature independence of the orientational dynamics in the whole range from 55 °C to 135 °C has been referred to the nonhydrodynamic behavior of the system, arising when local pseudonematic structures persist for times longer than the orientational relaxation. The occurrence of the process of resonant vibrational energy transfer between the C=O groups of adjacent molecules has been revealed in the isotropic phase by a slightly positive Raman noncoincidence effect in the band associated with the ν(C=O) mode. A qualitative interpretation is tentatively given in terms of partial cancellation of contributions deriving from structures having opposite orientations of their C=O groups.

Perspective: Echoes in 2D-Raman-THz spectroscopy.

PubMed

Hamm, Peter; Shalit, Andrey

2017-04-07

Recently, various spectroscopic techniques have been developed, which can measure the 2D response of the inter-molecular degrees of freedom of liquids in the THz regime. By employing hybrid Raman-THz pulse sequences, the inherent experimental problems of 2D-Raman spectroscopy are circumvented completely, culminating in the recent measurement of the 2D-Raman-THz responses of water and aqueous salt solutions. This review article focuses on the possibility to observe echoes in such experiments, which would directly reveal the inhomogeneity of the typically extremely blurred THz bands of liquids, and hence the heterogeneity of local structures that are transiently formed, in particular, in a hydrogen-bonding liquid such as water. The generation mechanisms of echoes in 2D-Raman-THz spectroscopy are explained, which differ from those in "conventional" 2D-IR spectroscopy in a subtle but important manner. Subsequently, the circumstances are discussed, under which echoes are expected, revealing a physical picture of the information content of an echo. That is, the echo decay reflects the lifetime of local structures in the liquid on a length scale that equals the delocalization length of the intermolecular modes. Finally, recent experimental results are reviewed from an echo perspective.

Tunable hybrid optical modes in a bounded cholesteric liquid crystal with a twist defect

NASA Astrophysics Data System (ADS)

Pyatnov, Maxim V.; Vetrov, Stepan Ya.; Timofeev, Ivan V.

2018-03-01

Coupling between the defect mode of a cholesteric liquid crystal and the localized mode of a cholesteric liquid crystal-phase plate-metal structure is theoretically demonstrated. It is shown that the transmittance spectrum can be tuned by changing the twist-defect angle and helix pitch, which are governed by external factors. The spectra for different circular polarizations of the incident light are different; specifically, at the nondiffracting polarization, there is no defect-mode transmittance peak.

Segregation of liquid crystal mixtures in topological defects

DOE PAGES

Rahimi, Mohammad; Ramezani-Dakhel, Hadi; Zhang, Rui; ...

2017-04-28

The structure and physical properties of liquid crystal (LC) mixtures are a function of composition, and small changes can have pronounced effects on observables, such as phase-transition temperatures. Traditionally, LC mixtures have been assumed to be compositionally homogenous. The results of chemically detailed simulations presented here show that this is not the case; pronounced deviations of the local order from that observed in the bulk at defects and interfaces lead to significant compositional segregation effects. More specifically, two disclination lines are stabilized in this work by introducing into a nematic liquid crystal mixture a cylindrical body that exhibits perpendicular anchoring.more » Here, it is found that the local composition deviates considerably from that of the bulk at the interface with the cylinder and in the defects, thereby suggesting new assembly and synthetic strategies that may capitalize on the unusual molecular environment provided by liquid crystal mixtures.« less

Surface dynamics and mechanics in liquid crystal polymer coatings

NASA Astrophysics Data System (ADS)

Liu, Danqing; Broer, Dirk J.

2015-03-01

Based on liquid crystal networks we developed `smart' coatings with responsive surface topographies. Either by prepatterning or by the formation of self-organized structures they can be switched on and off in a pre-designed manner. Here we provide an overview of our methods to generate coatings that form surface structures upon the actuation by light. The coating oscillates between a flat surface and a surface with pre-designed 3D micro-patterns by modulating a light source. With recent developments in solid state lighting, light is an attractive trigger medium as it can be integrated in a device for local control or can be used remotely for flood or localized exposure. The basic principle of formation of surface topographies is based on the change of molecular organization in ordered liquid crystal polymer networks. The change in order leads to anisotropic dimensional changes with contraction along the director and expansion to the two perpendicular directions and an increase in volume by the formation of free volume. These two effects work in concert to provide local expansion and contraction in the coating steered by the local direction of molecular orientation. The surface deformation, expressed as the height difference between the activated regions and the non-activated regions divided by the initial film thickness, is of the order of 20%. Switching occurs immediately when the light is switched `on' and `off' and takes several tens of seconds.

Solar steam generation by heat localization.

PubMed

Ghasemi, Hadi; Ni, George; Marconnet, Amy Marie; Loomis, James; Yerci, Selcuk; Miljkovic, Nenad; Chen, Gang

2014-07-21

Currently, steam generation using solar energy is based on heating bulk liquid to high temperatures. This approach requires either costly high optical concentrations leading to heat loss by the hot bulk liquid and heated surfaces or vacuum. New solar receiver concepts such as porous volumetric receivers or nanofluids have been proposed to decrease these losses. Here we report development of an approach and corresponding material structure for solar steam generation while maintaining low optical concentration and keeping the bulk liquid at low temperature with no vacuum. We achieve solar thermal efficiency up to 85% at only 10 kW m(-2). This high performance results from four structure characteristics: absorbing in the solar spectrum, thermally insulating, hydrophilic and interconnected pores. The structure concentrates thermal energy and fluid flow where needed for phase change and minimizes dissipated energy. This new structure provides a novel approach to harvesting solar energy for a broad range of phase-change applications.

Relationship between structural and dynamic properties of Al-rich Al-Cu melts: Beyond the Stokes-Einstein relation

NASA Astrophysics Data System (ADS)

Jakse, N.; Pasturel, A.

2016-12-01

We perform ab initio molecular dynamics simulations to study structural and transport properties in liquid A l1 -xC ux alloys, with copper composition x ≤0.4 , in relation to the applicability of the Stokes-Einstein (SE) equation in these melts. To begin, we find that self-diffusion coefficients and viscosity are composition dependent, while their temperature dependence follows an Arrhenius-type behavior, except for x =0.4 at low temperature. Then, we find that the applicability of the SE equation is also composition dependent, and its breakdown in the liquid regime above the liquidus temperature can be related to different local ordering around each species. In this case, we emphasize the difficulty of extracting effective atomic radii from interatomic distances found in liquid phases, but we see a clear correlation between transport properties and local ordering described through the structural entropy approximated by the two-body contribution. We use these findings to reformulate the SE equation within the framework of Rosenfeld's scaling law in terms of partial structural entropies, and we demonstrate that the breakdown of the SE relation can be related to their temperature dependence. Finally, we also use this framework to derive a simple relation between the ratio of the self-diffusivities of the components and the ratio of their partial structural entropies.

Unveiling the complex network of interactions in Ionic Liquids: a combined EXAFS and Molecular Dynamics approach

NASA Astrophysics Data System (ADS)

Serva, A.; Migliorati, V.; Lapi, A.; D'Angelo, P.

2016-05-01

The structural properties of geminal dicationic ionic liquids ([Cn (mim)2]Br2)/water mixtures have been investigated by means of extended X-ray absorption fine structure (EXAFS) spectroscopy and Molecular Dynamics (MD) simulations. This synergic approach allowed us to assess the reliability of the MD results and to provide accurate structural information about the first coordination shell of the Br- ion. We found that the local environment around the anion changes as a function of the water concentration, while it is the same independently from the length of the bridge-alkyl chain. Moreover, as regards the long-range structural organization, no tail-tail aggregation occurs with increasing alkyl chain length.

EPR investigation of local structure for [Mn(H 2O) 6] 2+ cluster in [M(H 2O) 6]XCl 6:Mn 2+ (M = Zn, Mg, Cd, Ca; X = Pt, Sn) systems at different temperatures

NASA Astrophysics Data System (ADS)

Tian, Wen-Yan; Kuang, Xiao-Yu; Li, Hui-Fang; Li, Yan-Fang; Ying-Li

2009-01-01

A theoretical method for studying the inter-relation between the local structure and EPR spectra is established by diagonalizing the complete energy matrices. For [M(H 2O) 6]XCl 6:Mn 2+ (M = Zn, Mg, Cd, Ca; X = Pt, Sn) systems, the calculated results demonstrate that the local structures around the octahedral Mn 2+ centers in the doped systems are very similar despite of the host crystals being different. Furthermore, it is shown that the EPR zero-field parameter D depends simultaneously on the local structure parameters R and θ while ( a - F) depends mainly on R, whether the doped systems are at liquid-nitrogen temperature or room temperature.

Decrease in electrical resistivity on depletion of islands of mobility during aging of a bulk metal glass

NASA Astrophysics Data System (ADS)

Aji, Daisman P. B.; Johari, G. P.

2018-04-01

The effect of structural relaxation on electrical resistivity, ρglass, of strain-free Zr46.75Ti8.25Cu7.5Ni10Be27.5 bulk metallic glass was studied during isothermal aging at several temperatures, Tas. Since cooling of a liquid metal increases its resistivity ρliq, one expects ρglass to increase on aging toward ρliq at T = Ta. Instead, ρglass decreased non-exponentially with the aging time. The activation energy of aging kinetics is 189 kJ mol-1, which is higher than the activation energy of the Johari-Goldstein (JG) relaxation. After considering the sample's contraction, phase separation, and crystallization as possible causes of the decrease in ρglass, we attribute the decrease to depletion of islands of atomic mobility, soft spots, or static heterogeneity. Vibrations of the atoms in these local (loosely packed) regions and in the region's interfacial area contribute to electron scattering. As these deplete on aging, the contribution decreases and ρglass decreases, with a concomitant decrease in macroscopic volume, enthalpy, and entropy (V, H, and S). Local regions of faster mobility also decrease on cooling as V, H, and S of a liquid decrease, but structure fluctuations dominate electron scattering of a liquid metal and ρliq increases effectively according to the Ziman-Nagel theory for a homogenously disordered structure. Whether depletion of such local regions initiates the structural relaxation of a glass, or vice versa, may be resolved by finding a glass that physically ages but shows no JG relaxation.

Structure factor and radial distribution function of some liquid lanthanides using charged hard sphere

NASA Astrophysics Data System (ADS)

Patel, H. P.; Sonvane, Y. A.; Thakor, P. B.

2017-05-01

The structure factor S(q) and radial distribution function g(r) play vital role to study the various structural properties like electronic, dynamic, magnetic etc. The present paper deals with the structural studies of foresaid properties using our newly constructed parameter free model potential with the Charged Hard Sphere (CHS) approximation. The local field correction due to Sarkar et al. is used to incorporate exchange and correlation among the conduction electrons in dielectric screening. Here we report the S(q) and g(r) for some liquid lanthanides viz: La, Ce, Pr, Nd and Eu. Present computed results are compared with the available experimental data. Lastly we found that our parameter free model potential successfully explains the structural propertiesof4fliquidlanthanides.

Investigations of the local environment and macroscopic alignment behavior of novel polymerizeable lyotropic liquid crystals using nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Juang, Elizabeth

In this dissertation, a variety of NMR techniques were used to explore the local environment of novel polymerizeable lyotropic liquid crystals (LLC). The LLC monomers examined in this study self-assemble in the presence of a small amount of water to form uniform, nanometer-scale tubes with aqueous interiors. The phase architecture is retained upon photopolymerization to yield the resulting nanoporous material. By dissolving reactive precursors into the aqueous phase, well- structured nancomposite materials have also been formed. Proposed uses for these novel polymerizeable LLCs are as porous water filtration membranes, as heterogeneous organic catalysts, and as nanocomposite materials for load bearing and optical applications. In order to better exploit these polymerizeable LLCs for materials development, the local environment must be examined. In addition, the macroscopic orientation of these materials remains an important step in their advancement. Various NMR studies were conducted on these novel LLCs. NMR T1 relaxation measurements were conducted to elucidate the local environment and dynamics of the 23Na counterions located inside the aqueous channels. 2H NMR line shape analyses were used to characterize the local structure and dynamics near the hydrophilic headgroup. 29 Si NMR studies were performed on silica nanocomposites formed with these LLC structures. Finally, the macroscopic alignment behavior of these novel LLCs using shear and magnetic fields was examined.

Isobaric first-principles molecular dynamics of liquid water with nonlocal van der Waals interactions

NASA Astrophysics Data System (ADS)

Miceli, Giacomo; de Gironcoli, Stefano; Pasquarello, Alfredo

2015-01-01

We investigate the structural properties of liquid water at near ambient conditions using first-principles molecular dynamics simulations based on a semilocal density functional augmented with nonlocal van der Waals interactions. The adopted scheme offers the advantage of simulating liquid water at essentially the same computational cost of standard semilocal functionals. Applied to the water dimer and to ice Ih, we find that the hydrogen-bond energy is only slightly enhanced compared to a standard semilocal functional. We simulate liquid water through molecular dynamics in the NpH statistical ensemble allowing for fluctuations of the system density. The structure of the liquid departs from that found with a semilocal functional leading to more compact structural arrangements. This indicates that the directionality of the hydrogen-bond interaction has a diminished role as compared to the overall attractions, as expected when dispersion interactions are accounted for. This is substantiated through a detailed analysis comprising the study of the partial radial distribution functions, various local order indices, the hydrogen-bond network, and the selfdiffusion coefficient. The explicit treatment of the van der Waals interactions leads to an overall improved description of liquid water.

Microscopic structure of liquid 1-1-1-2-tetrafluoroethane (R134a) from Monte Carlo simulation.

PubMed

Do, Hainam; Wheatley, Richard J; Hirst, Jonathan D

2010-10-28

1-1-1-2-tetrafluoroethane (R134a) is one of the most commonly used refrigerants. Its thermophysical properties are important for evaluating the performance of refrigeration cycles. These can be obtained via computer simulation, with an insight into the microscopic structure of the liquid, which is not accessible to experiment. In this paper, vapour-liquid equilibrium properties of R134a and its liquid microscopic structure are investigated using coupled-decoupled configurational-bias Monte Carlo simulation in the Gibbs ensemble, with a recent potential [J. Phys. Chem. B 2009, 113, 178]. We find that the simulations agree well with the experimental data, except at the vicinity of the critical region. Liquid R134a packs like liquid argon, with a coordination number in the first solvation shell of 12 at 260 K. The nearest neighbours prefer to be localized in three different spaces around the central molecule, in such a manner that the dipole moments are in a parallel alignment. Analysis of the pair interaction energy shows clear association of R134a molecules, but no evidence for C-HF type hydrogen bonding is found. The above findings should be of relevance to a broad range of fluoroalkanes.

Four-dimensional Printing of Liquid Crystal Elastomers.

PubMed

Ambulo, Cedric P; Burroughs, Julia J; Boothby, Jennifer M; Kim, Hyun; Shankar, M Ravi; Ware, Taylor H

2017-10-25

Three-dimensional structures capable of reversible changes in shape, i.e., four-dimensional-printed structures, may enable new generations of soft robotics, implantable medical devices, and consumer products. Here, thermally responsive liquid crystal elastomers (LCEs) are direct-write printed into 3D structures with a controlled molecular order. Molecular order is locally programmed by controlling the print path used to build the 3D object, and this order controls the stimulus response. Each aligned LCE filament undergoes 40% reversible contraction along the print direction on heating. By printing objects with controlled geometry and stimulus response, magnified shape transformations, for example, volumetric contractions or rapid, repetitive snap-through transitions, are realized.

Wetting, meniscus structure, and capillary interactions of microspheres bound to a cylindrical liquid interface.

PubMed

Kim, Paul Y; Dinsmore, Anthony D; Hoagland, David A; Russell, Thomas P

2018-03-14

Wetting, meniscus structure, and capillary interactions for polystyrene microspheres deposited on constant curvature cylindrical liquid interfaces, constructed from nonvolatile ionic or oligomeric liquids, were studied by optical interferometry and optical microscopy. The liquid interface curvature resulted from the preferential wetting of finite width lines patterned onto planar silicon substrates. Key variables included sphere diameter, nominal (or average) contact angle, and deviatoric interfacial curvature. Menisci adopted the quadrupolar symmetry anticipated by theory, with interfacial deformation closely following predicted dependences on sphere diameter and nominal contact angle. Unexpectedly, the contact angle was not constant locally around the contact line, the nominal contact angle varied among seemingly identical spheres, and the maximum interface deviation did not follow the predicted dependence on deviatoric interfacial curvature. Instead, this deviation was up to an order-of-magnitude larger than predicted. Trajectories of neighboring microspheres visually manifested quadrupole-quadrupole interactions, eventually producing square sphere packings that foreshadow interfacial assembly as a potential route to hierarchical 2D particle structures.

Molecular dynamics study of response of liquid N,N-dimethylformamide to externally applied electric field using a polarizable force field

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

Gao, Weimin; Niu, Haitao; Lin, Tong

2014-01-28

The behavior of Liquid N,N-dimethylformamide subjected to a wide range of externally applied electric fields (from 0.001 V/nm to 1 V/nm) has been investigated through molecular dynamics simulation. To approach the objective the AMOEBA polarizable force field was extended to include the interaction of the external electric field with atomic partial charges and the contribution to the atomic polarization. The simulation results were evaluated with quantum mechanical calculations. The results from the present force field for the liquid at normal conditions were compared with the experimental and molecular dynamics results with non-polarizable and other polarizable force fields. The uniform externalmore » electric fields of higher than 0.01 V/nm have a significant effect on the structure of the liquid, which exhibits a variation in numerous properties, including molecular polarization, local cluster structure, rotation, alignment, energetics, and bulk thermodynamic and structural properties.« less

A liquid-liquid transition in supercooled aqueous solution related to the HDA-LDA transition.

PubMed

Woutersen, Sander; Ensing, Bernd; Hilbers, Michiel; Zhao, Zuofeng; Angell, C Austen

2018-03-09

Simulations and theory suggest that the thermodynamic anomalies of water may be related to a phase transition between two supercooled liquid states, but so far this phase transition has not been observed experimentally because of preemptive ice crystallization. We used calorimetry, infrared spectroscopy, and molecular dynamics simulations to investigate a water-rich hydrazinium trifluoroacetate solution in which the local hydrogen bond structure surrounding a water molecule resembles that in neat water at elevated pressure, but which does not crystallize upon cooling. Instead, this solution underwent a sharp, reversible phase transition between two homogeneous liquid states. The hydrogen-bond structures of these two states are similar to those established for high- and low-density amorphous (HDA and LDA) water. Such structural similarity supports theories that predict a similar sharp transition in pure water under pressure if ice crystallization could be suppressed. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Diffusion and viscosity of liquid tin: Green-Kubo relationship-based calculations from molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Mouas, Mohamed; Gasser, Jean-Georges; Hellal, Slimane; Grosdidier, Benoît; Makradi, Ahmed; Belouettar, Salim

2012-03-01

Molecular dynamics (MD) simulations of liquid tin between its melting point and 1600 °C have been performed in order to interpret and discuss the ionic structure. The interactions between ions are described by a new accurate pair potential built within the pseudopotential formalism and the linear response theory. The calculated structure factor that reflects the main information on the local atomic order in liquids is compared to diffraction measurements. Having some confidence in the ability of this pair potential to give a good representation of the atomic structure, we then focused our attention on the investigation of the atomic transport properties through the MD computations of the velocity autocorrelation function and stress autocorrelation function. Using the Green-Kubo formula (for the first time to our knowledge for liquid tin) we determine the macroscopic transport properties from the corresponding microscopic time autocorrelation functions. The selfdiffusion coefficient and the shear viscosity as functions of temperature are found to be in good agreement with the experimental data.

Nuclear quantum effects on structure and transport properties of dense liquid helium

NASA Astrophysics Data System (ADS)

Kang, Dongdong; Dai, Jiayu; Yuan, Jianmin

2015-11-01

Transport properties of dense liquid helium under the conditions of planet's core and cool atmosphere of white dwarfs are important for determining the structure and evolution of these astrophysical objects. We have investigated these properties of dense liquid helium by using the improved centroid path-integral simulations combined with density functional theory. The results show that with the inclusion of nuclear quantum effects (NQEs), the self-diffusion is largely higher while the shear viscosity is notably lower than the results of without the inclusion of NQEs due to the lower collision cross sections even when the NQEs have little effects on the static structures. The potential surface of helium atom along the simulation trajectory is quite different between MD and PIMD simulations. We have shown that the quantum nuclear character induces complex behaviors for ionic transport properties of dense liquid helium. NQEs bring more fluctuations of local electronic density of states than the classical treatment. Therefore, in order to construct more reasonable structure and evolution model for the planets and WDs, NQEs must be reconsidered when calculating the transport properties at certain temperature and density conditions.

From Glass Formation to Icosahedral Ordering by Curving Three-Dimensional Space.

PubMed

Turci, Francesco; Tarjus, Gilles; Royall, C Patrick

2017-05-26

Geometric frustration describes the inability of a local molecular arrangement, such as icosahedra found in metallic glasses and in model atomic glass formers, to tile space. Local icosahedral order, however, is strongly frustrated in Euclidean space, which obscures any causal relationship with the observed dynamical slowdown. Here we relieve frustration in a model glass-forming liquid by curving three-dimensional space onto the surface of a 4-dimensional hypersphere. For sufficient curvature, frustration vanishes and the liquid "freezes" in a fully icosahedral structure via a sharp "transition." Frustration increases upon reducing the curvature, and the transition to the icosahedral state smoothens while glassy dynamics emerge. Decreasing the curvature leads to decoupling between dynamical and structural length scales and the decrease of kinetic fragility. This sheds light on the observed glass-forming behavior in Euclidean space.

Topological Switching and Orbiting Dynamics of Colloidal Spheres Dressed with Chiral Nematic Solitons

PubMed Central

Porenta, T.; Čopar, S.; Ackerman, P. J.; Pandey, M. B.; Varney, M. C. M.; Smalyukh, I. I.; Žumer, S.

2014-01-01

Metastable configurations formed by defects, inclusions, elastic deformations and topological solitons in liquid crystals are a promising choice for building photonic crystals and metamaterials with a potential for new optical applications. Local optical modification of the director or introduction of colloidal inclusions into a moderately chiral nematic liquid crystal confined to a homeotropic cell creates localized multistable chiral solitons. Here we induce solitons that “dress” the dispersed spherical particles treated for tangential degenerate boundary conditions, and perform controlled switching of their state using focused optical beams. Two optically switchable distinct metastable states, toron and hopfion, bound to colloidal spheres into structures with different topological charges are investigated. Their structures are examined using Q-tensor based numerical simulations and compared to the profiles reconstructed from the experiments. A topological explanation of observed multistability is constructed. PMID:25477195

Topological switching and orbiting dynamics of colloidal spheres dressed with chiral nematic solitons.

PubMed

Porenta, T; Copar, S; Ackerman, P J; Pandey, M B; Varney, M C M; Smalyukh, I I; Žumer, S

2014-12-05

Metastable configurations formed by defects, inclusions, elastic deformations and topological solitons in liquid crystals are a promising choice for building photonic crystals and metamaterials with a potential for new optical applications. Local optical modification of the director or introduction of colloidal inclusions into a moderately chiral nematic liquid crystal confined to a homeotropic cell creates localized multistable chiral solitons. Here we induce solitons that "dress" the dispersed spherical particles treated for tangential degenerate boundary conditions, and perform controlled switching of their state using focused optical beams. Two optically switchable distinct metastable states, toron and hopfion, bound to colloidal spheres into structures with different topological charges are investigated. Their structures are examined using Q-tensor based numerical simulations and compared to the profiles reconstructed from the experiments. A topological explanation of observed multistability is constructed.

Optimal design of porous structures for the fastest liquid absorption.

PubMed

Shou, Dahua; Ye, Lin; Fan, Jintu; Fu, Kunkun

2014-01-14

Porous materials engineered for rapid liquid absorption are useful in many applications, including oil recovery, spacecraft life-support systems, moisture management fabrics, medical wound dressings, and microfluidic devices. Dynamic absorption in capillary tubes and porous media is driven by the capillary pressure, which is inversely proportional to the pore size. On the other hand, the permeability of porous materials scales with the square of the pore size. The dynamic competition between these two superimposed mechanisms for liquid absorption through a heterogeneous porous structure may lead to an overall minimum absorption time. In this work, we explore liquid absorption in two different heterogeneous porous structures [three-dimensional (3D) circular tubes and porous layers], which are composed of two sections with variations in radius/porosity and height. The absorption time to fill the voids of porous constructs is expressed as a function of radius/porosity and height of local sections, and the absorption process does not follow the classic Washburn's law. Under given height and void volume, these two-section structures with a negative gradient of radius/porosity against the absorption direction are shown to have faster absorption rates than control samples with uniform radius/porosity. In particular, optimal structural parameters, including radius/porosity and height, are found that account for the minimum absorption time. The liquid absorption in the optimized porous structure is up to 38% faster than in a control sample. The results obtained can be used a priori for the design of porous structures with excellent liquid management property in various fields.

Relating dynamics of model unentangled, crystallizable polymeric liquids to their local structure

NASA Astrophysics Data System (ADS)

Nguyen, Hong T.; Hoy, Robert S.

We study the liquid-state dynamics of a recently developed, crystallizable bead-spring polymer model. The model possesses a single ground state (NCP, wherein monomers close-pack and chains are nematically aligned) for all finite bending stiffnesses kb, but the solid morphologies formed under cooling vary strongly with kb, varying from NCP to amorphous. We find that systems with kb producing amorphous order are good glass-formers exhibiting the classic Vogel-Fulcher slowdown with decreasing temperature T. In contrast, systems with kb producing crystalline solids exhibit a simpler dynamics when kb is small. Larger kb produce more complex dynamics, but these are associated with the existence of an intermediate nematic liquid rather than glassy slowdown. We relate these differences to local, cluster-level structure measured via TCC analyses. Formation propensities and lifetimes of various clusters (associated with amorphous or crystalline order) vary strongly with kb and T. We relate these differences to those measured by the self-intermediate scattering function and other macroscopic measures of dynamics. Our results should aid in understanding the competition between crystallization and glass-formation in synthetic polymers.

Structural features of small benzene clusters (C6H6)n (n ≤ 30) as investigated with the all-atom OPLS potential.

PubMed

Takeuchi, Hiroshi

2012-10-18

The structures of the simplest aromatic clusters, benzene clusters (C(6)H(6))(n), are not well elucidated. In the present study, benzene clusters (C(6)H(6))(n) (n ≤ 30) were investigated with the all-atom optimized parameters for liquid simulation (OPLS) potential. The global minima and low-lying minima of the benzene clusters were searched with the heuristic method combined with geometrical perturbations. The structural features and growth sequence of the clusters were examined by carrying out local structure analyses and structural similarity evaluation with rotational constants. Because of the anisotropic interaction between the benzene molecules, the local structures consisting of 13 molecules are considerably deviated from regular icosahedron, and the geometries of some of the clusters are inconsistent with the shapes constructed by the interior molecules. The distribution of the angle between the lines normal to two neighboring benzene rings is anisotropic in the clusters, whereas that in the liquid benzene is nearly isotropic. The geometries and energies of the low-lying configurations and the saddle points between them suggest that most of the configurations previously detected in supersonic expansions take different orientations for one to four neighboring molecules.

Molecular dynamics simulations on the local order of liquid and amorphous ZnTe

NASA Astrophysics Data System (ADS)

Rino, José Pedro; Borges, Denilson; Mota, Rita C.; Silva, Maurício A. P.

2008-05-01

Molecular dynamics studies of structural and dynamical correlations of molten and vitreous states under several conditions of density and temperature were performed. We use an effective recently proposed interatomic potential, consisting of two- and three-body covalent interactions which has successfully described the structural, dynamical, and structural phase transformation induced by pressure in ZnTe [D. S. Borges and J. P. Rino, Phys. Rev. B 72, 014107 (2005)]. The two-body term of the interaction potential consists of Coulomb interaction resulting from charge transfer, steric repulsion due to atomic sizes, charge-dipole interaction to include the effect of electronic polarizability of anions, and dipole-dipole (van der Waals) interactions. The three-body covalent term is a modification of the Stillinger-Weber potential. Molecular dynamics simulations in isobaric-isenthalpic ensemble have been performed for systems amounting to 4096 and 64 000 particles. Starting from a crystalline zinc-blende (ZB) structure, the system is initially heated until a very homogeneous liquid is obtained. The vitreous zinc telluride phase is attained by cooling the liquid at sufficiently fast cooling rates, while slower cooling rates lead to a disordered ZB crystalline structure. Two- and three-body correlations for the liquid and vitreous phases are analyzed through pair distribution functions, static structure factors, and bond angle distributions. In particular, the neutron static structure factor for the liquid phase is in very good agreement with both the reported experimental data and first-principles simulations.

Pressure-induced structural change in liquid GaIn eutectic alloy.

PubMed

Yu, Q; Ahmad, A S; Ståhl, K; Wang, X D; Su, Y; Glazyrin, K; Liermann, H P; Franz, H; Cao, Q P; Zhang, D X; Jiang, J Z

2017-04-25

Synchrotron x-ray diffraction reveals a pressure induced crystallization at about 3.4 GPa and a polymorphic transition near 10.3 GPa when compressed a liquid GaIn eutectic alloy up to ~13 GPa at room temperature in a diamond anvil cell. Upon decompression, the high pressure crystalline phase remains almost unchanged until it transforms to the liquid state at around 2.3 GPa. The ab initio molecular dynamics calculations can reproduce the low pressure crystallization and give some hints on the understanding of the transition between the liquid and the crystalline phase on the atomic level. The calculated pair correlation function g(r) shows a non-uniform contraction reflected by the different compressibility between the short (1st shell) and the intermediate (2nd to 4th shells). It is concluded that the pressure-induced liquid-crystalline phase transformation likely arises from the changes in local atomic packing of the nearest neighbors as well as electronic structures at the transition pressure.

Theoretical and Experimental Study of Bacterial Colony Growth in 3D

NASA Astrophysics Data System (ADS)

Shao, Xinxian; Mugler, Andrew; Nemenman, Ilya

2014-03-01

Bacterial cells growing in liquid culture have been well studied and modeled. However, in nature, bacteria often grow as biofilms or colonies in physically structured habitats. A comprehensive model for population growth in such conditions has not yet been developed. Based on the well-established theory for bacterial growth in liquid culture, we develop a model for colony growth in 3D in which a homogeneous colony of cells locally consume a diffusing nutrient. We predict that colony growth is initially exponential, as in liquid culture, but quickly slows to sub-exponential after nutrient is locally depleted. This prediction is consistent with our experiments performed with E. coli in soft agar. Our model provides a baseline to which studies of complex growth process, such as such as spatially and phenotypically heterogeneous colonies, must be compared.

Physical vapor deposition as a route to hidden amorphous states

PubMed Central

Dawson, Kevin J.; Kearns, Kenneth L.; Yu, Lian; Steffen, Werner; Ediger, M. D.

2009-01-01

Stable glasses of indomethacin (IMC) were prepared by using physical vapor deposition. Wide-angle X-ray scattering measurements were performed to characterize the average local structure. IMC glasses prepared at a substrate temperature of 0.84 Tg (where Tg is the glass transition temperature) and a deposition rate of 0.2 nm/s show a broad, high-intensity peak at low q values that is not present in the supercooled liquid or melt-quenched glasses. When annealed slightly above Tg, the new WAXS pattern transforms into the melt-quenched glass pattern, but only after very long annealing times. For a series of samples prepared at the lowest deposition rate, the new local packing arrangement is present only for deposition temperatures below Tg −20 K, suggesting an underlying first-order liquid-to-liquid phase transition. PMID:19666494

Electronic properties of liquid Hg-In alloys : Ab-initio molecular dynamics study

NASA Astrophysics Data System (ADS)

Sharma, Nalini; Thakur, Anil; Ahluwalia, P. K.

2016-05-01

Ab-initio molecular dynamics simulations are performed to study the structural properties of liquid Hg-In alloys. The interatomic interactions are described by ab-initio pseudopotentials given by Troullier and Martins. Three liquid Hg-In alloys (Hg10In90, Hg30In70,. Hg50In50, Hg70In30, and Hg90Pb10) at 299 K are considered. The calculated results for liquid Hg (l-Hg) and lead (l-In) are also drawn. Along with the calculated results of considered five liquid alloys of Hg-In alloy. The results obtained from electronic properties namely total density of state and partial density of states help to find the local arrangement of Hg and In atoms and the presence of liquid state in the considered five alloys.

Electron doping a kagome spin liquid

DOE PAGES

Kelly, Z. A.; Gallagher, M. J.; McQueen, T. M.

2016-10-13

Herbertsmithite, ZnCu 3(OH) 6Cl 2, is a two-dimensional kagome lattice realization of a spin liquid, with evidence for fractionalized excitations and a gapped ground state. Such a quantum spin liquid has been proposed to underlie high-temperature superconductivity and is predicted to produce a wealth of new states, including a Dirac metal at 1/3 electron doping. Here, we report the topochemical synthesis of electron-doped ZnLi xCu 3(OH) 6Cl 2 from x=0 to x=1.8 (3/5 per Cu 2+). Contrary to expectations, no metallicity or superconductivity is induced. Instead, we find a systematic suppression of magnetic behavior across the phase diagram. Lastly, ourmore » results demonstrate that significant theoretical work is needed to understand and predict the role of doping in magnetically frustrated narrow band insulators, particularly the interplay between local structural disorder and tendency toward electron localization, and pave the way for future studies of doped spin liquids.« less

Color changing plasmonic surfaces utilizing liquid crystal (Conference Presentation)

NASA Astrophysics Data System (ADS)

Franklin, Daniel; Wu, Shin-Tson; Chanda, Debashis

2016-09-01

Plasmonic structural color has recently garnered significant interest as an alternative to the organic dyes standard in print media and liquid crystal displays. These nanostructured metallic systems can produce diffraction limited images, be made polarization dependent, and exhibit resistance to color bleaching. Perhaps even more advantageous, their optical characteristics can also be tuned, post-fabrication, by altering the surrounding media's refractive index parallel to the local plasmonic fields. A common material with which to achieve this is liquid crystal. By reorienting the liquid crystal molecules through external electric fields, the optical resonances of the plasmonic filters can be dynamically controlled. Demonstrations of this phenomenon, however, have been limited to modest shifts in plasmon resonance. Here, we report a liquid crystal-plasmonic system with an enhanced tuning range through the use of a shallow array of nano-wells and high birefringent liquid crystal. The continuous metallic nanostructure maximizes the overlap between plasmonic fields and liquid crystal while also allowing full reorientation of the liquid crystal upon an applied electric field. Sweeping over structural dimensions and voltages results in a color palette for these dynamic reflective pixels that can further be exploited to create color tunable images. These advances make plasmonic-liquid crystal systems more attractive candidates for filter, display, and other tunable optical technologies.

Rupture of thin liquid films on structured surfaces

NASA Astrophysics Data System (ADS)

Ajaev, Vladimir S.; Gatapova, Elizaveta Ya.; Kabov, Oleg A.

2011-10-01

We investigate stability and breakup of a thin liquid film on a solid surface under the action of disjoining pressure. The solid surface is structured by parallel grooves. Air is trapped in the grooves under the liquid film. Our mathematical model takes into account the effect of slip due to the presence of menisci separating the liquid film from the air inside the grooves, the deformation of these menisci due to local variations of pressure in the liquid film, and nonuniformities of the Hamaker constant which measures the strength of disjoining pressure. Both linear stability and strongly nonlinear evolution of the film are analyzed. Surface structuring results in decrease of the fastest growing instability wavelength and the rupture time. It is shown that a simplified description of film dynamics based on the standard formula for effective slip leads to significant deviations from the behavior seen in our simulations. Self-similar decay over several orders of magnitude of the film thickness near the rupture point is observed. We also show that the presence of the grooves can lead to instability in otherwise stable films if the relative groove width is above a critical value, found as a function of disjoining pressure parameters.

Finding the best density functional approximation to describe interaction energies and structures of ionic liquids in molecular dynamics studies

NASA Astrophysics Data System (ADS)

Perlt, Eva; Ray, Promit; Hansen, Andreas; Malberg, Friedrich; Grimme, Stefan; Kirchner, Barbara

2018-05-01

Ionic liquids raise interesting but complicated questions for theoretical investigations due to the fact that a number of different inter-molecular interactions, e.g., hydrogen bonding, long-range Coulomb interactions, and dispersion interactions, need to be described properly. Here, we present a detailed study on the ionic liquids ethylammonium nitrate and 1-ethyl-3-methylimidazolium acetate, in which we compare different dispersion corrected density functional approximations to accurate local coupled cluster data in static calculations on ionic liquid clusters. The efficient new composite method B97-3c is tested and has been implemented in CP2K for future studies. Furthermore, tight-binding based approaches which may be used in large scale simulations are assessed. Subsequently, ab initio as well as classical molecular dynamics simulations are conducted and structural analyses are presented in order to shed light on the different short- and long-range structural patterns depending on the method and the system size considered in the simulation. Our results indicate the presence of strong hydrogen bonds in ionic liquids as well as the aggregation of alkyl side chains due to dispersion interactions.

Direct-write liquid phase transformations with a scanning transmission electron microscope

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

Unocic, Raymond R.; Lupini, Andrew R.; Borisevich, Albina Y.

The highly energetic electron beam from a scanning transmission electron microscope (STEM) can induce local changes in the state of matter, ranging from local knock-out and atomic movement, to amorphization/crystallization, and chemical/electrochemical reactions occuring at localized liquid-solid and gas-solid interfaces. To date, fundamental studies of e-beam induced phenomena and practical applications have been limited by conventional e-beam rastering modes that allow only for uniform e-beam exposures. Here we develop an automated liquid phase nanolithography method that is capable of directly writing nanometer scaled features within silicon nitride encapsulated liquid cells. An external beam control system, connected to the scan coilsmore » of an aberration-corrected STEM, is used to precisely control the position, dwell time, and scan velocity of a sub-nanometer STEM probe. Site-specific locations in a sealed liquid cell containing an aqueous solution of H 2PdCl 4 are irradiated to controllably deposit palladium onto silicon nitride membranes. We determine the threshold electron dose required for the radiolytic deposition of metallic palladium, explore the influence of electron dose on the feature size and morphology of nanolithographically patterned nanostructures, and propose a feedback-controlled monitoring method for active control of the nanofabricated structures through STEM detector signal monitoring. As a result, this approach enables both fundamental studies of electron beam induced interactions with matter, as well as opens a pathway to fabricate nanostructures with tailored architectures and chemistries via shape-controlled nanolithographic patterning from liquid phase precursors.« less

Direct-write liquid phase transformations with a scanning transmission electron microscope

DOE PAGES

Unocic, Raymond R.; Lupini, Andrew R.; Borisevich, Albina Y.; ...

2016-08-03

The highly energetic electron beam from a scanning transmission electron microscope (STEM) can induce local changes in the state of matter, ranging from local knock-out and atomic movement, to amorphization/crystallization, and chemical/electrochemical reactions occuring at localized liquid-solid and gas-solid interfaces. To date, fundamental studies of e-beam induced phenomena and practical applications have been limited by conventional e-beam rastering modes that allow only for uniform e-beam exposures. Here we develop an automated liquid phase nanolithography method that is capable of directly writing nanometer scaled features within silicon nitride encapsulated liquid cells. An external beam control system, connected to the scan coilsmore » of an aberration-corrected STEM, is used to precisely control the position, dwell time, and scan velocity of a sub-nanometer STEM probe. Site-specific locations in a sealed liquid cell containing an aqueous solution of H 2PdCl 4 are irradiated to controllably deposit palladium onto silicon nitride membranes. We determine the threshold electron dose required for the radiolytic deposition of metallic palladium, explore the influence of electron dose on the feature size and morphology of nanolithographically patterned nanostructures, and propose a feedback-controlled monitoring method for active control of the nanofabricated structures through STEM detector signal monitoring. As a result, this approach enables both fundamental studies of electron beam induced interactions with matter, as well as opens a pathway to fabricate nanostructures with tailored architectures and chemistries via shape-controlled nanolithographic patterning from liquid phase precursors.« less

Localized treatments using commercial dust and liquid formulations of fipronil against Coptotermes formosanus (Isoptera: Rhinotermitidae) in the laboratory.

PubMed

Gautam, Bal K; Henderson, Gregg; Wang, Cai

2014-04-01

Use of proper application methods and formulations of termiticides are important to reduce their negative impact to the environment. In this study, we conducted laboratory experiments to determine the effect of localized treatments with commercial dust and liquid formulations of fipronil against Formosan subterranean termites, Coptotermes formosanus Shiraki. The test arena consisted of a specially designed 16-chambered structure with a center chamber connected to 5 foraging chambers that themselves were connected to 10 additional foraging chambers. One peripheral chamber received a liquid or dust treatment and termites were released in the center chamber. Results showed that >91% of the termites were dead within the 9-d test period despite the localized treatment of only 1 foraging chamber. Termites that were still alive after 9 d were transferred to an untreated dish and held for 10 more days. The majority of those termites were dead and the rest were moribund on day 19. Regardless of the specific dish treated, both formulations of fipronil were found to be highly efficacious. Termites did not exhibit repellency to either formulation. Our results suggest that localized (or spot) treatment with either commercially available dust or liquid formulations of fipronil can be a viable option for control of a termite infestation where complete soil drenching is not desirable. © 2013 Institute of Zoology, Chinese Academy of Sciences.

Theory of complicated liquids. Investigation of liquids, solvents and solvent effects with modern theoretical methods

NASA Astrophysics Data System (ADS)

Kirchner, Barbara

2007-03-01

It is the aim of this work to elucidate the usefulness and feasibility of the first-principles approach and to extend it to the regime of liquid molecular substances of complex structure. Physical and thermodynamic properties of complicated liquids are investigated by means of Car-Parrinello molecular dynamics (CPMD) and also with static quantum chemical methods. The connection between the dynamic and static approach is given by the quantum cluster equilibrium (QCE) theory. Since the QCE theory is not yet well established, a new implementation in the MD post-processing program P EACEMAKER is presented. It can be shown that it is by far more important to include cooperative effects rather than to concentrate the effort on the inclusion of weak dispersion forces not present in current density functionals. Traditionally, investigations of complicated liquids were also undertaken with the tools of simple liquids, because for some problems the size of the system does not allow for a more accurate description. Although linear-scaling techniques are simplifications from the point of view of quantum chemistry, they might be severe improvements when compared to traditional molecular dynamics simulations. For the interpretation of the liquid state the introduction of local properties is inevitable. New methods are presented for the calculation of local dipole moments and for the estimation of hydrogen bond energies in quantum mechanically nondecomposable systems. The latter also allows for the detection of hydrogen bonds in simulations through a wavefunction-based criterion instead of one which is solely grounded on the geometric structure of the atomic nuclei involved. The article then discusses prominent liquids which show properties that are not yet understood. Another part of the work analyzes the effect of solvent molecules on solutes and their reactions in the solvent. Finaly, neoteric solvents, such as ionic liquids are discussed.

Three-dimensional localized coherent structures of surface turbulence: Model validation with experiments and further computations.

PubMed

Demekhin, E A; Kalaidin, E N; Kalliadasis, S; Vlaskin, S Yu

2010-09-01

We validate experimentally the Kapitsa-Shkadov model utilized in the theoretical studies by Demekhin [Phys. Fluids 19, 114103 (2007)10.1063/1.2793148; Phys. Fluids 19, 114104 (2007)]10.1063/1.2793149 of surface turbulence on a thin liquid film flowing down a vertical planar wall. For water at 15° , surface turbulence typically occurs at an inlet Reynolds number of ≃40 . Of particular interest is to assess experimentally the predictions of the model for three-dimensional nonlinear localized coherent structures, which represent elementary processes of surface turbulence. For this purpose we devise simple experiments to investigate the instabilities and transitions leading to such structures. Our experimental results are in good agreement with the theoretical predictions of the model. We also perform time-dependent computations for the formation of coherent structures and their interaction with localized structures of smaller amplitude on the surface of the film.

Simulation studies of ionic liquids: Orientational correlations and static dielectric properties

NASA Astrophysics Data System (ADS)

Schröder, C.; Rudas, T.; Steinhauser, O.

2006-12-01

The ionic liquids BMIM+I-, BMIM+BF4-, and BMIM+PF6- were simulated by means of the molecular dynamics method over a time period of more than 100ns. Besides the common structural analysis, e.g., radial distribution functions and three dimensional occupancy plots, a more sophisticated orientational analysis was performed. The angular correlation functions g00110(r) and g00101(r) are the first distance dependent coefficients of the pairwise orientational distribution function g(rij,Ω1,Ω2,Ω12). These functions help to interpret the three dimensional plot and reveal interesting insights into the local structure of the analyzed ionic liquids. Furthermore, the collective network of ionic liquids can be characterized by the Kirkwood factor Gκ(r ) [J. Chem. Phys. 7, 911 (1939)]. The short-range behavior (r<10Å) of this factor may be suitable to predict the water miscibility of the ionic liquid. The long-range limit of Gk∞ is below 1 which demonstrates the strongly coupled nature of the ionic liquid networks. In addition, this factor relates the orientational structure and the dielectric properties of the ionic liquids. The static dielectric constant ɛ(ω =0) for the simulated system is 8.9-9.5. Since in ionic liquids the very same molecule contributes to the total dipole moment as well as carries a net charge, a small, but significant contribution of the cross term between the total dipole moment and the electric current to ɛ(ω =0) is observed.

Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor.

PubMed

Zheng, Jian; Zhang, Wei; Wang, Feng; Yu, Xiao-Ying

2018-05-10

In this paper, a vacuum compatible microfluidic device, system for analysis at the liquid vacuum interface, is integrated to hard x-ray absorption spectroscopy to obtain the local structure of K 3 [Fe(CN) 6 ] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel 500 µm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra indicate a presence of Fe(III) in the complex in water, with an octahedral geometry coordinated with 6 C atoms in the first shell with a distance of ~1.92 Å and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K 3 [Fe(CN) 6 ]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities. Using portable microfludic reactors provides a viable approach to enable multifaceted measurements of liquids in the future.

Communication: Relationship between local structure and the stability of water in hydrophobic confinement

NASA Astrophysics Data System (ADS)

Altabet, Y. Elia; Debenedetti, Pablo G.

2017-12-01

Liquid water confined between nanoscale hydrophobic objects can become metastable with respect to its vapor at nanoscale separations. While the separations are only several molecular diameters, macroscopic theories are often invoked to interpret the thermodynamics and kinetics of water under confinement. We perform detailed rate and free energy calculations via molecular simulations in order to assess the dependence of the rate of evaporation, free energy barriers, and free energy differences between confined liquid and vapor upon object separation and compare them to the relevant macroscopic theories. At small enough separations, the rate of evaporation appears to deviate significantly from the predictions of classical nucleation theory, and we attribute such deviations to changes in the structure of the confined liquid film. However, the free energy difference between the confined liquid and vapor phases agrees quantitatively with macroscopic theory, and the free energy barrier to condensation displays qualitative agreement. Overall, the present work suggests that theories attempting to capture the kinetic behavior of nanoscale systems should incorporate structural details rather than treating it as a continuum.

Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor

NASA Astrophysics Data System (ADS)

Zheng, Jian; Zhang, Wei; Wang, Feng; Yu, Xiao-Ying

2018-05-01

In this paper, a vacuum compatible microfluidic device, system for analysis at the liquid vacuum interface, is integrated to hard x-ray absorption spectroscopy to obtain the local structure of K3[Fe(CN)6] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel 500 µm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra indicate a presence of Fe(III) in the complex in water, with an octahedral geometry coordinated with 6 C atoms in the first shell with a distance of ~1.92 Å and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K3[Fe(CN)6]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities. Using portable microfludic reactors provides a viable approach to enable multifaceted measurements of liquids in the future.

Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor

DOE PAGES

Zheng, Jian; Zhang, Wei; Wang, Feng; ...

2018-04-11

In this study, a vacuum compatible microfluidic device, system for analysis at the liquid vacuum interface, is integrated to hard x-ray absorption spectroscopy to obtain the local structure of K 3[Fe(CN) 6] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel 500 µm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra indicate a presence of Fe(III) in the complex in water, with an octahedral geometry coordinated with 6 C atoms in the first shell with a distance of ~1.92 Åmore » and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K 3[Fe(CN) 6]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities. Using portable microfludic reactors provides a viable approach to enable multifaceted measurements of liquids in the future.« less

Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor

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

Zheng, Jian; Zhang, Wei; Wang, Feng

In this study, a vacuum compatible microfluidic device, system for analysis at the liquid vacuum interface, is integrated to hard x-ray absorption spectroscopy to obtain the local structure of K 3[Fe(CN) 6] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel 500 µm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra indicate a presence of Fe(III) in the complex in water, with an octahedral geometry coordinated with 6 C atoms in the first shell with a distance of ~1.92 Åmore » and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K 3[Fe(CN) 6]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities. Using portable microfludic reactors provides a viable approach to enable multifaceted measurements of liquids in the future.« less

Enabling liquid solvent structure analysis using hard x-ray absorption spectroscopy with a transferrable microfluidic reactor

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

Zheng, Jian; Zhang, Wei; Wang, Feng

In this paper, a vacuum compatible microfluidic device, System for Analysis at the Liquid Vacuum Interface (SALVI), is integrated to hard x-ray absorption spectroscopy (XAS) to obtain the local structure of K3[Fe(CN)6] in aqueous solutions with three concentrations of 0.5 M, 0.05 M, and 0.005 M. The solutions were sealed in a microchannel of 500 μm wide and 300 µm deep in a portable microfluidic device. The Fe K-edge x-ray absorption spectra show that the complex in water is Fe(III). The complex is present with octahedral geometry coordinated with 6 C atoms in the first shell with a distance ofmore » ~1.92 Å and 6 N atoms in the second shell with a distance of ~3.10 Å. Varying the concentration has no observable influence on the structure of K3[Fe(CN)6]. Our results demonstrate the feasibility of using microfluidic based liquid cells in large synchrotron facilities and it is a viable approach to enable multifaceted measurements of liquids in the future.« less

What Can Interfacial Water Molecules Tell Us About Solute Structure?

NASA Astrophysics Data System (ADS)

Willard, Adam

The molecular structure of bulk liquid water reflects a molecular tendency to engage in tetrahedrally coordinated hydrogen bonding. At a solute interface waters preferred three-dimensional hydrogen bonding network must conform to a locally anisotropy interfacial environment. Interfacial water molecules adopt configurations that balance water-solute and water-water interactions. The arrangements of interfacial water molecules, therefore encode information about the effective solute-water interactions. This solute-specific information is difficult to extract, however, because interfacial structure also reflects waters collective response to an anisotropic hydrogen bonding environment. Here I present a methodology for characterizing the molecular-level structure of liquid water interface from simulation data. This method can be used to explore waters static and/or dynamic response to a wide range of chemically and topologically heterogeneous solutes such as proteins.

Ab initio study of the structure and dynamics of bulk liquid Fe

NASA Astrophysics Data System (ADS)

Marqués, M.; González, L. E.; González, D. J.

2015-10-01

Several static and dynamic properties of bulk liquid Fe at a thermodynamic state near its triple point have been evaluated by ab initio molecular dynamics simulations. The calculated static structure shows very good agreement with the available experimental data, including an asymmetric second peak in the structure factor which underlines a substantial local icosahedral short-range order in the liquid. The dynamical structure reveals propagating density fluctuations, with an associated dispersion relation which closely follows the experimental data. The dynamic structure factors S (q ,ω ) show a good agreement with their experimental counterparts which have been recently measured by an inelastic x-ray scattering experiment. The dynamical processes behind the S (q ,ω ) have been analyzed by using a model with two decay channels (a fast and a slow) associated with the relaxations of the collective excitations. The recent finding of transverselike excitation modes in the IXS data is analyzed by using the present ab initio simulation results. Several transport coefficients have been evaluated and the results are compared with the available experimental data.

Electrical resistivity of Al-Cu liquid binary alloy

NASA Astrophysics Data System (ADS)

Thakor, P. P.; Patel, J. J.; Sonvane, Y. A.; Jani, A. R.

2013-06-01

Present paper deals with the electrical resistivity (ρ) of liquid Al-Cu binary alloy. To describe electron-ion interaction we have used our parameter free model potential along with Faber-Ziman formulation combined with Ashcroft-Langreth (AL) partial structure factor. To see the influence of exchange and correlation effect, Hartree, Taylor and Sarkar et al local field correlation functions are used. From present results, it is seen that good agreements between present results and experimental data have been achieved. Lastly we conclude that our model potential successfully produces the data of electrical resistivity (ρ) of liquid Al-Cu binary alloy.

Discrete elastic model for two-dimensional melting.

PubMed

Lansac, Yves; Glaser, Matthew A; Clark, Noel A

2006-04-01

We present a network model for the study of melting and liquid structure in two dimensions, the first in which the presence and energy of topological defects (dislocations and disclinations) and of geometrical defects (elemental voids) can be independently controlled. Interparticle interaction is via harmonic springs and control is achieved by Monte Carlo moves which springs can either be orientationally "flipped" between particles to generate topological defects, or can be "popped" in force-free shape, to generate geometrical defects. With the geometrical defects suppressed the transition to the liquid phase occurs via disclination unbinding, as described by the Kosterlitz-Thouless-Halperin-Nelson-Young model and found in soft potential two-dimensional (2D) systems, such as the dipole-dipole potential [H. H. von Grünberg, Phys. Rev. Lett. 93, 255703 (2004)]. By contrast, with topological defects suppressed, a disordering transition, the Glaser-Clark condensation of geometrical defects [M. A. Glaser and N. A. Clark, Adv. Chem. Phys. 83, 543 (1993); M. A. Glaser, (Springer-Verlag, Berlin, 1990), Vol. 52, p. 141], produces a state that accurately characterizes the local liquid structure and first-order melting observed in hard-potential 2D systems, such as hard disk and the Weeks-Chandler-Andersen (WCA) potentials (M. A. Glaser and co-workers, see above). Thus both the geometrical and topological defect systems play a role in melting. The present work introduces a system in which the relative roles of topological and geometrical defects and their interactions can be explored. We perform Monte Carlo simulations of this model in the isobaric-isothermal ensemble, and present the phase diagram as well as various thermodynamic, statistical, and structural quantities as a function of the relative populations of geometrical and topological defects. The model exhibits a rich phase behavior including hexagonal and square crystals, expanded crystal, dodecagonal quasicrystal, and isotropic liquid phases. In this system the geometrical defects effectively control the melting, reducing the solid-liquid transition temperature by a factor of relative to the topological-only case. The local structure of the dense liquid has been investigated and the results are compared to that from simulations of WCA systems.

Structure of liquid tricalcium aluminate

NASA Astrophysics Data System (ADS)

Drewitt, James W. E.; Barnes, Adrian C.; Jahn, Sandro; Kohn, Simon C.; Walter, Michael J.; Novikov, Alexey N.; Neuville, Daniel R.; Fischer, Henry E.; Hennet, Louis

2017-02-01

The atomic-scale structure of aerodynamically levitated and laser-heated liquid tricalcium aluminate (Ca3Al2O6 ) was measured at 2073(30) K by using the method of neutron diffraction with Ca isotope substitution (NDIS). The results enable the detailed resolution of the local coordination environment around calcium and aluminum atoms, including the direct determination of the liquid partial structure factor, SCaCa(Q ) , and partial pair distribution function, gCaCa(r ) . Molecular dynamics (MD) simulation and reverse Monte Carlo (RMC) refinement methods were employed to obtain a detailed atomistic model of the liquid structure. The composition Ca3Al2O6 lies at the CaO-rich limit of the CaO:Al2O3 glass-forming system. Our results show that, although significantly depolymerized, liquid Ca3Al2O6 is largely composed of AlO4 tetrahedra forming an infinite network with a slightly higher fraction of bridging oxygen atoms than expected for the composition. Calcium-centered polyhedra exhibit a wide distribution of four- to sevenfold coordinated sites, with higher coordinated calcium preferentially bonding to bridging oxygens. Analysis of the MD configuration reveals the presence of ˜10 % unconnected AlO4 monomers and Al2O7 dimers in the liquid. As the CaO concentration increases, the number of these isolated units increases, such that the upper value for the glass-forming composition of CaO:Al2O3 liquids could be described in terms of a percolation threshold at which the glass can no longer support the formation of an infinitely connected AlO4 network.

Electronic and structural transitions in dense liquid sodium.

PubMed

Raty, Jean-Yves; Schwegler, Eric; Bonev, Stanimir A

2007-09-27

At ambient conditions, the light alkali metals are free-electron-like crystals with a highly symmetric structure. However, they were found recently to exhibit unexpected complexity under pressure. It was predicted from theory--and later confirmed by experiment--that lithium and sodium undergo a sequence of symmetry-breaking transitions, driven by a Peierls mechanism, at high pressures. Measurements of the sodium melting curve have subsequently revealed an unprecedented (and still unexplained) pressure-induced drop in melting temperature from 1,000 K at 30 GPa down to room temperature at 120 GPa. Here we report results from ab initio calculations that explain the unusual melting behaviour in dense sodium. We show that molten sodium undergoes a series of pressure-induced structural and electronic transitions, analogous to those observed in solid sodium but commencing at much lower pressure in the presence of liquid disorder. As pressure is increased, liquid sodium initially evolves by assuming a more compact local structure. However, a transition to a lower-coordinated liquid takes place at a pressure of around 65 GPa, accompanied by a threefold drop in electrical conductivity. This transition is driven by the opening of a pseudogap, at the Fermi level, in the electronic density of states--an effect that has not hitherto been observed in a liquid metal. The lower-coordinated liquid emerges at high temperatures and above the stability region of a close-packed free-electron-like metal. We predict that similar exotic behaviour is possible in other materials as well.

Temperature- and pressure-dependent infrared spectroscopy of 1-butyl-3-methylimidazolium trifluoromethanesulfonate: A dipolar coupling theory analysis

NASA Astrophysics Data System (ADS)

Burba, Christopher M.; Chang, Hai-Chou

2018-03-01

Continued growth and development of ionic liquids requires a thorough understanding of how cation and anion molecular structure defines the liquid structure of the materials as well as the various properties that make them technologically useful. Infrared spectroscopy is frequently used to assess molecular-level interactions among the cations and anions of ionic liquids because the intramolecular vibrational modes of the ions are sensitive to the local potential energy environments in which they reside. Thus, different interaction modes among the ions may lead to different spectroscopic signatures in the vibrational spectra. Charge organization present in ionic liquids, such as 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C4mim]CF3SO3), is frequently modeled in terms of a quasicrystalline structure. Highly structured quasilattices enable the dynamic coupling of vibrationally-induced dipole moments to produce optical dispersion and transverse optical-longitudinal optical (TO-LO) splitting of vibrational modes of the ionic liquid. According to dipolar coupling theory, the degree of TO-LO splitting is predicted to have a linear dependence on the number density of the ionic liquid. Both temperature and pressure will affect the number density of the ionic liquid and, therefore, the amount of TO-LO splitting for this mode. Therefore, we test these relationships through temperature- and pressure-dependent FT-IR spectroscopic studies of [C4mim]CF3SO3, focusing on the totally symmetric Ssbnd O stretching mode for the anion, νs(SO3). Increased temperature decreases the amount of TO-LO splitting for νs(SO3), whereas elevated pressure is found to increase the amount of band splitting. In both cases, the experimental observations follow the general predictions of dipolar coupling theory, thereby supporting the quasilattice model for this ionic liquid.

Pressure Effect on the Boson Peak in Deeply Cooled Confined Water: Evidence of a Liquid-Liquid Transition.

PubMed

Wang, Zhe; Kolesnikov, Alexander I; Ito, Kanae; Podlesnyak, Andrey; Chen, Sow-Hsin

2015-12-04

The boson peak in deeply cooled water confined in nanopores is studied to examine the liquid-liquid transition (LLT). Below ∼180  K, the boson peaks at pressures P higher than ∼3.5  kbar are evidently distinct from those at low pressures by higher mean frequencies and lower heights. Moreover, the higher-P boson peaks can be rescaled to a master curve while the lower-P boson peaks can be rescaled to a different one. These phenomena agree with the existence of two liquid phases with different densities and local structures and the associated LLT in the measured (P, T) region. In addition, the P dependence of the librational band also agrees with the above conclusion.

Pressure Effect on the Boson Peak in Deeply Cooled Confined Water: Evidence of a Liquid-Liquid Transition

DOE PAGES

Wang, Zhe; Kolesnikov, Alexander I.; Ito, Kanae; ...

2015-12-03

We studied the boson peak in deeply cooled water confined in nanopores in order to examine the liquid-liquid transition (LLT). Below ~180 K, the boson peaks at pressures P higher than ~3.5 kbar are evidently distinct from those at low pressures by higher mean frequencies and lower heights. Moreover, the higher-P boson peaks can be rescaled to a master curve while the lower-P boson peaks can be rescaled to a different one. Moreover, these phenomena agree with the existence of two liquid phases with different densities and local structures and the associated LLT in the measured (P, T) region. Additionally,more » the P dependence of the librational band also agrees with the above conclusion.« less

Ab initio study of several static and dynamic properties of bulk liquid Ni near melting

NASA Astrophysics Data System (ADS)

del Rio, B. G.; González, L. E.; González, D. J.

2017-01-01

Several static and dynamic properties of bulk liquid Ni at a thermodynamic state near its triple point have been evaluated by ab initio molecular dynamics simulations. The calculated static structure shows very good agreement with the available experimental data, including an asymmetric second peak in the static structure factor, which underlines a marked local icosahedral short-range order in the liquid. The dynamical structure reveals propagating density fluctuations, and the calculated dynamic structure factors, S (q ,ω ) , show a good agreement with the inelastic x-ray scattering measurements. The obtained dispersion relation closely follows that obtained from the inelastic x-ray scattering measurements; moreover we analyze the possible reasons behind its discrepancy with respect to the dispersion relation derived from the inelastic neutron scattering data. The dynamical processes behind the S (q ,ω ) have been analyzed by using a model with two decay channels (a fast and a slow) associated with the relaxations of the collective excitations. We have found that the transverse current spectral functions exhibit some features which, so far, had previously been shown by high pressure liquid metals only. Furthermore, the calculated S (q ,ω ) show, within some q-range, the appearance of transverse-like excitation modes, similar to those recently found in other liquid metals. Finally, results are also reported for several transport coefficients.

A Molecular Dynamics Study of the Structure-Dynamics Relationships of Supercooled Liquids and Glasses

NASA Astrophysics Data System (ADS)

Soklaski, Ryan

Central to the field of condensed matter physics is a decades old outstanding problem in the study of glasses -- namely explaining the extreme slowing of dynamics in a liquid as it is supercooled towards the so-called glass transition. Efforts to universally describe the stretched relaxation processes and heterogeneous dynamics that characteristically develop in supercooled liquids remain divided in both their approaches and successes. Towards this end, a consensus on the role that atomic and molecular structures play in the liquid is even more tenuous. However, mounting material science research efforts have culminated to reveal that the vast diversity of metallic glass species and their properties are rooted in an equally-broad set of structural archetypes. Herein lies the motivation of this dissertation: the detailed information available regarding the structure-property relationships of metallic glasses provides a new context in which one can study the evolution of a supercooled liquid by utilizing a structural motif that is known to dominate the glass. Cu64Zr36 is a binary alloy whose good glass-forming ability and simple composition makes it a canonical material to both empirical and numerical studies. Here, we perform classical molecular dynamics simulations and conduct a comprehensive analysis of the dynamical regimes of liquid Cu64Zr36, while focusing on the roles played by atomic icosahedral ordering -- a structural motif which ultimately percolates the glass' structure. Large data analysis techniques are leveraged to obtain uniquely detailed structural and dynamical information in this context. In doing so, we develop the first account of the origin of icosahedral order in this alloy, revealing deep connections between this incipient structural ordering, frustration-limited domain theory, and recent important empirical findings that are relevant to the nature of metallic liquids at large. Furthermore, important dynamical landmarks such as the breakdown of the Stokes-Einstein relationship, the decoupling of particle diffusivities, and the development of general "glassy" relaxation features are found to coincide with successive manifestation of icosahedral ordering that arise as the liquid is supercooled. Remarkably, we detect critical-like features in the growth of the icosahedron network, with signatures that suggest that a liquid-liquid phase transition may occur in the deeply supercooled regime to precede glass formation. Such a transition is predicted to occur in many supercooled liquids, although explicit evidence of this phenomenon in realistic systems is scarce. Ultimately this work concludes that icosahedral order characterizes all dynamical regimes of Cu64Zr 36, demonstrating the importance and utility of studying supercooled liquids in the context of locally-preferred structure. More broadly, it serves to confirm and inform recent theoretical and empirical findings that are central to understanding the physics underlying the glass transition.

Heterogeneous activation in 2D colloidal glass-forming liquids classified by machine learning

NASA Astrophysics Data System (ADS)

Ma, Xiaoguang; Davidson, Zoey; Still, Tim; Ivancic, Robert; Schoenholz, Sam S.; Sussman, Daniel M.; Liu, A. J.; Yodh, A. G.

The trajectories of particles in colloidal glass-forming liquids are often characterized by long periods of ``in-cage'' fluctuations and rapid ``cage-breaking'' rearrangements. We study the rate of such rearrangements and its connection with local cage structures in a 2D binary mixture of poly(N-isopropyl acrylamide) spheres. We use the hopping function, Phop (t) , to identify rearrangements within particle trajectories. Then we obtain distributions of the residence time tR between consecutive rearrangements. The mean residence time tR (S) is found to correlate with the local configurations for the rearranging particles, characterized by 70 radial structural features and softness S, which ranks the structural similarities with respect to rearranging particles. Furthermore, tR (S) for particles with similar softness decays monotonically with increasing softness, indicating correlation between rearrangement rates and softness S. Finally we find that the conditional and full probability distribution functions, P (tR | S) and P (tR) , are well explained by a thermal activation model. We acknowledge financial supports from NSF-MRSEC DMR11-20901, NSF DMR16-07378, and NASA NNX08AO0G.

Ion transport and structural dynamics in homologous ammonium and phosphonium-based room temperature ionic liquids

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

Griffin, Philip J., E-mail: pgrif@seas.upenn.edu; Holt, Adam P.; Tsunashima, Katsuhiko

2015-02-28

Charge transport and structural dynamics in a homologous pair of ammonium and phosphonium based room temperature ionic liquids (ILs) have been characterized over a wide temperature range using broadband dielectric spectroscopy and quasi-elastic light scattering spectroscopy. We have found that the ionic conductivity of the phosphonium based IL is significantly enhanced relative to the ammonium homolog, and this increase is primarily a result of a lower glass transition temperature and higher ion mobility. Additionally, these ILs exhibit pronounced secondary relaxations which are strongly influenced by the atomic identity of the cation charge center. While the secondary relaxation in the phosphoniummore » IL has the expected Arrhenius temperature dependence characteristic of local beta relaxations, the corresponding relaxation process in the ammonium IL was found to exhibit a mildly non-Arrhenius temperature dependence in the measured temperature range—indicative of molecular cooperativity. These differences in both local and long-range molecular dynamics are a direct reflection of the subtly different inter-ionic interactions and mesoscale structures found in these homologous ILs.« less

Ion transport and structural dynamics in homologous ammonium and phosphonium-based room temperature ionic liquids

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

Griffin, Phillip J.; Holt, Adam P.; Tsunashima, Katsuhiko

2015-02-01

Charge transport and structural dynamics in a homologous pair of ammonium and phosphonium based room temperature ionic liquids (ILs) have been characterized over a wide temperature range using broadband dielectric spectroscopy and quasi-elastic light scattering spectroscopy. We have found that the ionic conductivity of the phosphonium based IL is significantly enhanced relative to the ammonium homolog, and this increase is primarily a result of a lower glass transition temperature and higher ion mobility. Additionally, these ILs exhibit pronounced secondary relaxations which are strongly influenced by the atomic identity of the cation charge center. While the secondary relaxation in the phosphoniummore » IL has the expected Arrhenius temperature dependence characteristic of local beta relaxations, the corresponding relaxation process in the ammonium IL was found to exhibit a mildly non-Arrhenius temperature dependence in the measured temperature range-indicative of molecular cooperativity. These differences in both local and long-range molecular dynamics are a direct reflection of the subtly different inter-ionic interactions and mesoscale structures found in these homologous ILs.« less

How Properties of Solid Surfaces Modulate the Nucleation of Gas Hydrate

PubMed Central

Bai, Dongsheng; Chen, Guangjin; Zhang, Xianren; Sum, Amadeu K.; Wang, Wenchuan

2015-01-01

Molecular dynamics simulations were performed for CO2 dissolved in water near silica surfaces to investigate how the hydrophilicity and crystallinity of solid surfaces modulate the local structure of adjacent molecules and the nucleation of CO2 hydrates. Our simulations reveal that the hydrophilicity of solid surfaces can change the local structure of water molecules and gas distribution near liquid-solid interfaces, and thus alter the mechanism and dynamics of gas hydrate nucleation. Interestingly, we find that hydrate nucleation tends to occur more easily on relatively less hydrophilic surfaces. Different from surface hydrophilicity, surface crystallinity shows a weak effect on the local structure of adjacent water molecules and on gas hydrate nucleation. At the initial stage of gas hydrate growth, however, the structuring of molecules induced by crystalline surfaces are more ordered than that induced by amorphous solid surfaces. PMID:26227239

Spin-liquid polymorphism in a correlated electron system on the threshold of superconductivity.

PubMed

Zaliznyak, Igor; Savici, Andrei T; Lumsden, Mark; Tsvelik, Alexei; Hu, Rongwei; Petrovic, Cedomir

2015-08-18

We report neutron scattering measurements which reveal spin-liquid polymorphism in an "11" iron chalcogenide superconductor. It occurs when a poorly metallic magnetic state of FeTe is tuned toward superconductivity by substitution of a small amount of tellurium with isoelectronic sulfur. We observe a liquid-like magnetic response, which is described by the coexistence of two disordered magnetic phases with different local structures whose relative abundance depends on temperature. One is the ferromagnetic (FM) plaquette phase observed in undoped, nonsuperconducting FeTe, which preserves the C4 symmetry of the underlying square lattice and is favored at high temperatures, whereas the other is the antiferromagnetic plaquette phase with broken C4 symmetry, which emerges with doping and is predominant at low temperatures. These findings suggest the coexistence of and competition between two distinct liquid states, and a liquid-liquid phase transformation between these states, in the electronic spin system of FeTe(1-x)(S,Se)(x). We have thus discovered the remarkable physics of competing spin-liquid polymorphs in a correlated electron system approaching superconductivity. Our results facilitate an understanding of large swaths of recent experimental data in unconventional superconductors. In particular, the phase with lower C2 local symmetry, whose emergence precedes superconductivity, naturally accounts for a propensity for forming electronic nematic states which have been observed experimentally, in cuprate and iron-based superconductors alike.

Charge ordering and scattering pre-peaks in ionic liquids and alcohols.

PubMed

Perera, Aurélien

2017-01-04

The structural properties of ionic liquids and alcohols are viewed under the charge ordering process as a common basis to explain the peculiarity of their radiation scattering properties, namely the presence, or absence, of a scattering pre-peak. Through the analysis of models, it is shown that the presence, or absence, of a radiation scattering pre-peak is principally related to the symmetry breaking, or not, of the global charge order, induced by the peculiarities of the molecular shapes. This symmetry breaking is achieved, in practice, by the emergence of specific types of clusters, which manifests how the global charge order has changed into a local form. Various atom-atom correlations witness the symmetry breaking induced by this re organization, and this is manifested into a pre-peak in the structure factor. This approach explains why associated liquids such as water do not show a scattering pre-peak. It also explains under which conditions core-soft models can mimic associating liquids.

Investigation of partitionless growth of ɛ-Al60Sm11 phase in Al-10 at% Sm liquid

NASA Astrophysics Data System (ADS)

Sun, Yang; Ye, Zhuo; Zhang, Feng; Ding, Ze Jun; Wang, Cai-Zhuang; Kramer, Matthew J.; Ho, Kai-Ming

2018-01-01

Recent experiments on devitrification of Al90Sm10 amorphous alloys revealed an unusual polymorphic transformation to a complex cubic crystal structure called the ɛ-Al60Sm11 phase. Molecular dynamics simulations of the growth of the stoichiometric ɛ-phase seed in contact with an undercooled Al-10 at% Sm liquid are performed to elucidate the microscopic process of transformation. The as-grown crystal and undercooled liquid possess similar local order around Al atoms whereas a rigid network defined by the Sm sub-lattice develops during the growth. Using a template-cluster alignment method, we define an order parameter to characterize the structural evolution in the system. Estimates of the attachment rate is {R}{{a}}=8.70× {10}-4 Å-2 ns-1 and detachment rate is {R}{{d}}=3.83× {10}-4 Å-2 ns-1 at the interface between ɛ-Al60Sm11 and Al-10 at% Sm liquid at 800 K.

Zwitterionization of glycine in water environment: Stabilization mechanism and NMR spectral signatures

NASA Astrophysics Data System (ADS)

Valverde, Danillo; da Costa Ludwig, Zélia Maria; da Costa, Célia Regina; Ludwig, Valdemir; Georg, Herbert C.

2018-01-01

At physiological conditions, myriads of biomolecules (e.g., amino acids, peptides, and proteins) exist predominantly in the zwitterionic structural form and their biological functions will result in these conditions. However these geometrical structures are inaccessible energetically in the gas phase, and at this point, stabilization of amino-acids in physiological conditions is still under debate. In this paper, the electronic properties of a glycine molecule in the liquid environment were studied by performing a relaxation of the glycine geometry in liquid water using the free energy gradient method combined with a sequential quantum mechanics/molecular mechanics approach. A series of Monte Carlo Metropolis simulations of the glycine molecule embedded in liquid water, followed by only a quantum mechanical calculation in each of them were carried out. Both the local and global liquid environments were emphasized to obtain nuclear magnetic resonance (NMR) parameters for the glycine molecule in liquid water. The results of the equilibrium structure in solution and the systematic study of the hydrogen bonds were used to discard the direct proton transfer from the carboxyl group to the ammonium group of the glycine molecule in water solution. The calculations of the Density Functional Theory (DFT) were performed to study the polarization of the solvent in the parameters of nuclear magnetic resonance of the glycine molecule in liquid water. DFT calculations predicted isotropic chemical changes on the H, C, N, and O atoms of glycine in liquid water solution which agree with the available experimental data.

Onset of ice VII phase during ps laser pulse propagation through liquid water

NASA Astrophysics Data System (ADS)

Kumar, V. Rakesh; Kiran, P. Prem

2017-01-01

Water dominantly present in liquid state on earth gets transformed to crystalline polymorphs under different dynamic loading conditions. Out of different crystalline phases discovered till date, ice VII is observed to be stable over wide pressure (2-63 GPa) and temperature (>273 K) ranges. The formation of ice VII crystalline structure has been vastly reported during high pressure static compression using diamond anvil cell and propagation of high energy (>50 mJ/pulse) nanosecond laser pulse induced dynamic high pressures through liquid water. We present the onset of ice VII phase at low threshold of 2 mJ/pulse during 30 ps (532 nm, 10 Hz) laser pulse induced shock propagating through liquid water. Role of input pulse energy on the evolution of Stoke's and anti-Stoke's Raman shift of the dominant A1g mode of ice VII, filamentation, free-electrons, plasma shielding is presented. The H-bond network rearrangement, electron ion energy transfer time coinciding with the excitation pulse duration supported by the filamentation and plasma shielding of the ps laser pulses reduced the threshold of ice VII structure formation. Filamentation and the plasma shielding have shown the localized creation and sustenance of ice VII structure in liquid water over 3 mm length and 50 μm area of cross-section.

Magnetic and optical holonomic manipulation of colloids, structures and topological defects in liquid crystals for characterization of mesoscale self-assembly and dynamics

NASA Astrophysics Data System (ADS)

Varney, Michael C. M.

Colloidal systems find important applications ranging from fabrication of photonic crystals to direct probing of phenomena encountered in atomic crystals and glasses; topics of great interest for physicists exploring a broad range of scientific, industrial and biomedical fields. The ability to accurately control particles of mesoscale size in various liquid host media is usually accomplished through optical trapping methods, which suffer limitations intrinsic to trap laser intensity and force generation. Other limitations are due to colloid properties, such as optical absorptivity, and host properties, such as viscosity, opacity and structure. Therefore, alternative and/or novel methods of colloidal manipulation are of utmost importance in order to advance the state of the art in technical applications and fundamental science. In this thesis, I demonstrate a magnetic-optical holonomic control system to manipulate magnetic and optical colloids in liquid crystals and show that the elastic structure inherent to nematic and cholesteric liquid crystals may be used to assist in tweezing of particles in a manner impossible in other media. Furthermore, I demonstrate the utility of this manipulation in characterizing the structure and microrheology of liquid crystals, and elucidating the energetics and dynamics of colloids interacting with these structures. I also demonstrate the utility of liquid crystal systems as a table top model system to probe topological defects in a manner that may lead to insights into topologically related phenomena in other fields, such as early universe cosmology, sub-atomic and high energy systems, or Skrymionic structures. I explore the interaction of colloid surface anchoring with the structure inherent in cholesteric liquid crystals, and how this affects the periodic dynamics and localization metastability of spherical colloids undergoing a "falling" motion within the sample. These so called "metastable states" cause colloidal dynamics to deviate from Stokes-like behavior at very low Reynolds numbers and is understood by accounting for periodic landscapes of elastic interaction potential between the particle and cholesteric host medium due to surface anchoring. This work extends our understanding of how colloids interact with liquid crystals and topological defects, and introduces a powerful method of colloidal manipulation with many potential applications.

Modeling the structural, dynamical, and magnetic properties of liquid Al1-xMnx ( x=0.14 , 0.2, and 0.4): A first-principles investigation

NASA Astrophysics Data System (ADS)

Jakse, N.; Pasturel, A.

2007-07-01

We report the results of first-principles molecular dynamics simulations of liquid Al1-xMnx alloys at three different compositions. The local structure as defined by the Bhatia-Thornton partial structure factors is found to display significant changes at x=0.4 . In addition, a structural analysis using three-dimensional pair-analysis techniques evidences a fivefold symmetry around x=0.14 , in agreement with the experimental quasicrystal-forming range, and an increasing complexity of the Frank-Kasper polytetrahedral symmetry around Mn atoms at x=0.4 . We also examine the time evolution of the configurations at the three compositions in terms of the mean-square displacements and self-diffusion coefficients. Finally, we show a strong interplay between the structural changes and the evolution of the magnetic properties of the Mn atoms as a function of composition.

Computational Modeling of Liquid and Gaseous Control Valves

NASA Technical Reports Server (NTRS)

Daines, Russell; Ahuja, Vineet; Hosangadi, Ashvin; Shipman, Jeremy; Moore, Arden; Sulyma, Peter

2005-01-01

In this paper computational modeling efforts undertaken at NASA Stennis Space Center in support of rocket engine component testing are discussed. Such analyses include structurally complex cryogenic liquid valves and gas valves operating at high pressures and flow rates. Basic modeling and initial successes are documented, and other issues that make valve modeling at SSC somewhat unique are also addressed. These include transient behavior, valve stall, and the determination of flow patterns in LOX valves. Hexahedral structured grids are used for valves that can be simplifies through the use of axisymmetric approximation. Hybrid unstructured methodology is used for structurally complex valves that have disparate length scales and complex flow paths that include strong swirl, local recirculation zones/secondary flow effects. Hexahedral (structured), unstructured, and hybrid meshes are compared for accuracy and computational efficiency. Accuracy is determined using verification and validation techniques.

Evaluation of the Thermodynamic Consistency of Closure Approximations in Several Models Proposed for the Description of Liquid Crystalline Dynamics

NASA Astrophysics Data System (ADS)

Edwards, Brian J.

2002-05-01

Given the premise that a set of dynamical equations must possess a definite, underlying mathematical structure to ensure local and global thermodynamic stability, as has been well documented, several different models for describing liquid crystalline dynamics are examined with respect to said structure. These models, each derived during the past several years using a specific closure approximation for the fourth moment of the distribution function in Doi's rigid rod theory, are all shown to be inconsistent with this basic mathematical structure. The source of this inconsistency lies in Doi's expressions for the extra stress tensor and temporal evolution of the order parameter, which are rederived herein using a transformation that allows for internal compatibility with the underlying mathematical structure that is present on the distribution function level of description.

Validity of the Stokes-Einstein relation in liquids: simple rules from the excess entropy.

PubMed

Pasturel, A; Jakse, N

2016-12-07

It is becoming common practice to consider that the Stokes-Einstein relation D/T~ η -1 usually works for liquids above their melting temperatures although there is also experimental evidence for its failure. Here we investigate numerically this commonly-invoked assumption for simple liquid metals as well as for their liquid alloys. Using ab initio molecular dynamics simulations we show how entropy scaling relationships developed by Rosenfeld can be used to predict the conditions for the validity of the Stokes-Einstein relation in the liquid phase. Specifically, we demonstrate the Stokes-Einstein relation may break down in the liquid phase of some liquid alloys mainly due to the presence of local structural ordering as evidenced in their partial two-body excess entropies. Our findings shed new light on the understanding of transport properties of liquid materials and will trigger more experimental and theoretical studies since excess entropy and its two-body approximation are readily obtainable from standard experiments and simulations.

Soft X-ray emission spectroscopy of liquids and lithium batterymaterials

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

Augustsson, Andreas

2004-01-01

Lithium ion insertion into electrode materials is commonly used in rechargeable battery technology. The insertion implies changes in both the crystal structure and the electronic structure of the electrode material. Side-reactions may occur on the surface of the electrode which is exposed to the electrolyte and form a solid electrolyte interface (SEI). The understanding of these processes is of great importance for improving battery performance. The chemical and physical properties of water and alcohols are complicated by the presence of strong hydrogen bonding. Various experimental techniques have been used to study geometrical structures and different models have been proposed tomore » view the details of how these liquids are geometrically organized by hydrogen bonding. However, very little is known about the electronic structure of these liquids, mainly due to the lack of suitable experimental tools. In this thesis examples of studies of lithium battery electrodes and liquid systems using soft x-ray emission spectroscopy will be presented. Monochromatized synchrotron radiation has been used to accomplish selective excitation, in terms of energy and polarization. The electronic structure of graphite electrodes has been studied, before and after lithium intercalation. Changes in the electronic structure upon lithiation due to transfer of electrons into the graphite π-bands have been observed. Transfer of electrons in to the 3d states of transition metal oxides upon lithiation have been studied, through low energy excitations as dd- and charge transfer-excitations. A SEI was detected on cycled graphite electrodes. By the use of selective excitation different carbon sites were probed in the SEI. The local electronic structure of water, methanol and mixtures of the two have been examined using a special liquid cell, to separate the liquid from the vacuum in the experimental chamber. Results from the study of liquid water showed a strong influence on the 3a1 molecular orbital and orbital mixing between water molecules upon hydrogen bonding. Apart from the four-hydrogen-bonding structure in water, a structure where one hydrogen bond is broken could be separated and identified. The soft x-ray emission study of methanol showed the existence of ring and chain formations in the liquid phase and the dominating structures are formed of 6 and 8 molecules. Upon mixing of the two liquids, a segregation at the molecular level was found and the formation of new structures, which could explain the unexpected low increase of the entropy.« less

Liquid/liquid interface layering of 1-butanol and [bmim]PF6 ionic liquid: a nonlinear vibrational spectroscopy and molecular dynamics simulation study.

PubMed

Iwahashi, Takashi; Ishiyama, Tatsuya; Sakai, Yasunari; Morita, Akihiro; Kim, Doseok; Ouchi, Yukio

2015-10-14

IR-visible sum-frequency generation (IV-SFG) vibrational spectroscopy and a molecular dynamics (MD) simulation were used to study the local layering order at the interface of 1-butanol-d9 and 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]PF6), a room-temperature ionic liquid (RTIL). The presence of a local non-polar layer at the interface of the two polar liquids was successfully demonstrated. In the SFG spectra of 1-butanol-d9, we observed significant reduction and enhancement in the strength of the CD3 symmetric stretching (r(+)) mode and the antisymmetric stretching (r(-)) mode peaks, respectively. The results can be well explained by the presence of an oppositely oriented quasi-bilayer structure of butanol molecules, where the bottom layer is strongly bound by hydrogen-bonding with the PF6(-) anion. MD simulations reveal that the hydrogen-bonding of butanol with the PF6(-) anion causes the preferential orientation of the butanols; the restriction on the rotational distribution of the terminal methyl group along their C3 axis enhances the r(-) mode. As for the [bmim](+) cations, the SFG spectra taken within the CH stretch region indicate that the butyl chain of [bmim](+) points away from the bulk RTIL phase to the butanol phase at the interface. Combining the SFG spectroscopy and MD simulation results, we propose an interfacial model structure of layering, in which the butyl chains of the butanol molecules form a non-polar interfacial layer with the butyl chains of the [bmim](+) cations at the interface.

Room-temperature ionic liquids: slow dynamics, viscosity, and the red edge effect.

PubMed

Hu, Zhonghan; Margulis, Claudio J

2007-11-01

Ionic liquids (ILs) have recently attracted significant attention from academic and industrial sources. This is because, while their vapor pressures are negligible, many of them are liquids at room temperature and can dissolve a wide range of polar and nonpolar organic and inorganic molecules. In this Account, we discuss the progress of our laboratory in understanding the dynamics, spectroscopy, and fluid dynamics of selected imidazolium-based ILs using computational and analytical tools that we have recently developed. Our results indicate that the red edge effect, the non-Newtonian behavior, and the existence of locally heterogeneous environments on a time scale relevant to chemical and photochemical reactivity are closely linked to the viscosity and highly structured character of these liquids.

Nondestructive optical testing of the materials surface structure based on liquid crystals

NASA Astrophysics Data System (ADS)

Tomilin, M. G.; Stafeev, S. K.

2011-08-01

Thin layers of nematic liquid crystals (NLCs) may be used as recording media for visualizing structural and microrelief defects, distribution of low power physical fields and modifications of the surface. NLCs are more sensitive in comparison with cholesteric and smectic LCs having super molecular structures. The detecting properties of NLCs are based on local layers deformation, induced by surface fields and observed in polarizing microscope. The structural surface defects or physical field's distribution are dramatically change the distribution of surface tension. Surface defects recording becomes possible if NLC deformed structure is illuminated in transparent or reflective modes and observed in optical polarizing microscope and appearing image is compared with background structure. In this case one observes not the real defect but the local deformation in NLCs. The theory was developed to find out the real size of defects. The resolution of NLC layer is more than 2000 lines/mm. The fields of NLC application are solid crystals symmetry, minerals, metals, semiconductors, polymers and glasses structure inhomogeneities and optical coatings defects detecting. The efficiency of NLC method in biophotonics is illustrated by objective detecting cancer tissues character and visualizing the interaction traces of grippe viruses with antibodies. NLCs may detect solvent components structure in tea, wine and perfume giving unique information of their structure. It presents diagnostic information alternative to dyes and fluorescence methods. For the first time the structures of some juices and beverages are visualized to illustrate the unique possibilities of NLCs.

Thermal convection of liquid metal in the titanium reduction reactor

NASA Astrophysics Data System (ADS)

Teimurazov, A.; Frick, P.; Stefani, F.

2017-06-01

The structure of the convective flow of molten magnesium in a metallothermic titanium reduction reactor has been studied numerically in a three-dimensional non-stationary formulation with conjugated heat transfer between liquid magnesium and solids (steel walls of the cavity and titanium block). A nonuniform computational mesh with a total of 3.7 million grid points was used. The Large Eddy Simulation technique was applied to take into account the turbulence in the liquid phase. The instantaneous and average characteristics of the process and the velocity and temperature pulsation fields are analyzed. The simulations have been performed for three specific heating regimes: with furnace heaters operating at full power, with furnace heaters switched on at the bottom of the vessel only, and with switched-off furnace heaters. It is shown that the localization of the cooling zone can completely reorganize the structure of the large-scale flow. Therefore, by changing heating regimes, it is possible to influence the flow structure for the purpose of creating the most favorable conditions for the reaction. It is also shown that the presence of the titanium block strongly affects the flow structure.

Externally driven magnetic granular layers at a liquid/air interface: self-organization, flows and magnetic order

NASA Astrophysics Data System (ADS)

Snezhko, Alexey

2007-03-01

Collective dynamics and pattern formation in ensembles of magnetic microparticles suspended at the liquid/air interface and subjected to an alternating magnetic field are studied. Experiments reveal a new type of nontrivially ordered dynamic self-assembled structures (``snakes'') emerging in such systems in a certain range of field magnitudes and frequencies. These remarkable structures are directly related to surface waves in the liquid generated by the collective response of magnetic microparticles to the alternating magnetic field. In addition, a large-scale vortex flows are induced in the vicinity of the dynamic structures. Some features of the self-localized snake structures can be understood in the framework of an amplitude equation for parametric waves coupled to the conservation law equation describing the evolution of the magnetic particle density. Self-assembled snakes have a complex magnetic order: the segments of the snake exhibit long-range antiferromagnetic ordering mediated by the surface wave, while each segment is composed of ferromagnetically aligned chains of microparticles. A phenomenological model describing magnetic behavior of the magnetic snakes in external magnetic fields is proposed.

Shaping liquid drops by vibration

NASA Astrophysics Data System (ADS)

Pototsky, Andrey; Bestehorn, Michael

2018-02-01

We present and analyze a minimal hydrodynamic model of a vertically vibrated liquid drop that undergoes dynamic shape transformations. In agreement with experiments, a circular lens-shaped drop is unstable above a critical vibration amplitude, spontaneously elongating in the horizontal direction. Smaller drops elongate into localized states that oscillate with half of the vibration frequency. Larger drops evolve by transforming into a snake-like structure with gradually increasing length. The worm state is long-lasting with a potential to fragment into smaller drops.

Vapor-liquid coexistence of the Stockmayer fluid in nonuniform external fields.

PubMed

Samin, Sela; Tsori, Yoav; Holm, Christian

2013-05-01

We investigate the structure and phase behavior of the Stockmayer fluid in the presence of nonuniform electric fields using molecular simulation. We find that an initially homogeneous vapor phase undergoes a local phase separation in a nonuniform field due to the combined effect of the field gradient and the fluid vapor-liquid equilibrium. This results in a high-density fluid condensing in the strong field region. The system polarization exhibits a strong field dependence due to the fluid condensation.

Molecular dynamics simulation of the ionic liquid N-octylpyridinium tetrafluoroborate and acetonitrile: Thermodynamic and structural properties

NASA Astrophysics Data System (ADS)

Zhou, Siwen; Zhu, Guanglai; Kang, Xianqu; Li, Qiang; Sha, Maolin; Cui, Zhifeng; Xu, Xinsheng

2018-06-01

Using molecular dynamics simulation, the research obtained the thermodynamic properties and microstructures of the mixture of N-octylpyridinium tetrafluoroborate and acetonitrile, including density, self-diffusion coefficients, excess properties, radial distribution functions (RDFs) and spatial distribution functions (SDFs). Both RDFs and SDFs indicate that the local microstructure of the polar region is different from the nonpolar region with different mole fraction of ionic liquids. Acetonitrile could increase the order of the polar regions. While with acetonitrile increasing, the orderliness of the nonpolar region increases firstly and then decreases. In relatively dilute solution, ionic liquids were dispersed to form small aggregates wrapped by acetonitrile.

Two-structure thermodynamics for the TIP4P/2005 model of water covering supercooled and deeply stretched regions.

PubMed

Biddle, John W; Singh, Rakesh S; Sparano, Evan M; Ricci, Francesco; González, Miguel A; Valeriani, Chantal; Abascal, José L F; Debenedetti, Pablo G; Anisimov, Mikhail A; Caupin, Frédéric

2017-01-21

One of the most promising frameworks for understanding the anomalies of cold and supercooled water postulates the existence of two competing, interconvertible local structures. If the non-ideality in the Gibbs energy of mixing overcomes the ideal entropy of mixing of these two structures, a liquid-liquid phase transition, terminated at a liquid-liquid critical point, is predicted. Various versions of the "two-structure equation of state" (TSEOS) based on this concept have shown remarkable agreement with both experimental data for metastable, deeply supercooled water and simulations of molecular water models. However, existing TSEOSs were not designed to describe the negative pressure region and do not account for the stability limit of the liquid state with respect to the vapor. While experimental data on supercooled water at negative pressures may shed additional light on the source of the anomalies of water, such data are very limited. To fill this gap, we have analyzed simulation results for TIP4P/2005, one of the most accurate classical water models available. We have used recently published simulation data, and performed additional simulations, over a broad range of positive and negative pressures, from ambient temperature to deeply supercooled conditions. We show that, by explicitly incorporating the liquid-vapor spinodal into a TSEOS, we are able to match the simulation data for TIP4P/2005 with remarkable accuracy. In particular, this equation of state quantitatively reproduces the lines of extrema in density, isothermal compressibility, and isobaric heat capacity. Contrary to an explanation of the thermodynamic anomalies of water based on a "retracing spinodal," the liquid-vapor spinodal in the present TSEOS continues monotonically to lower pressures upon cooling, influencing but not giving rise to density extrema and other thermodynamic anomalies.

Structural and dynamical properties of liquid Al-Au alloys

NASA Astrophysics Data System (ADS)

Peng, H. L.; Voigtmann, Th.; Kolland, G.; Kobatake, H.; Brillo, J.

2015-11-01

We investigate temperature- and composition-dependent structural and dynamical properties of Al-Au melts. Experiments are performed to obtain accurate density and viscosity data. The system shows a strong negative excess volume, similar to other Al-based binary alloys. We develop a molecular-dynamics (MD) model of the melt based on the embedded-atom method (EAM), gauged against the available experimental liquid-state data. A rescaling of previous EAM potentials for solid-state Au and Al improves the quantitative agreement with experimental data in the melt. In the MD simulation, the admixture of Au to Al can be interpreted as causing a local compression of the less dense Al system, driven by less soft Au-Au interactions. This local compression provides a microscopic mechanism explaining the strong negative excess volume of the melt. We further discuss the concentration dependence of self- and interdiffusion and viscosity in the MD model. Al atoms are more mobile than Au, and their increased mobility is linked to a lower viscosity of the melt.

Physics of microstructures enhancement of thin film evaporation heat transfer in microchannels flow boiling

PubMed Central

Bigham, Sajjad; Fazeli, Abdolreza; Moghaddam, Saeed

2017-01-01

Performance enhancement of the two-phase flow boiling heat transfer process in microchannels through implementation of surface micro- and nanostructures has gained substantial interest in recent years. However, the reported results range widely from a decline to improvements in performance depending on the test conditions and fluid properties, without a consensus on the physical mechanisms responsible for the observed behavior. This gap in knowledge stems from a lack of understanding of the physics of surface structures interactions with microscale heat and mass transfer events involved in the microchannel flow boiling process. Here, using a novel measurement technique, the heat and mass transfer process is analyzed within surface structures with unprecedented detail. The local heat flux and dryout time scale are measured as the liquid wicks through surface structures and evaporates. The physics governing heat transfer enhancement on textured surfaces is explained by a deterministic model that involves three key parameters: the drying time scale of the liquid film wicking into the surface structures (τd), the heating length scale of the liquid film (δH) and the area fraction of the evaporating liquid film (Ar). It is shown that the model accurately predicts the optimum spacing between surface structures (i.e. pillars fabricated on the microchannel wall) in boiling of two fluids FC-72 and water with fundamentally different wicking characteristics. PMID:28303952

Two-state thermodynamics and the possibility of a liquid-liquid phase transition in supercooled TIP4P/2005 water

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

Singh, Rakesh S.; Debenedetti, Pablo G.; Biddle, John W.

Water shows intriguing thermodynamic and dynamic anomalies in the supercooled liquid state. One possible explanation of the origin of these anomalies lies in the existence of a metastable liquid-liquid phase transition (LLPT) between two (high and low density) forms of water. While the anomalies are observed in experiments on bulk and confined water and by computer simulation studies of different water-like models, the existence of a LLPT in water is still debated. Unambiguous experimental proof of the existence of a LLPT in bulk supercooled water is hampered by fast ice nucleation which is a precursor of the hypothesized LLPT. Moreover,more » the hypothesized LLPT, being metastable, in principle cannot exist in the thermodynamic limit (infinite size, infinite time). Therefore, computer simulations of water models are crucial for exploring the possibility of the metastable LLPT and the nature of the anomalies. In this work, we present new simulation results in the NVT ensemble for one of the most accurate classical molecular models of water, TIP4P/2005. To describe the computed properties and explore the possibility of a LLPT, we have applied two-structure thermodynamics, viewing water as a non-ideal mixture of two interconvertible local structures (“states”). The results suggest the presence of a liquid-liquid critical point and are consistent with the existence of a LLPT in this model for the simulated length and time scales. We have compared the behavior of TIP4P/2005 with other popular water-like models, namely, mW and ST2, and with real water, all of which are well described by two-state thermodynamics. In view of the current debate involving different studies of TIP4P/2005, we discuss consequences of metastability and finite size in observing the liquid-liquid separation. We also address the relationship between the phenomenological order parameter of two-structure thermodynamics and the microscopic nature of the low-density structure.« less

Transparency and damage tolerance of patternable omniphobic lubricated surfaces based on inverse colloidal monolayers

DOE PAGES

Vogel, Nicolas; Belisle, Rebecca A.; Hatton, Benjamin; ...

2013-07-31

A transparent coating that repels a wide variety of liquids, prevents staining, is capable of self-repair and is robust towards mechanical damage can have a broad technological impact, from solar cell coatings to self-cleaning optical devices. Here we employ colloidal templating to design transparent, nanoporous surface structures. A lubricant can be firmly locked into the structures and, owing to its fluidic nature, forms a defect-free, self-healing interface that eliminates the pinning of a second liquid applied to its surface, leading to efficient liquid repellency, prevention of adsorption of liquid-borne contaminants, and reduction of ice adhesion strength. We further show howmore » this method can be applied to locally pattern the repellent character of the substrate, thus opening opportunities to spatially confine any simple or complex fluids. The coating is highly defect-tolerant due to its interconnected, honeycomb wall structure, and repellency prevails after the application of strong shear forces and mechanical damage. The regularity of the coating allows us to understand and predict the stability or failure of repellency as a function of lubricant layer thickness and defect distribution based on a simple geometric model.« less

Revolving supramolecular chiral structures powered by light in nanomotor-doped liquid crystals

NASA Astrophysics Data System (ADS)

Orlova, Tetiana; Lancia, Federico; Loussert, Charles; Iamsaard, Supitchaya; Katsonis, Nathalie; Brasselet, Etienne

2018-04-01

Molecular machines operated by light have been recently shown to be able to produce oriented motion at the molecular scale1,2 as well as do macroscopic work when embedded in supramolecular structures3-5. However, any supramolecular movement irremediably ceases as soon as the concentration of the interconverting molecular motors or switches reaches a photo-stationary state6,7. To circumvent this limitation, researchers have typically relied on establishing oscillating illumination conditions—either by modulating the source intensity8,9 or by using bespoke illumination arrangements10-13. In contrast, here we report a supramolecular system in which the emergence of oscillating patterns is encoded at the molecular level. Our system comprises chiral liquid crystal structures that revolve continuously when illuminated, under the action of embedded light-driven molecular motors. The rotation at the supramolecular level is sustained by the diffusion of the motors away from a localized illumination area. Above a critical irradiation power, we observe a spontaneous symmetry breaking that dictates the directionality of the supramolecular rotation. The interplay between the twist of the supramolecular structure and the diffusion14 of the chiral molecular motors creates continuous, regular and unidirectional rotation of the liquid crystal structure under non-equilibrium conditions.

Three-dimensional structure and multistable optical switching of triple-twisted particle-like excitations in anisotropic fluids.

PubMed

Smalyukh, Ivan I; Lansac, Yves; Clark, Noel A; Trivedi, Rahul P

2010-02-01

Control of structures in soft materials with long-range order forms the basis for applications such as displays, liquid-crystal biosensors, tunable lenses, distributed feedback lasers, muscle-like actuators and beam-steering devices. Bistable, tristable and multistable switching of well-defined structures of molecular alignment is of special interest for all of these applications. Here we describe the facile optical creation and multistable switching of localized configurations in the molecular orientation field of a chiral nematic anisotropic fluid. These localized chiro-elastic particle-like excitations--dubbed 'triple-twist torons'--are generated by vortex laser beams and embed the localized three-dimensional (3D) twist into a uniform background. Confocal polarizing microscopy and computer simulations reveal their equilibrium internal structures, manifesting both skyrmion-like and Hopf fibration features. Robust generation of torons at predetermined locations combined with both optical and electrical reversible switching can lead to new ways of multistable structuring of complex photonic architectures in soft materials.

Condensed-matter research at the Los Alamos pulsed neutron source (WNR)

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

Eckert, J.

1982-01-01

The experimental program at the WNR in condensed matter research at present is aimed principally at utilizing the high epithermal neutron flux available at a spallation neutron source. Interesting new results have been obtained in several areas including hydrogen vibrations in metals, chemical vibrational spectroscopy and the structure of liquids. For example, extensive vibrational spectra were obtained of hydrogen in Nb which could be described in terms of a three-dimensional localized anharmonic oscillator, deuterium substitution methods were used to determine the variation with 0-0 distance of the hydrogen bending mode frequency in extremely short intramolecular hydrogen bonds, and model-independent partialmore » structure factors were determined for liquid water.« less

SAW-Based Phononic Crystal Microfluidic Sensor—Microscale Realization of Velocimetry Approaches for Integrated Analytical Platform Applications

PubMed Central

Lucklum, Ralf; Zubtsov, Mikhail; Schmidt, Marc-Peter; Mukhin, Nikolay V.; Hirsch, Soeren

2017-01-01

The current work demonstrates a novel surface acoustic wave (SAW) based phononic crystal sensor approach that allows the integration of a velocimetry-based sensor concept into single chip integrated solutions, such as Lab-on-a-Chip devices. The introduced sensor platform merges advantages of ultrasonic velocimetry analytic systems and a microacoustic sensor approach. It is based on the analysis of structural resonances in a periodic composite arrangement of microfluidic channels confined within a liquid analyte. Completed theoretical and experimental investigations show the ability to utilize periodic structure localized modes for the detection of volumetric properties of liquids and prove the efficacy of the proposed sensor concept. PMID:28946609

SAW-Based Phononic Crystal Microfluidic Sensor-Microscale Realization of Velocimetry Approaches for Integrated Analytical Platform Applications.

PubMed

Oseev, Aleksandr; Lucklum, Ralf; Zubtsov, Mikhail; Schmidt, Marc-Peter; Mukhin, Nikolay V; Hirsch, Soeren

2017-09-23

The current work demonstrates a novel surface acoustic wave (SAW) based phononic crystal sensor approach that allows the integration of a velocimetry-based sensor concept into single chip integrated solutions, such as Lab-on-a-Chip devices. The introduced sensor platform merges advantages of ultrasonic velocimetry analytic systems and a microacoustic sensor approach. It is based on the analysis of structural resonances in a periodic composite arrangement of microfluidic channels confined within a liquid analyte. Completed theoretical and experimental investigations show the ability to utilize periodic structure localized modes for the detection of volumetric properties of liquids and prove the efficacy of the proposed sensor concept.

Entanglement entropy of critical spin liquids.

PubMed

Zhang, Yi; Grover, Tarun; Vishwanath, Ashvin

2011-08-05

Quantum spin liquids are phases of matter whose internal structure is not captured by a local order parameter. Particularly intriguing are critical spin liquids, where strongly interacting excitations control low energy properties. Here we calculate their bipartite entanglement entropy that characterizes their quantum structure. In particular we calculate the Renyi entropy S(2) on model wave functions obtained by Gutzwiller projection of a Fermi sea. Although the wave functions are not sign positive, S(2) can be calculated on relatively large systems (>324 spins) using the variational Monte Carlo technique. On the triangular lattice we find that entanglement entropy of the projected Fermi sea state violates the boundary law, with S(2) enhanced by a logarithmic factor. This is an unusual result for a bosonic wave function reflecting the presence of emergent fermions. These techniques can be extended to study a wide class of other phases.

The hydrogen-bond network of water supports propagating optical phonon-like modes.

PubMed

Elton, Daniel C; Fernández-Serra, Marivi

2016-01-04

The local structure of liquid water as a function of temperature is a source of intense research. This structure is intimately linked to the dynamics of water molecules, which can be measured using Raman and infrared spectroscopies. The assignment of spectral peaks depends on whether they are collective modes or single-molecule motions. Vibrational modes in liquids are usually considered to be associated to the motions of single molecules or small clusters. Using molecular dynamics simulations, here we find dispersive optical phonon-like modes in the librational and OH-stretching bands. We argue that on subpicosecond time scales these modes propagate through water's hydrogen-bond network over distances of up to 2 nm. In the long wavelength limit these optical modes exhibit longitudinal-transverse splitting, indicating the presence of coherent long-range dipole-dipole interactions, as in ice. Our results indicate the dynamics of liquid water have more similarities to ice than previously thought.

Thermal conductivity of Glycerol’s liquid, glass, and crystal states, glass-liquid-glass transition, and crystallization at high pressures

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

Andersson, Ove; Johari, G. P., E-mail: joharig@mcmaster.ca

2016-02-14

To investigate the effects of local density fluctuations on phonon propagation in a hydrogen bonded structure, we studied the thermal conductivity κ of the crystal, liquid, and glassy states of pure glycerol as a function of the temperature, T, and the pressure, p. We find that the following: (i) κ{sub crystal} is 3.6-times the κ{sub liquid} value at 140 K at 0.1 MPa and 2.2-times at 290 K, and it varies with T according to 138 × T{sup −0.95}; (ii) the ratio κ{sub liquid} (p)/κ{sub liquid} (0.1 MPa) is 1.45 GPa{sup −1} at 280 K, which, unexpectedly, is about themore » same as κ{sub crystal} (p)/κ{sub crystal} (0.1 MPa) of 1.42 GPa{sup −1} at 298 K; (iii) κ{sub glass} is relatively insensitive to T but sensitive to the applied p (1.38 GPa{sup −1} at 150 K); (iv) κ{sub glass}-T plots show an enhanced, pressure-dependent peak-like feature, which is due to the glass to liquid transition on heating; (v) continuous heating cold-crystallizes ultraviscous glycerol under pressure, at a higher T when p is high; and (vi) glycerol formed by cooling at a high p and then measured at a low p has a significantly higher κ than the glass formed by cooling at a low p. On heating at a fixed low p, its κ decreases before its glass-liquid transition range at that p is reached. We attribute this effect to thermally assisted loss of the configurational and vibrational instabilities of a glass formed at high p and recovered at low p, which is different from the usual glass-aging effect. While the heat capacity, entropy, and volume of glycerol crystal are less than those for its glass and liquid, κ{sub crystal} of glycerol, like its elastic modulus and refractive index, is higher. We discuss these findings in terms of the role of fluctuations in local density and structure, and the relations between κ and the thermodynamic quantities.« less

Erasing no-man’s land by thermodynamically stabilizing the liquid-liquid transition in tetrahedral particles

NASA Astrophysics Data System (ADS)

Smallenburg, Frank; Filion, Laura; Sciortino, Francesco

2014-09-01

One of the most controversial hypotheses for explaining the origin of the thermodynamic anomalies characterizing liquid water postulates the presence of a metastable second-order liquid-liquid critical point located in the `no-man’s land’. In this scenario, two liquids with distinct local structure emerge near the critical temperature. Unfortunately, as spontaneous crystallization is rapid in this region, experimental support for this hypothesis relies on significant extrapolations, either from the metastable liquid or from amorphous solid water. Although the liquid-liquid transition is expected to feature in many tetrahedrally coordinated liquids, including silicon, carbon and silica, even numerical studies of atomic and molecular models have been unable to conclusively prove the existence of this transition. Here we provide such evidence for a model in which it is possible to continuously tune the softness of the interparticle interaction and the flexibility of the bonds, the key ingredients controlling the existence of the critical point. We show that conditions exist where the full coexistence is thermodynamically stable with respect to crystallization. Our work offers a basis for designing colloidal analogues of water exhibiting liquid-liquid transitions in equilibrium, opening the way for experimental confirmation of the original hypothesis.

Probing the solvation structure and dynamics in ionic liquids by time-resolved infrared spectroscopy of 4-(dimethylamino)benzonitrile.

PubMed

Ando, Rômulo A; Brown-Xu, Samantha E; Nguyen, Lisa N Q; Gustafson, Terry L

2017-09-20

In this work we demonstrate the use of the push-pull model system 4-(dimethylamino)benzonitrile (DMABN) as a convenient molecular probe to investigate the local solvation structure and dynamics by means of time-resolved infrared spectroscopy (TRIR). The photochemical features associated with this system provide several advantages due to the high charge separation between the ground and charge transfer states involving the characteristic nitrile bond, and an excited state lifetime that is long enough to observe the slow solvation dynamics in organic solvents and ionic liquids. The conversion from a locally excited state to an intramolecular charge transfer state (LE-ICT) in ionic liquids shows similar kinetic lifetimes in comparison to organic solvents. This similarity confirms that such conversion depends solely on the intramolecular reorganization of DMABN in the excited state, and not by the dynamics of solvation. In contrast, the relative shift of the ν(CN) vibration during the relaxation of the ICT state reveals two distinct lifetimes that are sensitive to the solvent environment. This study reveals a fast time component which is attributed to the dipolar relaxation of the solvent and a slower time component related to the rotation of the dimethylamino group of DMABN.

Why glass elasticity affects the thermodynamics and fragility of supercooled liquids

PubMed Central

Yan, Le; Düring, Gustavo; Wyart, Matthieu

2013-01-01

Supercooled liquids are characterized by their fragility: The slowing down of the dynamics under cooling is more sudden and the jump of specific heat at the glass transition is generally larger in fragile liquids than in strong ones. Despite the importance of this quantity in classifying liquids, explaining what aspects of the microscopic structure controls fragility remains a challenge. Surprisingly, experiments indicate that the linear elasticity of the glass—a purely local property of the free energy landscape—is a good predictor of fragility. In particular, materials presenting a large excess of soft elastic modes, the so-called boson peak, are strong. This is also the case for network liquids near the rigidity percolation, known to affect elasticity. Here we introduce a model of the glass transition based on the assumption that particles can organize locally into distinct configurations that are coupled spatially via elasticity. The model captures the mentioned observations connecting elasticity and fragility. We find that materials presenting an abundance of soft elastic modes have little elastic frustration: Energy is insensitive to most directions in phase space, leading to a small jump of specific heat. In this framework strong liquids turn out to lie the closest to a critical point associated with a rigidity or jamming transition, and their thermodynamic properties are related to the problem of number partitioning and to Hopfield nets in the limit of small memory. PMID:23576746

Why glass elasticity affects the thermodynamics and fragility of supercooled liquids.

PubMed

Yan, Le; Düring, Gustavo; Wyart, Matthieu

2013-04-16

Supercooled liquids are characterized by their fragility: The slowing down of the dynamics under cooling is more sudden and the jump of specific heat at the glass transition is generally larger in fragile liquids than in strong ones. Despite the importance of this quantity in classifying liquids, explaining what aspects of the microscopic structure controls fragility remains a challenge. Surprisingly, experiments indicate that the linear elasticity of the glass--a purely local property of the free energy landscape--is a good predictor of fragility. In particular, materials presenting a large excess of soft elastic modes, the so-called boson peak, are strong. This is also the case for network liquids near the rigidity percolation, known to affect elasticity. Here we introduce a model of the glass transition based on the assumption that particles can organize locally into distinct configurations that are coupled spatially via elasticity. The model captures the mentioned observations connecting elasticity and fragility. We find that materials presenting an abundance of soft elastic modes have little elastic frustration: Energy is insensitive to most directions in phase space, leading to a small jump of specific heat. In this framework strong liquids turn out to lie the closest to a critical point associated with a rigidity or jamming transition, and their thermodynamic properties are related to the problem of number partitioning and to Hopfield nets in the limit of small memory.

Spin-liquid polymorphism in a correlated electron system on the threshold of superconductivity

PubMed Central

Zaliznyak, Igor; Savici, Andrei T.; Lumsden, Mark; Tsvelik, Alexei; Hu, Rongwei; Petrovic, Cedomir

2015-01-01

We report neutron scattering measurements which reveal spin-liquid polymorphism in an “11” iron chalcogenide superconductor. It occurs when a poorly metallic magnetic state of FeTe is tuned toward superconductivity by substitution of a small amount of tellurium with isoelectronic sulfur. We observe a liquid-like magnetic response, which is described by the coexistence of two disordered magnetic phases with different local structures whose relative abundance depends on temperature. One is the ferromagnetic (FM) plaquette phase observed in undoped, nonsuperconducting FeTe, which preserves the C4 symmetry of the underlying square lattice and is favored at high temperatures, whereas the other is the antiferromagnetic plaquette phase with broken C4 symmetry, which emerges with doping and is predominant at low temperatures. These findings suggest the coexistence of and competition between two distinct liquid states, and a liquid–liquid phase transformation between these states, in the electronic spin system of FeTe1−x(S,Se)x. We have thus discovered the remarkable physics of competing spin-liquid polymorphs in a correlated electron system approaching superconductivity. Our results facilitate an understanding of large swaths of recent experimental data in unconventional superconductors. In particular, the phase with lower C2 local symmetry, whose emergence precedes superconductivity, naturally accounts for a propensity for forming electronic nematic states which have been observed experimentally, in cuprate and iron-based superconductors alike. PMID:26240327

Real Space Imaging of Nanoparticle Assembly at Liquid-Liquid Interfaces with Nanoscale Resolution.

PubMed

Costa, Luca; Li-Destri, Giovanni; Thomson, Neil H; Konovalov, Oleg; Pontoni, Diego

2016-09-14

Bottom up self-assembly of functional materials at liquid-liquid interfaces has recently emerged as method to design and produce novel two-dimensional (2D) nanostructured membranes and devices with tailored properties. Liquid-liquid interfaces can be seen as a "factory floor" for nanoparticle (NP) self-assembly, because NPs are driven there by a reduction of interfacial energy. Such 2D assembly can be characterized by reciprocal space techniques, namely X-ray and neutron scattering or reflectivity. These techniques have drawbacks, however, as the structural information is averaged over the finite size of the radiation beam and nonperiodic isolated assemblies in 3D or defects may not be easily detected. Real-space in situ imaging methods are more appropriate in this context, but they often suffer from limited resolution and underperform or fail when applied to challenging liquid-liquid interfaces. Here, we study the surfactant-induced assembly of SiO2 nanoparticle monolayers at a water-oil interface using in situ atomic force microscopy (AFM) achieving nanoscale resolved imaging capabilities. Hitherto, AFM imaging has been restricted to solid-liquid interfaces because applications to liquid interfaces have been hindered by their softness and intrinsic dynamics, requiring accurate sample preparation methods and nonconventional AFM operational schemes. Comparing both AFM and grazing incidence X-ray small angle scattering data, we unambiguously demonstrate correlation between real and reciprocal space structure determination showing that the average interfacial NP density is found to vary with surfactant concentration. Additionally, the interaction between the tip and the interface can be exploited to locally determine the acting interfacial interactions. This work opens up the way to studying complex nanostructure formation and phase behavior in a range of liquid-liquid and complex liquid interfaces.

Coarse-grained theory of a realistic tetrahedral liquid model

NASA Astrophysics Data System (ADS)

Procaccia, I.; Regev, I.

2012-02-01

Tetrahedral liquids such as water and silica-melt show unusual thermodynamic behavior such as a density maximum and an increase in specific heat when cooled to low temperatures. Previous work had shown that Monte Carlo and mean-field solutions of a lattice model can exhibit these anomalous properties with or without a phase transition, depending on the values of the different terms in the Hamiltonian. Here we use a somewhat different approach, where we start from a very popular empirical model of tetrahedral liquids —the Stillinger-Weber model— and construct a coarse-grained theory which directly quantifies the local structure of the liquid as a function of volume and temperature. We compare the theory to molecular-dynamics simulations and show that the theory can rationalize the simulation results and the anomalous behavior.

Communication: On the origin of the non-Arrhenius behavior in water reorientation dynamics.

PubMed

Stirnemann, Guillaume; Laage, Damien

2012-07-21

We combine molecular dynamics simulations and analytic modeling to determine the origin of the non-Arrhenius temperature dependence of liquid water's reorientation and hydrogen-bond dynamics between 235 K and 350 K. We present a quantitative model connecting hydrogen-bond exchange dynamics to local structural fluctuations, measured by the asphericity of Voronoi cells associated with each water molecule. For a fixed local structure the regular Arrhenius behavior is recovered, and the global anomalous temperature dependence is demonstrated to essentially result from a continuous shift in the unimodal structure distribution upon cooling. The non-Arrhenius behavior can thus be explained without invoking an equilibrium between distinct structures. In addition, the large width of the homogeneous structural distribution is shown to cause a growing dynamical heterogeneity and a non-exponential relaxation at low temperature.

Amyotrophic lateral sclerosis-linked mutations increase the viscosity of liquid-like TDP-43 RNP granules in neurons.

PubMed

Gopal, Pallavi P; Nirschl, Jeffrey J; Klinman, Eva; Holzbaur, Erika L F

2017-03-21

Ribonucleoprotein (RNP) granules are enriched in specific RNAs and RNA-binding proteins (RBPs) and mediate critical cellular processes. Purified RBPs form liquid droplets in vitro through liquid-liquid phase separation and liquid-like non-membrane-bound structures in cells. Mutations in the human RBPs TAR-DNA binding protein 43 (TDP-43) and RNA-binding protein FUS cause amyotrophic lateral sclerosis (ALS), but the biophysical properties of these proteins have not yet been studied in neurons. Here, we show that TDP-43 RNP granules in axons of rodent primary cortical neurons display liquid-like properties, including fusion with rapid relaxation to circular shape, shear stress-induced deformation, and rapid fluorescence recovery after photobleaching. RNP granules formed from wild-type TDP-43 show distinct biophysical properties depending on axonal location, suggesting maturation to a more stabilized structure is dependent on subcellular context, including local density and aging. Superresolution microscopy demonstrates that the stabilized population of TDP-43 RNP granules in the proximal axon is less circular and shows spiculated edges, whereas more distal granules are both more spherical and more dynamic. RNP granules formed by ALS-linked mutant TDP-43 are more viscous and exhibit disrupted transport dynamics. We propose these altered properties may confer toxic gain of function and reflect differential propensity for pathological transformation.

Replica-exchange molecular dynamics simulations of cellulose solvated in water and in the ionic liquid 1-butyl-3-methylimidazolium chloride

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

Mostofian, Barmak; Cheng, Xiaolin; Smith, Jeremy C.

2014-09-02

Ionic liquids have become a popular solvent for cellulose pretreatment in biorefineries due to their efficiency in dissolution and their reusability. Understanding the interactions between cations, anions, and cellulose is key to the development of better solvents and the improvement of pretreatment conditions. While previous studies described the interactions between ionic liquids and cellulose fibers, shedding light on the initial stages of the cellulose dissolution process, we study the end state of that process by exploring the structure and dynamics of a single cellulose decamer solvated in 1-butyl-3-methyl-imidazolium chloride (BmimCl) and in water using replica-exchange molecular dynamics. In both solvents,more » global structural features of the cellulose chain are similar. However, analyses of local structural properties show that cellulose explores greater conformational variability in the ionic liquid than in water. For instance, in BmimCl the cellulose intramolecular hydrogen bond O3H'••• O5 is disrupted more often resulting in greater flexibility of the solute. Our results indicate that the cellulose chain is more dynamic in BmimCl than in water, which may play a role in the favorable dissolution of cellulose in the ionic liquid. Here, the calculation of the configurational entropy of the cellulose decamer confirms its higher conformational flexibility in BmimCl than in water at elevated temperatures.« less

Nematic Liquid-Crystal Colloids

PubMed Central

Muševič, Igor

2017-01-01

This article provides a concise review of a new state of colloidal matter called nematic liquid-crystal colloids. These colloids are obtained by dispersing microparticles of different shapes in a nematic liquid crystal that acts as a solvent for the dispersed particles. The microparticles induce a local deformation of the liquid crystal, which then generates topological defects and long-range forces between the neighboring particles. The colloidal forces in nematic colloids are much stronger than the forces in ordinary colloids in isotropic solvents, exceeding thousands of kBT per micrometer-sized particle. Of special interest are the topological defects in nematic colloids, which appear in many fascinating forms, such as singular points, closed loops, multitudes of interlinked and knotted loops or soliton-like structures. The richness of the topological phenomena and the possibility to design and control topological defects with laser tweezers make colloids in nematic liquid crystals an excellent playground for testing the basic theorems of topology. PMID:29295574

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

Mamontov, Eugene; Zolnierczuk, Piotr A.; Ohl, Michael E.

Using neutron spin-echo and backscattering spectroscopy, we have found that at low temperatures water molecules in an aqueous solution engage in center-of-mass dynamics that are different from both the main structural relaxations and the well-known localized motions in the transient cages of the nearest neighbor molecules. While the latter localized motions are known to take place on the picosecond time scale and Angstrom length scale, the slower motions that we have observed are found on the nanosecond time scale and nanometer length scale. They are associated with the slow secondary relaxations, or excess wing dynamics, in glass-forming liquids. Our approach,more » therefore, can be applied to probe the characteristic length scale of the dynamic entities associated with slow dynamics in glass-forming liquids, which presently cannot be studied by other experimental techniques.« less

Electronic transport properties of some liquid semiconductor

NASA Astrophysics Data System (ADS)

Sonvane, Y. A.; Thakor, P. B.; Jani, A. R.

2012-06-01

Electronic transport properties like electrical resistivity (ρ) and thermoelectric power (Q) of liquid semiconductor (Si, Ga, Ge, In, Sn, Tl and Bi) are calculated in the present study. Our well established single parametric model potential alongwith Percus Yevick hard sphere (PYHS) reference system are used to describe the structural information. To see the influence of exchange and correlation effect, Hartree, Taylor and Sarkar et al local field correlation functions are used. From present results, it is seen that good agreements between present results and experimental data have been achieved. Lastly we conclude that our model potential successfully produces the data of electronic transport properties for some liquid semiconductor (Si, Ga, Ge, In, Sn, Tl and Bi).

Effect of diet grinding and pelleting fed either dry or liquid feed on dry matter and pH in the stomach of pigs and the development of gastric ulcers.

PubMed

Mösseler, A; Wintermann, M; Sander, S J; Kamphues, J

2012-12-01

The physical form of diets has a marked impact on the development of gastric ulcers in pigs. Earlier studies showed effects of fine grinding and pelleting on the integrity of gastric mucosa as well as on local intragastric milieu. This study was conducted to evaluate the effects of dry or liquid feeding on intragastric milieu (DM and pH) in pigs. The 23 piglets were housed individually and fed with test diets and water ad lib for 6 wk. Both experimental diets [coarsely ground diet fed as mash (CM) vs. finely ground pelleted diet (FP)] were identical in ingredients (39.5% wheat, 34% barley, 20% soybean meal) and chemical composition and were either offered dry or in liquid (25% DM) form. At the end of the trial the animals were slaughtered; the stomach was removed and samples were taken from different localizations. Feeding diets dry or liquid had no effect on the pH (P > 0.05). The diet noticeably affected the gastric content. The FP diets resulted in a more liquid chyme (P < 0.05), and the intragastric pH did not differ between regions. Feeding CM caused marked effects of localization regarding pH (highest values: pars nonglandularis; lowest values: fundus). None of the pigs fed CM showed signs of gastric ulcers, but the score was markedly higher (P < 0.05) when pigs were fed FP. Therefore the predominant factor for development of gastric ulcers seems to be the structure (particle size) of the diet.

Crystallization of accessory phases in magmas by local saturation adjacent to phenocrysts

USGS Publications Warehouse

Bacon, C.R.

1989-01-01

Accessory minerals commonly occur attached to or included in the major crystalline phases of felsic and some intermediate igneous rocks. Apatite is particularly common as inclusions, but Fe-Ti oxides, pyrrhotite, zircon, monazite, chevkinite and xenotime are also known from silicic rocks. Accessories may nucleate near the host crystal/ liquid interface as a result of local saturation owing to formation of a differentiated chemical boundary layer in which accessory mineral solubility would be lower than in the surrounding liquid. Differentiation of this boundary layer would be greatest adjacent to ferromagnesian phenocrysts, especially Fe-Ti oxides; it is with oxides that accessories are most commonly associated in rocks. A boundary layer may develop if the crystal grows more rapidly than diffusion can transport incorporated and rejected elements to and from the phenocryst. Diffusion must dominate over convection as a mode of mass transfer near the advancing crystal/liquid interface in order for a boundary layer to exist. Accumulation of essential structural constituent elements of accessory minerals owing to their slow diffusion in evolved silicate melt also may force local saturation, but this is not a process that applies to all cases. Local saturation is an attractive mechanism for enhancing fractionation during crystallization differentiation. If accessory minerals attached to or included in phenocrysts formed because of local saturation, their host phenocrysts must have grown rapidly when accessories nucleated in comparison to lifetimes of magma reservoirs. Some inconsistencies remain in a local saturation origin for accessory phases that cannot be evaluated without additional information. ?? 1989.

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

Ding, Jun; Ma, Evan; Asta, Mark

Using molecular dynamics simulations, we have studied the atomic correlations characterizing the second peak in the radial distribution function (RDF) of metallic glasses and liquids. The analysis was conducted from the perspective of different connection schemes of atomic packing motifs, based on the number of shared atoms between two linked coordination polyhedra. The results demonstrate that the cluster connections by face-sharing, specifically with three common atoms, are most favored when transitioning from the liquid to glassy state, and exhibit the stiffest elastic response during shear deformation. These properties of the connections and the resultant atomic correlations are generally the samemore » for different types of packing motifs in different alloys. Splitting of the second RDF peak was observed for the inherent structure of the equilibrium liquid, originating solely from cluster connections; this trait can then be inherited in the metallic glass formed via subsequent quenching of the parent liquid through the glass transition, in the absence of any additional type of local structural order. In conclusion, increasing ordering and cluster connection during cooling, however, may tune the position and intensity of the split peaks.« less

Development of a transferline connecting a helium liquefier coldbox and a liquid helium Dewar

NASA Astrophysics Data System (ADS)

Menon, Rajendran S.; Rane, Tejas; Chakravarty, Anindya; Joemon, V.

2017-02-01

A helium liquefier with demonstrated capacity of 32 1/hr has been developed by BARC. Mumbai. A transferline for two way flow of helium between the helium liquefier coldbox and receiver Dewar has been developed in-house at BARC. Further, a functionally similar, but structurally improved transferline has been developed through a local fabricator. This paper describes and discusses issues related to the development of these cryogenic transferlines. The developed transferlines have been tested with a flow of liquid nitrogen and successfully utilised later in the helium liquefier plant.

Suppression of the "Quasiclassical" proximity gap in correlated-metal--superconductor structures.

PubMed

Nikolić, Branislav K; Freericks, J K; Miller, P

2002-02-18

We study the energy and spatial dependence of the local density of states in a superconductor--correlated-metal--superconductor Josephson junction, where the correlated metal is a non-Fermi liquid (described by the Falicov-Kimball model). Many-body correlations are treated with dynamical mean-field theory, extended to inhomogeneous systems. While quasiclassical theories predict a minigap in the spectrum of a disordered Fermi liquid which is proximity-coupled within a mesoscopic junction, we find that increasing electron correlations destroy any minigap that might be opened in the absence of many-body correlations.

Water: two liquids divided by a common hydrogen bond.

PubMed

Soper, Alan K

2011-12-08

The structure of water is the subject of a long and ongoing controversy. Unlike simpler liquids, where atomic interactions are dominated by strong repulsive forces at short distances and weaker attractive (van der Waals) forces at longer distances, giving rise to local atomic coordination numbers of order 12, water has pronounced and directional hydrogen bonds which cause the dense liquid close-packed structure to open out into a disordered and dynamic network, with coordination number 4-5. Here I show that water structure can be accurately represented as a mixture of two identical, interpenetrating, molecular species separated by common hydrogen bonds. Molecules of one type can form hydrogen bonds with molecules of the other type but cannot form hydrogen bonds with molecules of the same type. These hydrogen bonds are strong along the bond but weak with respect to changes in the angle between neighboring bonds. The observed pressure and temperature dependence of water structure and thermodynamic properties follow naturally from this choice of water model, and it also gives a simple explanation of the enduring claims based on spectroscopic evidence that water is a mixture of two components. © 2011 American Chemical Society

Conductivity-Relaxation Relations in Nanocomposite Polymer Electrolytes Containing Ionic Liquid.

PubMed

Shojaatalhosseini, Mansoureh; Elamin, Khalid; Swenson, Jan

2017-10-19

In this study, we have used nanocomposite polymer electrolytes, consisting of poly(ethylene oxide) (PEO), δ-Al 2 O 3 nanoparticles, and lithium bis(trifluoromethanesolfonyl)imide (LiTFSI) salt (with 4 wt % δ-Al 2 O 3 and PEO:Li ratios of 16:1 and 8:1), and added different amounts of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesolfonyl)imide (BMITFSI). The aim was to elucidate whether the ionic liquid is able to dissociate the Li-ions from the ether oxygens and thereby decouple the ionic conductivity from the segmental polymer dynamics. The results from DSC and dielectric spectroscopy show that the ionic liquid speeds up both the segmental polymer dynamics and the motion of the Li + ions. However, a close comparison between the structural (α) relaxation process, given by the segmental polymer dynamics, and the ionic conductivity shows that the motion of the Li + ions decouples from the segmental polymer dynamics at higher concentrations of the ionic liquid (≥20 wt %) and instead becomes more related to the viscosity of the ionic liquid. This decoupling increases with decreasing temperature. In addition to the structural α-relaxation, two more local relaxation processes, denoted β and γ, are observed. The β-relaxation becomes slightly faster at the highest concentration of the ionic liquid (at least for the lower salt concentration), whereas the γ-relaxation is unaffected by the ionic liquid, over the whole concentration range 0-40 wt %.

Experimental Evidence for a Structural-Dynamical Transition in Trajectory Space.

PubMed

Pinchaipat, Rattachai; Campo, Matteo; Turci, Francesco; Hallett, James E; Speck, Thomas; Royall, C Patrick

2017-07-14

Among the key insights into the glass transition has been the identification of a nonequilibrium phase transition in trajectory space which reveals phase coexistence between the normal supercooled liquid (active phase) and a glassy state (inactive phase). Here, we present evidence that such a transition occurs in experiments. In colloidal hard spheres, we find a non-Gaussian distribution of trajectories leaning towards those rich in locally favored structures (LFSs), associated with the emergence of slow dynamics. This we interpret as evidence for a nonequilibrium transition to an inactive LFS-rich phase. Reweighting trajectories reveals a first-order phase transition in trajectory space between a normal liquid and a LFS-rich phase. We also find evidence for a purely dynamical transition in trajectory space.

The Boson peak in confined water: An experimental investigation of the liquid-liquid phase transition hypothesis

NASA Astrophysics Data System (ADS)

Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; Wang, Zhe; Chen, Sow-Hsin

2015-10-01

The Boson peak (BP) of deeply cooled confined water is studied by using inelastic neutron scattering (INS) in a large interval of the ( P, T) phase plane. By taking into account the different behavior of such a collective vibrational mode in both strong and fragile glasses as well as in glass-forming materials, we were able to determine the Widom line that characterizes supercooled bulk water within the frame of the liquid-liquid phase transition (LLPT) hypothesis. The peak frequency and width of the BP correlated with the water polymorphism of the LLPT scenario, allowing us to distinguish the "low-density liquid" (LDL) and "high-density liquid" (HDL) phases in deeply cooled bulk water.Moreover, the BP properties afford a further confirmation of theWidom line temperature T W as the ( P, T) locus in which the local structure of water transforms from a predominately LDL form to a predominately HDL form.

Surface structure and structural point defects of liquid and amorphous aluminosilicate nanoparticles.

PubMed

Linh, Nguyen Ngoc; Hoang, Vo Van

2008-07-02

The surface structure of liquid and amorphous aluminosilicate nanoparticles of composition Al(2)O(3)·2SiO(2) has been investigated in a model of different sizes ranging from 2.0 to 5.0 nm with the Born-Mayer type pair potential under non-periodic boundary conditions. Models have been obtained by cooling from the melts at a constant density of 2.6 g cm(-3) via molecular dynamics (MD) simulation. The surface structure has been investigated via the coordination number, bond-angle distributions and structural point defects. Calculations show that surface effects on surface static and thermodynamic properties of models are significant according to the change in the number of Al atoms in the surface layers. Evolution of the local environment of oxygen in the surface shell of nanoparticles upon cooling from the melt toward the glassy state was also found and discussed. In addition, the nanosize dependence of the glass transition temperature was presented.

Surface structure and structural point defects of liquid and amorphous aluminosilicate nanoparticles

NASA Astrophysics Data System (ADS)

Linh, Nguyen Ngoc; Van Hoang, Vo

2008-07-01

The surface structure of liquid and amorphous aluminosilicate nanoparticles of composition Al2O3·2SiO2 has been investigated in a model of different sizes ranging from 2.0 to 5.0 nm with the Born-Mayer type pair potential under non-periodic boundary conditions. Models have been obtained by cooling from the melts at a constant density of 2.6 g cm-3 via molecular dynamics (MD) simulation. The surface structure has been investigated via the coordination number, bond-angle distributions and structural point defects. Calculations show that surface effects on surface static and thermodynamic properties of models are significant according to the change in the number of Al atoms in the surface layers. Evolution of the local environment of oxygen in the surface shell of nanoparticles upon cooling from the melt toward the glassy state was also found and discussed. In addition, the nanosize dependence of the glass transition temperature was presented.

Hairy root culture in a liquid-dispersed bioreactor: characterization of spatial heterogeneity.

PubMed

Williams, G R; Doran, P M

2000-01-01

A liquid-dispersed reactor equipped with a vertical mesh cylinder for inoculum support was developed for culture of Atropa belladonna hairy roots. The working volume of the culture vessel was 4.4 L with an aspect ratio of 1.7. Medium was dispersed as a spray onto the top of the root bed, and the roots grew radially outward from the central mesh cylinder to the vessel wall. Significant benefits in terms of liquid drainage and reduced interstitial liquid holdup were obtained using a vertical rather than horizontal support structure for the biomass and by operating the reactor with cocurrent air and liquid flow. With root growth, a pattern of spatial heterogeneity developed in the vessel. Higher local biomass densities, lower volumes of interstitial liquid, lower sugar concentrations, and higher root atropine contents were found in the upper sections of the root bed compared with the lower sections, suggesting a greater level of metabolic activity toward the top of the reactor. Although gas-liquid oxygen transfer to the spray droplets was very rapid, there was evidence of significant oxygen limitations in the reactor. Substantial volumes of non-free-draining interstitial liquid accumulated in the root bed. Roots near the bottom of the vessel trapped up to 3-4 times their own weight in liquid, thus eliminating the advantages of improved contact with the gas phase offered by liquid-dispersed culture systems. Local nutrient and product concentrations in the non-free-draining liquid were significantly different from those in the bulk medium, indicating poor liquid mixing within the root bed. Oxygen enrichment of the gas phase improved neither growth nor atropine production, highlighting the greater importance of liquid-solid compared with gas-liquid oxygen transfer resistance. The absence of mechanical or pneumatic agitation and the tendency of the root bed to accumulate liquid and impede drainage were identified as the major limitations to reactor performance. Improved reactor operating strategies and selection or development of root lines offering minimal resistance to liquid flow and low liquid retention characteristics are possible solutions to these problems.

Topological framework for local structure analysis in condensed matter

PubMed Central

Lazar, Emanuel A.; Han, Jian; Srolovitz, David J.

2015-01-01

Physical systems are frequently modeled as sets of points in space, each representing the position of an atom, molecule, or mesoscale particle. As many properties of such systems depend on the underlying ordering of their constituent particles, understanding that structure is a primary objective of condensed matter research. Although perfect crystals are fully described by a set of translation and basis vectors, real-world materials are never perfect, as thermal vibrations and defects introduce significant deviation from ideal order. Meanwhile, liquids and glasses present yet more complexity. A complete understanding of structure thus remains a central, open problem. Here we propose a unified mathematical framework, based on the topology of the Voronoi cell of a particle, for classifying local structure in ordered and disordered systems that is powerful and practical. We explain the underlying reason why this topological description of local structure is better suited for structural analysis than continuous descriptions. We demonstrate the connection of this approach to the behavior of physical systems and explore how crystalline structure is compromised at elevated temperatures. We also illustrate potential applications to identifying defects in plastically deformed polycrystals at high temperatures, automating analysis of complex structures, and characterizing general disordered systems. PMID:26460045

Molecular dynamic simulation of dicationic ionic liquids: effects of anions and alkyl chain length on liquid structure and diffusion.

PubMed

Yeganegi, Saeid; Soltanabadi, Azim; Farmanzadeh, Davood

2012-09-20

Structures and dynamics of nine geminal dicationic ionic liquids (DILs) Cn(mim)2X2, where n = 3, 6, and 9 and X = PF6(-), BF4(-), and Br(-), were studied by molecular dynamic simulations (J. Phys. Chem.B2004, 108, 2038-2047). A force field with a minor modification for C3(mim)2 × 2 was adopted for the simulations. Densities, detailed microscopic structures, mean-square displacements (MSD), and self-diffusivities for various ion pairs from MD simulations have been presented. The calculated densities for C9(mim)2X2 (X = Br(-) and BF4(-)) agreed well with the experimental values. The calculated RDFs show that anions are well organized around the imidazolium rings. The calculated RDFs indicate that, unlike the mono cationic ILs, the anions and cations in DILs distribute homogeneously. Enthalpies of vaporization were calculated and correlated with the structural features of DILs. The local structure of C9(mim)2X2 (X = Br, PF6) was examined by the spatial distribution function (SDF). The calculated SDFs show that similar trends were found by other groups for mono cationic ionic liquids (ILs). The highest probability densities are located around the imidazolium ring hydrogens. The calculated diffusion coefficients show that the ion diffusivities are 1 order of magnitude smaller than that of the mono cationic ionic liquids. The effects of alkyl chain length and anion type on the diffusion coefficient were also studied. The dynamics of the imidazolium rings and the alkyl chain in different time scales have also discussed. The calculated transference numbers show that the anions have the major role in carrying the electric current in a DIL.

Colloidal membranes: The rich confluence of geometry and liquid crystals

NASA Astrophysics Data System (ADS)

Kaplan, Cihan Nadir

A simple and experimentally realizable model system of chiral symmetry breaking is liquid-crystalline monolayers of aligned, identical hard rods. In these materials, tuning the chirality at the molecular level affects the geometry at systems level, thereby inducing a myriad of morphological transitions. This thesis presents theoretical studies motivated by the rich phenomenology of these colloidal monolayers. High molecular chirality leads to assemblages of rods exhibiting macroscopic handedness. In the first part we consider one such geometry, twisted ribbons, which are minimal surfaces to a double helix. By employing a theoretical approach that combines liquid-crystalline order with the preferred shape, we focus on the phase transition from simple flat monolayers to these twisted structures. In these monolayers, regions of broken chiral symmetry nucleate at the interfaces, as in a chiral smectic A sample. The second part particularly focuses on the detailed structure and thermodynamic stability of two types of observed interfaces, the monolayer edge and domain walls in simple flat monolayers. Both the edge and "twist-walls" are quasi-one-dimensional bands of molecular twist deformations dictated by local chiral interactions and surface energy considerations. We develop a unified theory of these interfaces by utilizing the de Gennes framework accompanied by appropriate surface energy terms. The last part turns to colloidal "cookies", which form in mixtures of rods with opposite handedness. These elegant structures are essentially flat monolayers surrounded by an array of local, three dimensional cusp defects. We reveal the thermodynamic and structural characteristics of cookies. Furthermore, cookies provide us with a simple relation to determine the intrinsic curvature modulus of our model system, an important constant associated with topological properties of membranes. Our results may have impacts on a broader class of soft thin films.

Toward understanding the structural heterogeneity and ion pair stability in dicationic ionic liquids.

PubMed

Li, Song; Bañuelos, José Leobardo; Zhang, Pengfei; Feng, Guang; Dai, Sheng; Rother, Gernot; Cummings, Peter T

2014-12-07

The structural and dynamical properties of dicationic ionic liquids (DILs) [Cn(mim)2](Tf2N)2, that is, 3-methylimidazolium dications separated by an alkyl chain and with bis(trifluoromethylsulfonyl)amide as the anion, were investigated by molecular dynamics (MD) simulation in combination with small/wide-angle X-ray scattering (SWAXS) measurements. Enhanced spatial heterogeneity is observed as the DIL chain length is increased, characterized by the changes in the scattering and the increased heterogeneity order parameter (HOP). Temperature variation imposes only slight influences on the local structures of DILs compared to monocationic ionic liquids (MILs). The peaks at 0.9 Å(-1) and 1.4 Å(-1) of the structure function shift towards low Q as the temperature increases, in a similar manner to MILs, and changes in peak positions in response to temperature changes are reflected in HOP variations. However, the prepeak shift with increasing temperature is ∼3 times smaller in DILs compared to MILs, and both MD and SWAXS indicate a DIL-specific prepeak shifting. Furthermore, the high ion pair/ion cage stability in DILs is indicative of high thermal stability and relative insensitivity of structural heterogeneity to temperature variation, which might be caused by the stronger Coulombic interactions in DILs.

Mapping the Free Energy of Lithium Solvation in the Protic Ionic Liquid Ethylammonuim Nitrate: A Metadynamics Study.

PubMed

Kachmar, Ali; Carignano, Marcelo; Laino, Teodoro; Iannuzzi, Marcella; Hutter, Jürg

2017-08-10

Understanding lithium solvation and transport in ionic liquids is important due to their possible application in electrochemical devices. Using first-principles simulations aided by a metadynamics approach we study the free-energy landscape for lithium ions at infinite dilution in ethylammonium nitrate, a protic ionic liquid. We analyze the local structure of the liquid around the lithium cation and obtain a quantitative picture in agreement with experimental findings. Our simulations show that the lowest two free energy minima correspond to conformations with the lithium ion being solvated either by three or four nitrate ions with a transition barrier between them of 0.2 eV. Other less probable conformations having different solvation pattern are also investigated. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling of Dendritic Structure and Microsegregation in Solidification of Al-Rich Quaternary Alloys

NASA Astrophysics Data System (ADS)

Dai, Ting; Zhu, Mingfang; Chen, Shuanglin; Cao, Weisheng

A two-dimensional cellular automaton (CA) model is coupled with a CALPHAD tool for the simulation of dendritic growth and microsegregation in solidification of quaternary alloys. The dynamics of dendritic growth is calculated according to the difference between the local equilibrium liquidus temperature and the actual temperature, incorporating with the Gibbs—Thomson effect and preferential dendritic growth orientations. Based on the local liquid compositions determined by solving the solutal transport equation in the domain, the local equilibrium liquidus temperature and the solid concentrations at the solid/liquid (SL) interface are calculated by the CALPHAD tool. The model was validated through the comparisons of the simulated results with the Scheil predictions for the solid composition profiles as a function of solid fraction in an Al-6wt%Cu-0.6wt%Mg-1wt%Si alloy. It is demonstrated that the model is capable of not only reproducing realistic dendrite morphologies, but also reasonably predicting microsegregation patterns in solidification of Al-rich quaternary alloys.

Ab-initio atomic level stress and role of d-orbitals in CuZr, CuZn and CuY

NASA Astrophysics Data System (ADS)

Ojha, Madhusudan; Nicholson, Don M.; Egami, Takeshi

2015-03-01

Atomic level stress offers a new tool to characterize materials within the local approximation to density functional theory (DFT). Ab-initio atomic level stresses in B2 structures of CuZr, CuZn and CuY are calculated and results are explained on the basis of d-orbital contributions to Density of States (DOS). The overlap of d-orbital DOS plays an important role in the relative magnitude of atomic level stresses in these structures. The trends in atomic level stresses that we observed in these simple B2 structures are also seen in complex structures such as liquids, glasses and solid solutions. The stresses are however modified by the different coordination and relaxed separation distances in these complex structures. We used the Locally Self-Consistent Multiple Scattering (LSMS) code and Vienna Ab-initio Simulation Package (VASP) for ab-initio calculations.

Variations of water's local-structure induced by solvation of NaCl

NASA Astrophysics Data System (ADS)

Gu, Bin; Zhang, Feng-Shou; Huang, Yu-Gai; Fang, Xia

2010-03-01

The researches on the structure of water and its changes induced by solutes are of enduring interests. The changes of the local structure of liquid water induced by NaCl solute under ambient conditions are studied and presented quantitatively with some order parameters and visualized with 2-body and 3-body correlation functions. The results show that, after the NaCl are solvated, the translational order t of water is decreased for the suppression of the second hydration shells around H2O molecules; the tetrahedral order (q) of water is also decreased and its favorite distribution peak moves from 0.76 to 0.5. In addition, the orientational freedom k and the diffusion coefficient D of water molecules are reduced because of new formed hydrogen-bonding structures between water and solvated ions.

Holographic Methods for the Investigation of Photophysical Properties.

DTIC Science & Technology

1983-04-22

terphenyl doped with 10- 3 mol/mol of pentacene . Obtaining k from decay curves as in * A -Fig. 14a and plotting k as a function of 02 (see Fig. 14b...translation diffusion of molecules in liquid solvents can be used to probe solute conformations, solvent-solute interactions and local solvent structure...eiion of 1.7omoAr WauW by TrArWAOn GFarinP So far, local heating by the absorption of the two interfering light pulses has not been taken into

Cross Flow Effects on Glaze Ice Roughness Formation

NASA Technical Reports Server (NTRS)

Tsao, Jen-Ching

2004-01-01

The present study examines the impact of large-scale cross flow on the creation of ice roughness elements on the leading edge of a swept wing under glaze icing conditions. A three-dimensional triple-deck structure is developed to describe the local interaction of a 3 D air boundary layer with ice sheets and liquid films. A linear stability analysis is presented here. It is found that, as the sweep angle increases, the local icing instabilities enhance and the most linearly unstable modes are strictly three dimensional.

A Liquid-Liquid Transition in an Undercooled Ti-Zr-Ni Liquid

NASA Technical Reports Server (NTRS)

Lee, G. W.; Gangopadhyay, A. K.; Kelton, K. F.; Hyers, R. W.; Rathz, T. J.; Rogers, J. R.

2003-01-01

If crystallization can be avoided, liquids enter a metastable (undercooled) state below their equilibrium liquidus temperatures, TI, finally freezing into a glass below a characteristic temperature called the glass transition temperature, T,. In rare cases, the undercooled liquid may undergo a liquid-liquid phase transition (liquid polymorphism) before entering the glassy state. This has been suggested from experimental studies of HzO and Si4. Such phase transitions have been predicted in some stable liquids, i.e. above TI at atmospheric pressure, for Si02 and BeF;, but these have not been verified experimentally. They have been observed in liquids of P7, Sis and C9, but only under high pressure. All of these transitions are driven by an anomalous density change, i.e. change in local structure, with temperature or pressure. In this letter we present the first experimental evidence for a phase transition in a low viscosity liquid that is not driven by an anomalous density change, but by an approach to a constant configuration state. A maximum in the specific heat at constant pressure, similar to what is normally observed near T,, is reported here for undercooled low viscosity liquids of quasicrystal- forming Ti-Zr-Ni alloys. that includes cooperativity, by incorporating a temperature dependent excitation energy fits the data well, signaling a phase transition.

Erasing no-man's land by thermodynamically stabilizing the liquid-liquid transition in tetrahedral particles.

PubMed

Smallenburg, Frank; Filion, Laura; Sciortino, Francesco

2014-09-01

One of the most controversial hypotheses for explaining the origin of the thermodynamic anomalies characterizing liquid water postulates the presence of a metastable second-order liquid-liquid critical point [1] located in the "no-man's land" [2]. In this scenario, two liquids with distinct local structure emerge near the critical temperature. Unfortunately, since spontaneous crystallization is rapid in this region, experimental support for this hypothesis relies on significant extrapolations, either from the metastable liquid or from amorphous solid water [3, 4]. Although the liquid-liquid transition is expected to feature in many tetrahedrally coordinated liquids, including silicon [5], carbon [6] and silica, even numerical studies of atomic and molecular models have been unable to conclusively prove the existence of this transition. Here we provide such evidence for a model in which it is possible to continuously tune the softness of the interparticle interaction and the flexibility of the bonds, the key ingredients controlling the existence of the critical point. We show that conditions exist where the full coexistence is thermodynamically stable with respect to crystallization. Our work offers a basis for designing colloidal analogues of water exhibiting liquid-liquid transitions in equilibrium, opening the way for experimental confirmation of the original hypothesis.

On the chain length dependence of local correlations in polymer melts and a perturbation theory of symmetric polymer blends.

PubMed

Morse, David C; Chung, Jun Kyung

2009-06-14

The self-consistent field (SCF) approach to the thermodynamics of dense polymer liquids is based on the idea that short-range correlations in a polymer liquid are almost independent of how monomers are connected into polymers over larger scales. Some limits of this idea are explored in the context of a perturbation theory for symmetric polymer blends. We consider mixtures of two structurally identical polymers, A and B, in which the AB monomer pair interaction differs slightly from the AA and BB interactions by an amount proportional to a parameter alpha. An expansion of the free energy to first order in alpha yields an excess free energy of mixing per monomer of the form alphaz(N)phi(A)phi(B) in both lattice and continuum models, where z(N) is a measure of the number of intermolecular near neighbors per monomer in a one-component (alpha=0) reference liquid with chains of length N. The quantity z(N) decreases slightly with increasing N because the concentration of intramolecular near neighbors is slightly higher for longer chains, creating a slightly deeper intermolecular correlation hole. We predict that z(N)=z(infinity)[1+betaN(-1/2)], where N is an invariant degree of polymerization and beta=(6/pi)(3/2) is a universal coefficient. This and related predictions about the slight N dependence of local correlations are confirmed by comparison to simulations of a continuum bead-spring model and to published lattice Monte Carlo simulations. We show that a renormalized one-loop theory for blends correctly describes this N dependence of local liquid structure. We also propose a way to estimate the effective interaction parameter appropriate for comparisons of simulation data to SCF theory and to coarse-grained theories of corrections to SCF theory, which is based on an extrapolation of perturbation theory to the limit N-->infinity.

Interface colloidal robotic manipulator

DOEpatents

Aronson, Igor; Snezhko, Oleksiy

2015-08-04

A magnetic colloidal system confined at the interface between two immiscible liquids and energized by an alternating magnetic field dynamically self-assembles into localized asters and arrays of asters. The colloidal system exhibits locomotion and shape change. By controlling a small external magnetic field applied parallel to the interface, structures can capture, transport, and position target particles.

Spin liquid polymorphism in a correlated electron system on the threshold of superconductivity

DOE PAGES

Zalinznyak, Igor; Savici, Andrei T.; Lumsden, Mark D.; ...

2015-08-18

We report neutron scattering measurements which reveal spin-liquid polymorphism in an “11” iron chalcogenide superconductor. It occurs when a poorly metallic magnetic state of FeTe is tuned toward superconductivity by substitution of a small amount of tellurium with isoelectronic sulfur. We also observe a liquid-like magnetic response, which is described by the coexistence of two disordered magnetic phases with different local structures whose relative abundance depends on temperature. One is the ferromagnetic (FM) plaquette phase observed in undoped, nonsuperconducting FeTe, which preserves the C 4 symmetry of the underlying square lattice and is favored at high temperatures, whereas the othermore » is the antiferromagnetic plaquette phase with broken C 4 symmetry, which emerges with doping and is predominant at low temperatures. These findings suggest the coexistence of and competition between two distinct liquid states, and a liquid–liquid phase transformation between these states, in the electronic spin system of FeTe 1-x(S,Se) x. We have thus discovered the remarkable physics of competing spin-liquid polymorphs in a correlated electron system approaching superconductivity. These results facilitate an understanding of large swaths of recent experimental data in unconventional superconductors. In particular, the phase with lower C 2 local symmetry, whose emergence precedes superconductivity, naturally accounts for a propensity for forming electronic nematic states which have been observed experimentally, in cuprate and iron-based superconductors alike.« less

Science Using an Electrostatic Levitation Furnace in the MUCAT Sector at the APS

NASA Technical Reports Server (NTRS)

Goldman, A.; Kelton, K. F.; Rogers, J. R.

2004-01-01

The original motivation for the construction of the BESL prototype was to obtain the first proof of a 50-year-old hypothesis regarding the solidification of liquid metals. Since the 1950s it has been known that under proper conditions liquid metals can be cooled below their melting temperature (undercooled) without crystallizing to the stable solid phase. In 1952 Frank proposed that this was because the atoms in the metallic liquid were arranged with the symmetry of an icosahedron, a Platonic solid consisting of 20 tetrahedra (4-sided pyramid-shaped polyhedra) arranged around a common center. Since this local atomic order is incompatible with the long-range translational periodicity of crystal phases, a barrier is formed to the formation of small regions of the crystal phase, the nucleation barrier. A proof of Frank's hypothesis required a direct correlation between measured icosahedral order in the undercooled liquid and the nucleation barrier. The tendency of sample containers to catalyze nucleation obscured this relation, requiring containerless techniques. Combining containerless processing techniques for electrostatically levitated droplets (ESL) with x-ray synchrotron methods, a team from Washington University, St. Louis, MO, NASA Marshall Space Flight Center, and MUCAT at the APS demonstrated an increasing icosahedral order in TiZrNi liquids with decreasing temperature below the melting temperature. The increased icosahedral order caused the transformation of the liquid to a metastable icosahedral quasicrystal phase, instead of the stable tetrahedrally-coordinated crystal intermetallic, giving the first clear demonstration of the connection between the nucleation barrier and the local structure of the liquid, verifying Frank's hypothesis for this alloy.

The local structure and EPR parameter of compressed tetrahedral CuIIX4 components in proteins, liquid precursors and nanomaterials

NASA Astrophysics Data System (ADS)

Kuang, Min-Quan; Yuan, Hong-Kuan; Chen, Hong; Wang, Li-Dan; Duan, Shu-Kai

2017-11-01

The local structures and EPR parameters of flatten CuIIX4 (X = N, O, S, Se, Cl and Br) compositions in proteins, liquid precursors and nanocrystals are analyzed and computed based on the cluster approach and perturbation method. The g and A components of copper(II) under D2d symmetry are well explained in terms of a global parameter β characterizing the local angular distortion away from the ideal Td tetrahedron where β0 ≈ 109.4712°. The calculated isotropy and anisotropy of g factors (gav and Δg) are found suffering an increase with the enlargement of the obtained βcal, which is consistent with the increasing trends of both experimental Δg and gav. The variation trend of gav can also be interpreted by the decreasing covalence of the studied system (or the increasing covalency factor ρ). On the other hand, the hyperfine structure constant A‖ decreases with increasing βcal. The obtained cubic crystal field parameter Dq and the core polarization constant κ experience the dropping and growing tendencies, respectively, with the enlarging copper-ligand bond length R. The above correlations are appropriate for all the studied CuIIX4 complexes and thus this work would be helpful to establish the complete physical scheme for uniform analysis on spectroscopic and magnetic behaviours of MX4 (M = transition metal and X = halides and pseudohalides) compounds.

Viewpoint 9--molecular structure of aqueous interfaces

NASA Technical Reports Server (NTRS)

Pohorille, A.; Wilson, M. A.

1993-01-01

In this review we summarize recent progress in our understanding of the structure of aqueous interfaces emerging from molecular level computer simulations. It is emphasized that the presence of the interface induces specific structural effects which, in turn, influence a wide variety of phenomena occurring near the phase boundaries. At the liquid-vapor interface, the most probable orientations of a water molecule is such that its dipole moment lies parallel to the interface, one O-H bond points toward the vapor and the other O-H bond is directed toward the liquid. The orientational distributions are broad and slightly asymmetric, resulting in an excess dipole moment pointing toward the liquid. These structural preferences persist at interfaces between water and nonpolar liquids, indicating that the interactions between the two liquids in contact are weak. It was found that liquid-liquid interfaces are locally sharp but broadened by capillary waves. One consequence of anisotropic orientations of interfacial water molecules is asymmetric interactions, with respect to the sign of the charge, of ions with the water surface. It was found that even very close to the surface ions retain their hydration shells. New features of aqueous interfaces have been revealed in studies of water-membrane and water-monolayer systems. In particular, water molecules are strongly oriented by the polar head groups of the amphiphilic phase, and they penetrate the hydrophilic head-group region, but not the hydrophobic core. At infinite dilution near interfaces, amphiphilic molecules exhibit behavior different from that in the gas phase or in bulk water. This result sheds new light on the nature of hydrophobic effect in the interfacial regions. The presence of interfaces was also shown to affect both equilibrium and dynamic components of rates of chemical reactions. Applications of continuum models to interfacial problems have been, so far, unsuccessful. This, again, underscores the importance of molecular-level information about interfaces.

Versatile application of indirect Fourier transformation to structure factor analysis: from X-ray diffraction of molecular liquids to small angle scattering of protein solutions.

PubMed

Fukasawa, Toshiko; Sato, Takaaki

2011-02-28

We highlight versatile applicability of a structure-factor indirect Fourier transformation (IFT) technique, hereafter called SQ-IFT. The original IFT aims at the pair distance distribution function, p(r), of colloidal particles from small angle scattering of X-rays (SAXS) and neutrons (SANS), allowing the conversion of the experimental form factor, P(q), into a more intuitive real-space spatial autocorrelation function. Instead, SQ-IFT is an interaction potential model-free approach to the 'effective' or 'experimental' structure factor to yield the pair correlation functions (PCFs), g(r), of colloidal dispersions like globular protein solutions for small-angle scattering data as well as the radial distribution functions (RDFs) of molecular liquids in liquid diffraction (LD) experiments. We show that SQ-IFT yields accurate RDFs of liquid H(2)O and monohydric alcohol reflecting their local intermolecular structures, in which q-weighted structure function, qH(q), conventionally utilized in many LD studies out of necessity of performing direct Fourier transformation, is no longer required. We also show that SQ-IFT applied to theoretically calculated structure factors for uncharged and charged colloidal dispersions almost perfectly reproduces g(r) obtained as a solution of the Ornstein-Zernike (OZ) equation. We further demonstrate the relevance of SQ-IFT in its practical applications, using SANS effective structure factors of lysozyme solutions reported in recent literatures which revealed the equilibrium cluster formation due to coexisting long range electrostatic repulsion and short range attraction between the proteins. Finally, we present SAXS experiments on human serum albumin (HSA) at different ionic strength and protein concentration, in which we discuss the real space picture of spatial distributions of the proteins via the interaction potential model-free route.

Mass density fluctuations in quantum and classical descriptions of liquid water

NASA Astrophysics Data System (ADS)

Galib, Mirza; Duignan, Timothy T.; Misteli, Yannick; Baer, Marcel D.; Schenter, Gregory K.; Hutter, Jürg; Mundy, Christopher J.

2017-06-01

First principles molecular dynamics simulation protocol is established using revised functional of Perdew-Burke-Ernzerhof (revPBE) in conjunction with Grimme's third generation of dispersion (D3) correction to describe the properties of water at ambient conditions. This study also demonstrates the consistency of the structure of water across both isobaric (NpT) and isothermal (NVT) ensembles. Going beyond the standard structural benchmarks for liquid water, we compute properties that are connected to both local structure and mass density fluctuations that are related to concepts of solvation and hydrophobicity. We directly compare our revPBE results to the Becke-Lee-Yang-Parr (BLYP) plus Grimme dispersion corrections (D2) and both the empirical fixed charged model (SPC/E) and many body interaction potential model (MB-pol) to further our understanding of how the computed properties herein depend on the form of the interaction potential.

Mass density fluctuations in quantum and classical descriptions of liquid water

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

Galib, Mirza; Duignan, Timothy T.; Misteli, Yannick

First principles molecular dynamics simulation protocol is established using revised functional of Perdew-Burke-Ernzerhof (revPBE) in conjunction with Grimme's third generation of dispersion (D3) correction to describe properties of water at ambient conditions. This study also demonstrates the consistency of the structure of water across both isobaric (NpT) and isothermal (NVT) ensembles. Going beyond the standard structural benchmarks for liquid water, we compute properties that are connected to both local structure and mass density fluctuations that are related to concepts of solvation and hydrophobicity. We directly compare our revPBE results to the Becke-Lee-Yang-Parr (BLYP) plus Grimme dispersion corrections (D2) and bothmore » the empirical fixed charged model (SPC/E) and many body interaction potential model (MB-pol) to further our understanding of how the computed properties herein depend on the form of the interaction potential.« less

Liquid Crystal Mediated Nano-assembled Gold Micro-shells

NASA Astrophysics Data System (ADS)

Quint, Makiko; Sarang, Som; Quint, David; Huang, Kerwyn; Gopinathan, Ajay; Hirst, Linda; Ghosh, Sayantani

We have created 3D nano-assenbled micro-shell by using thermotropic liquid crystal (LC), 4-Cyano-4'-pentylbiphenyl (5CB), doped with mesogen-functionalized gold nanoparticles (AuNPs). The assembly process is driven by the isotropic-nematic phase transition dynamics. We uniformly disperse the functionalized AuNPs into isotropic liquid crystal matrix and the mixture is cooled from the isotropic to the nematic phase. During the phase transition, the separation of LC-AuNP rich isotropic and ordered 5CB rich domains cause the functionalized AuNPs to move into the shrinking isotropic regions. The mesogenic ligands are locally crystalized during this process, which leads to the formation of a spherical shell with a densely packed wall of AuNPs. These micro-shells are capable of encapsulating fluorescence dye without visible leakages for several months. Additionally, they demonstrate strong localized surface plasmon resonance, which leads to localized heating on optical excitation. This photothermal effect disrupts the structure, releasing contents within seconds. Our results exhibiting the capture and optically regulated release of encapsulated substances is a novel platform that combines drug-delivery and photothermal therapy in one versatile and multifunctional unit. This work is supported by the NSF Grants No. DMR-1056860, ECC-1227034, and a University of California Merced Faculty Mentor Fellowship.

Whisker Formation in Porosity in Al Alloys

NASA Astrophysics Data System (ADS)

Griffiths, William David; Elsayed, Ahmed; El-Sayed, Mahmoud Ahmed

2016-12-01

An examination of the fracture surfaces of tensile test bars from Al alloy castings held in the liquid state for up to 20 minutes revealed porosity which in some cases contained whisker-like features. Energy-dispersive X-ray analysis in a SEM suggested that these might be oxide whiskers forming in an oxide-related pore or double oxide film defect. Such entrainment defects (also known as bifilms) may entrap a small amount of the local atmosphere when they form and become incorporated into the liquid metal. This atmosphere may be predominantly air, which then subsequently reacts with the surrounding melt, firstly by reaction with oxygen and secondly by reaction with nitrogen. A CFD model of the heat distribution associated with the reactions between the interior atmosphere of a double oxide film defect and the surrounding liquid alloy suggested that highly localized increases in temperature, up to about 2000 K to 5000 K (1727 °C to 4727 °C), could occur, over a scale of a few hundred micrometers. Such localized increases in temperature might lead to the evaporation or disassociation of oxide within the pore, followed by condensation, to form the whisker structures observed. Hydrogen might also be expected to diffuse into the bifilm and may play a role in the chemical reactions associated with the development of the bifilm.

Coulomb spin liquid in anion-disordered pyrochlore Tb 2Hf 2O 7

DOE PAGES

Sibille, Romain; Lhotel, Elsa; Hatnean, Monica Ciomaga; ...

2017-10-12

Here, the charge ordered structure of ions and vacancies characterizing rare-earth pyrochlore oxides serves as a model for the study of geometrically frustrated magnetism. The organization of magnetic ions into networks of corner-sharing tetrahedra gives rise to highly correlated magnetic phases with strong fluctuations, including spin liquids and spin ices. It is an open question how these ground states governed by local rules are affected by disorder. Here we demonstrate in the pyrochlore Tb 2Hf 2O 7, that the vicinity of the disordering transition towards a defective fluorite structure translates into a tunable density of anion Frenkel disorder while cationsmore » remain ordered. Quenched random crystal fields and disordered exchange interactions can therefore be introduced into otherwise perfect pyrochlore lattices of magnetic ions. We show that disorder can play a crucial role in preventing long-range magnetic order at low temperatures, and instead induces a strongly fluctuating Coulomb spin liquid with defect-induced frozen magnetic degrees of freedom.« less

The hydrogen-bond network of water supports propagating optical phonon-like modes

DOE PAGES

Elton, Daniel C.; Fernández-Serra, Marivi

2016-01-04

The local structure of liquid water as a function of temperature is a source of intense research. This structure is intimately linked to the dynamics of water molecules, which can be measured using Raman and infrared spectroscopies. The assignment of spectral peaks depends on whether they are collective modes or single-molecule motions. Vibrational modes in liquids are usually considered to be associated to the motions of single molecules or small clusters. Using molecular dynamics simulations, here we find dispersive optical phonon-like modes in the librational and OH-stretching bands. We argue that on subpicosecond time scales these modes propagate through water’smore » hydrogen-bond network over distances of up to 2 nm. In the long wavelength limit these optical modes exhibit longitudinal–transverse splitting, indicating the presence of coherent long-range dipole–dipole interactions, as in ice. Lastly, our results indicate the dynamics of liquid water have more similarities to ice than previously thought.« less

Freezing lines of colloidal Yukawa spheres. II. Local structure and characteristic lengths

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

Gapinski, Jacek, E-mail: gapinski@amu.edu.pl; Patkowski, Adam; NanoBioMedical Center, A. Mickiewicz University, Umultowska 85, 61-614 Poznań

Using the Rogers-Young (RY) integral equation scheme for the static pair correlation functions combined with the liquid-phase Hansen-Verlet freezing rule, we study the generic behavior of the radial distribution function and static structure factor of monodisperse charge-stabilized suspensions with Yukawa-type repulsive particle interactions at freezing. In a related article, labeled Paper I [J. Gapinski, G. Nägele, and A. Patkowski, J. Chem. Phys. 136, 024507 (2012)], this hybrid method was used to determine two-parameter freezing lines for experimentally controllable parameters, characteristic of suspensions of charged silica spheres in dimethylformamide. A universal scaling of the RY radial distribution function maximum is shownmore » to apply to the liquid-bcc and liquid-fcc segments of the universal freezing line. A thorough analysis is made of the behavior of characteristic distances and wavenumbers, next-neighbor particle coordination numbers, osmotic compressibility factor, and the Ravaché-Mountain-Streett minimum-maximum radial distribution function ratio.« less

Oral and transdermal drug delivery systems: role of lipid-based lyotropic liquid crystals.

PubMed

Rajabalaya, Rajan; Musa, Muhammad Nuh; Kifli, Nurolaini; David, Sheba R

2017-01-01

Liquid crystal (LC) dosage forms, particularly those using lipid-based lyotropic LCs (LLCs), have generated considerable interest as potential drug delivery systems. LCs have the physical properties of liquids but retain some of the structural characteristics of crystalline solids. They are compatible with hydrophobic and hydrophilic compounds of many different classes and can protect even biologicals and nucleic acids from degradation. This review, focused on research conducted over the past 5 years, discusses the structural evaluation of LCs and their effects in drug formulations. The structural classification of LLCs into lamellar, hexagonal and micellar cubic phases is described. The structures of these phases are influenced by the addition of surfactants, which include a variety of nontoxic, biodegradable lipids; these also enhance drug solubility. LLC structure influences drug localization, particle size and viscosity, which, in turn, determine drug delivery properties. Through several specific examples, we describe the applications of LLCs in oral and topical drug formulations, the latter including transdermal and ocular delivery. In oral LLC formulations, micelle compositions and the resulting LLC structures can determine drug solubilization and stability as well as intestinal transport and absorption. Similarly, in topical LLC formulations, composition can influence whether the drug is retained in the skin or delivered transdermally. Owing to their enhancement of drug stability and promotion of controlled drug delivery, LLCs are becoming increasingly popular in pharmaceutical formulations.

Oral and transdermal drug delivery systems: role of lipid-based lyotropic liquid crystals

PubMed Central

Rajabalaya, Rajan; Musa, Muhammad Nuh; Kifli, Nurolaini; David, Sheba R

2017-01-01

Liquid crystal (LC) dosage forms, particularly those using lipid-based lyotropic LCs (LLCs), have generated considerable interest as potential drug delivery systems. LCs have the physical properties of liquids but retain some of the structural characteristics of crystalline solids. They are compatible with hydrophobic and hydrophilic compounds of many different classes and can protect even biologicals and nucleic acids from degradation. This review, focused on research conducted over the past 5 years, discusses the structural evaluation of LCs and their effects in drug formulations. The structural classification of LLCs into lamellar, hexagonal and micellar cubic phases is described. The structures of these phases are influenced by the addition of surfactants, which include a variety of nontoxic, biodegradable lipids; these also enhance drug solubility. LLC structure influences drug localization, particle size and viscosity, which, in turn, determine drug delivery properties. Through several specific examples, we describe the applications of LLCs in oral and topical drug formulations, the latter including transdermal and ocular delivery. In oral LLC formulations, micelle compositions and the resulting LLC structures can determine drug solubilization and stability as well as intestinal transport and absorption. Similarly, in topical LLC formulations, composition can influence whether the drug is retained in the skin or delivered transdermally. Owing to their enhancement of drug stability and promotion of controlled drug delivery, LLCs are becoming increasingly popular in pharmaceutical formulations. PMID:28243062

Gas-Expanded Liquids: Synergism of Experimental and Computational Determinations of Local Structure

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

Charles A. Eckert; Charles L. Liotta; Rigoberto Hernandez

2007-06-26

This project focuses on the characterization of a new class of solvent systems called gas-expanded liquids (GXLs), targeted for green-chemistry processing. The collaboration has adopted a synergistic approach combining elements of molecular dynamics (MD) simulation and spectroscopic experiments to explore the local solvent behavior that could not be studied by simulation or experiment alone. The major accomplishments from this project are: • Applied MD simulations to explore the non-uniform structure of CO2/methanol and CO2/acetone GXLs and studied their dynamic behavior with self-diffusion coefficients and correlation functions • Studied local solvent structure and solvation behavior with a combination of spectroscopy andmore » MD simulations • Measured transport properties of heterocyclic solutes in GXLs through Taylor-Aris diffusion techniques and compared these findings to those of MD simulations • Probed local polarity and specific solute-solvent interactions with Diels-Alder and SN2 reaction studies The broader scientific impact resulting from the research activities of this contract have been recognized by two recent awards: the Presidential Green Chemistry Award (Eckert & Liotta) and a fellowship in the American Association for the Advancement of Science (Hernandez). In addition to the technical aspects of this contract, the investigators have been engaged in a number of programs extending the broader impacts of this project. The project has directly supported the development of two postdoctoral researcher, four graduate students, and five undergraduate students. Several of the undergraduate students were co-funded by a Georgia Tech program, the Presidential Undergraduate Research Award. The other student, an African-American female graduated from Georgia Tech in December 2005, and was co-funded through an NSF Research and Education for Undergraduates (REU) award.« less

Mechanical heterogeneity in ionic liquids

NASA Astrophysics Data System (ADS)

Veldhorst, Arno A.; Ribeiro, Mauro C. C.

2018-05-01

Molecular dynamics (MD) simulations of five ionic liquids based on 1-alkyl-3-methylimidazolium cations, [CnC1im]+, have been performed in order to calculate high-frequency elastic moduli and to evaluate heterogeneity of local elastic moduli. The MD simulations of [CnC1im][NO3], n = 2, 4, 6, and 8, assessed the effect of domain segregation when the alkyl chain length increases, and [C8C1im][PF6] assessed the effect of strength of anion-cation interaction. Dispersion curves of excitation energies of longitudinal and transverse acoustic, LA and TA, modes were obtained from time correlation functions of mass currents at different wavevectors. High-frequency sound velocity of LA modes depends on the alkyl chain length, but sound velocity for TA modes does not. High-frequency bulk and shear moduli, K∞ and G∞, depend on the alkyl chain length because of a density effect. Both K∞ and G∞ are strongly dependent on the anion. The calculation of local bulk and shear moduli was accomplished by performing bulk and shear deformations of the systems cooled to 0 K. The simulations showed a clear connection between structural and elastic modulus heterogeneities. The development of nano-heterogeneous structure with increasing length of the alkyl chain in [CnC1im][NO3] implies lower values for local bulk and shear moduli in the non-polar domains. The mean value and the standard deviations of distributions of local elastic moduli decrease when [NO3]- is replaced by the less coordinating [PF6]- anion.

Local order and crystallization of dense polydisperse hard spheres

NASA Astrophysics Data System (ADS)

Coslovich, Daniele; Ozawa, Misaki; Berthier, Ludovic

2018-04-01

Computer simulations give precious insight into the microscopic behavior of supercooled liquids and glasses, but their typical time scales are orders of magnitude shorter than the experimentally relevant ones. We recently closed this gap for a class of models of size polydisperse fluids, which we successfully equilibrate beyond laboratory time scales by means of the swap Monte Carlo algorithm. In this contribution, we study the interplay between compositional and geometric local orders in a model of polydisperse hard spheres equilibrated with this algorithm. Local compositional order has a weak state dependence, while local geometric order associated to icosahedral arrangements grows more markedly but only at very high density. We quantify the correlation lengths and the degree of sphericity associated to icosahedral structures and compare these results to those for the Wahnström Lennard-Jones mixture. Finally, we analyze the structure of very dense samples that partially crystallized following a pattern incompatible with conventional fractionation scenarios. The crystal structure has the symmetry of aluminum diboride and involves a subset of small and large particles with size ratio approximately equal to 0.5.

Electronic structure Fermi liquid theory of high Tc superconductors: Comparison of predictions with experiments

NASA Technical Reports Server (NTRS)

Yu, Jaejun; Freeman, A. J.

1991-01-01

Predictions of local density functional (LDF) calculations of the electronic structure and transport properties of high T(sub c) superconductors are presented. As evidenced by the excellent agreement with both photoemission and positron annihilation experiments, a Fermi liquid nature of the 'normal' state of the high T(sub c) superconductors become clear for the metallic phase of these oxides. In addition, LDF predictions on the normal state transport properties are qualitatively in agreement with experiments on single crystals. It is emphasized that the signs of the Hall coefficients for the high T(sub c) superconductors are not consistent with the types of dopants (e.g., electron-doped or hole-doped) but are determined by the topology of the Fermi surfaces obtained from the LDF calculations.

Polar POLICRYPS diffractive structures generate cylindrical vector beams

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

Alj, Domenico; Caputo, Roberto, E-mail: roberto.caputo@fis.unical.it; Umeton, Cesare

2015-11-16

Local shaping of the polarization state of a light beam is appealing for a number of applications. This can be achieved by employing devices containing birefringent materials. In this article, we present one such enables converting a uniformly circularly polarized beam into a cylindrical vector beam (CVB). This device has been fabricated by exploiting the POLICRYPS (POlymer-LIquid CRYstals-Polymer-Slices) photocuring technique. It is a liquid-crystal-based optical diffraction grating featuring polar symmetry of the director alignment. We have characterized the resulting CVB profile and polarization for the cases of left and right circularly polarized incoming beams.

Mechanistic insight into formation and changes of nanoparticles in MgF2 sols evidenced by liquid and solid state NMR.

PubMed

Karg, M; Scholz, G; König, R; Kemnitz, E

2012-02-28

The fluorolytic sol-gel reaction of magnesium methoxide with HF in methanol was studied by (19)F, (1)H and (13)C liquid and solid state NMR. In (19)F NMR five different species were identified, three of which belong to magnesium fluoride nanoparticles, i.e. NMR gave access to local structures of solid particles in suspensions. The long-term evolution of (19)F signals was followed and along with (19)F MAS NMR experiments of sols rotating at 13 kHz mechanistic insights into the ageing processes were obtained.

Similar local order in disordered fluorite and aperiodic pyrochlore structures

DOE PAGES

Shamblin, Jacob; Tracy, Cameron; Palomares, Raul; ...

2017-10-01

A major challenge to understanding the response of materials to extreme environments (e.g., nuclear fuels/waste forms and fusion materials) is to unravel the processes by which a material can incorporate atomic-scale disorder, and at the same time, remain crystalline. While it has long been known that all condensed matter, even liquids and glasses, possess short-range order, the relation between fully-ordered, disordered, and aperiodic structures over multiple length scales is not well understood. For example, when defects are introduced (via pressure or irradiation) into materials adopting the pyrochlore structure, these complex oxides either disorder over specific crystallographic sites, remaining crystalline, ormore » become aperiodic. Here we present neutron total scattering results characterizing the irradiation response of two pyrochlores, one that is known to disorder (Er2Sn2O7) and the other to amorphize (Dy2Sn2O7) under ion irradiation. The results demonstrate that in both cases, the local pyrochlore structure is transformed into similar short range configurations that are best fit by the orthorhombic weberite structure, even though the two compositions have distinctly different structures, aperiodic vs. disordered-crystalline, at longer length scales. Thus, a material's resistance to amorphization may not depend primarily on local defect formation energies, but rather on the structure's compatibility with meso-scale modulations of the local order in a way that maintains long-range periodicity.« less

RNA stores tau reversibly in complex coacervates

PubMed Central

Lin, Yanxian; Eschmann, Neil A.; Zhou, Hongjun; Rauch, Jennifer N.; Hernandez, Israel; Guzman, Elmer; Kosik, Kenneth S.; Han, Songi

2017-01-01

Nonmembrane-bound organelles that behave like liquid droplets are widespread among eukaryotic cells. Their dysregulation appears to be a critical step in several neurodegenerative conditions. Here, we report that tau protein, the primary constituent of Alzheimer neurofibrillary tangles, can form liquid droplets and therefore has the necessary biophysical properties to undergo liquid-liquid phase separation (LLPS) in cells. Consonant with the factors that induce LLPS, tau is an intrinsically disordered protein that complexes with RNA to form droplets. Uniquely, the pool of RNAs to which tau binds in living cells are tRNAs. This phase state of tau is held in an approximately 1:1 charge balance across the protein and the nucleic acid constituents, and can thus be maximal at different RNA:tau mass ratios, depending on the biopolymer constituents involved. This feature is characteristic of complex coacervation. We furthermore show that the LLPS process is directly and sensitively tuned by salt concentration and temperature, implying it is modulated by both electrostatic interactions between the involved protein and nucleic acid constituents, as well as net changes in entropy. Despite the high protein concentration within the complex coacervate phase, tau is locally freely tumbling and capable of diffusing through the droplet interior. In fact, tau in the condensed phase state does not reveal any immediate changes in local protein packing, local conformations and local protein dynamics from that of tau in the dilute solution state. In contrast, the population of aggregation-prone tau as induced by the complexation with heparin is accompanied by large changes in local tau conformations and irreversible aggregation. However, prolonged residency within the droplet state eventually results in the emergence of detectable β-sheet structures according to thioflavin-T assay. These findings suggest that the droplet state can incubate tau and predispose the protein toward the formation of insoluble fibrils. PMID:28683104

Onset of ice VII phase during ps laser pulse propagation through liquid water

NASA Astrophysics Data System (ADS)

Paturi, Prem Kiran; Vaddapally, Rakesh Kumar; Acrhem Team

2015-06-01

Water dominantly present in liquid state on earth gets transformed to crystalline polymorphs under different dynamic loading conditions. Out of 15 different crystalline phases discovered till date, ice VII is observed to be stable over wide pressure (2-63 GPa) and temperature (>273 K) ranges. We present the onset of ice VII phase at low threshold of 2 mJ/pulse during 30 ps (532 nm, 10 Hz) laser pulse induced shock propagating through liquid water. Role of input pulse energy on the evolution of Stoke's and anti-Stoke's Raman shift of the dominant A1g mode of ice VII, filamentation, free-electrons, plasma shielding is presented. The H-bond network rearrangement, electron ion energy transfer time coinciding with the excitation pulse duration supported by the filamentation and plasma shielding of the ps laser pulses reduced the threshold of ice VII structure formation. Filamentation and the plasma shielding have shown the localized creation and sustenance of ice VII structure in liquid water over 3 mm length and 50 μm area of cross-section. The work is supported by Defence Research and Developement Organization, India through Grants-in-Aid Program.

Study of diffusion and local structure of sodium-silicate liquid: the molecular dynamic simulation

NASA Astrophysics Data System (ADS)

Hung, Pham Khac; Noritake, Fumiya; San, Luyen Thi; Van, To Ba; Vinh, Le The

2017-10-01

A systematic analysis on sodium-silicate melt with various silica contents was carried out. The simulation revealed two diffusion mechanisms occurred in the melt: the bond-breaking and hopping between sites. The local structure was analyzed through T-simplexes. It was revealed that T-clusters have a non-spherical shape and represent the diffusion channel, in which Na atoms are dominant, but no any O atoms are located. The SiO2-poor melt acquires a long channel. In contrast, the SiO2-rich melt consists of unconnected short channels. The simulation also revealed the immobile and mobile regions which differ in local structure and constituent composition. We propose a new CL-function to characterizing the spatial distribution of different atom component. The spatial distribution of mobile and immobile atoms is found quite different. In particular, the immobile atoms are concentrated in high-density regions possessing very large density of immobile atoms. The spatial distribution of mobile atoms in contrast is more homogeneous.

Structural Study of Liquid Lithium Niobate by Neutron Diffraction Role of the Li Atom in the Clustering Near Solidification

NASA Astrophysics Data System (ADS)

Andonov, P.; Fischer, H. E.; Palleau, P.; Kimura, S.

2001-05-01

The structure of liquid LiNbO3 has been investigated by neutron diffraction using samples with different isotopic composition of lithium. The intensity scattered by these samples has been measured for momentum transfers 0.4 Å-1 T> 1500 K, which include the undercooling domain. From an analysis of the correlation functions Gij(r) of the atomic pairs Li-Li, Li-Nb, Li-O and their structural evolutions, given by Δ Gi-j (r) = Gi-j(r)1500 -Gi-j(r)1550 made with reference to the crystalline LiNbO3 ferroelectric structure, it was possible to confirm a local ordering similar to that of the crystal. The presence of clusters (groupings of NbO3 octahedra) is confirmed. Both regular and irregular N b06 octahedra are observed in the liquid near solidification. With its high mobil­ity in the melt, the Li atom plays an important role in the clustering: the Li-O and Li-Nb bonds make possible the staking of four octahedra groups into clusters of eight octahedra or more. The Li-Li bonds join these groups. The diameter of the clusters is a least 22 Å in the undercooling regime.

Localized soft elasticity in liquid crystal elastomers (POSTPRINT)

DTIC Science & Technology

2016-02-23

AFRL-RX-WP-JA-2016-0280 LOCALIZED SOFT ELASTICITY IN LIQUID CRYSTAL ELASTOMER (POSTPRINT) Taylor H. Ware, Andreas F. Shick, and...MM-YY) 2. REPORT TYPE 3. DATES COVERED (From - To) 11 August 2015 Interim 31 January 2014 – 11 July 2015 4. TITLE AND SUBTITLE LOCALIZED SOFT ...2016 Localized soft elasticity in liquid crystal elastomers Taylor H. Ware1,2, John S. Biggins3, Andreas F. Shick1, Mark Warner3 & Timothy J. White1

Confinement-Driven Phase Separation of Quantum Liquid Mixtures

NASA Astrophysics Data System (ADS)

Prisk, T. R.; Pantalei, C.; Kaiser, H.; Sokol, P. E.

2012-08-01

We report small-angle neutron scattering studies of liquid helium mixtures confined in Mobil Crystalline Material-41 (MCM-41), a porous silica glass with narrow cylindrical nanopores (d=3.4nm). MCM-41 is an ideal model adsorbent for fundamental studies of gas sorption in porous media because its monodisperse pores are arranged in a 2D triangular lattice. The small-angle scattering consists of a series of diffraction peaks whose intensities are determined by how the imbibed liquid fills the pores. Pure He4 adsorbed in the pores show classic, layer-by-layer film growth as a function of pore filling, leaving the long range symmetry of the system intact. In contrast, the adsorption of He3-He4 mixtures produces a structure incommensurate with the pore lattice. Neither capillary condensation nor preferential adsorption of one helium isotope to the pore walls can provide the symmetry-breaking mechanism. The scattering is consistent with the formation of randomly distributed liquid-liquid microdomains ˜2.3nm in size, providing evidence that confinement in a nanometer scale capillary can drive local phase separation in quantum liquid mixtures.

String-like cooperative motion in homogeneous melting

PubMed Central

Zhang, Hao; Khalkhali, Mohammad; Liu, Qingxia; Douglas, Jack F.

2013-01-01

Despite the fundamental nature and practical importance of melting, there is still no generally accepted theory of this ubiquitous phenomenon. Even the earliest simulations of melting of hard discs by Alder and Wainwright indicated the active role of collective atomic motion in melting and here we utilize molecular dynamics simulation to determine whether these correlated motions are similar to those found in recent studies of glass-forming (GF) liquids and other condensed, strongly interacting, particle systems. We indeed find string-like collective atomic motion in our simulations of “superheated” Ni crystals, but other observations indicate significant differences from GF liquids. For example, we observe neither stretched exponential structural relaxation, nor any decoupling phenomenon, while we do find a boson peak, findings that have strong implications for understanding the physical origin of these universal properties of GF liquids. Our simulations also provide a novel view of “homogeneous” melting in which a small concentration of interstitial defects exerts a powerful effect on the crystal stability through their initiation and propagation of collective atomic motion. These relatively rare point defects are found to propagate down the strings like solitons, driving the collective motion. Crystal integrity remains preserved when the permutational atomic motions take the form of ring-like atomic exchanges, but a topological transition occurs at higher temperatures where the rings open to form linear chains similar in geometrical form and length distribution to the strings of GF liquids. The local symmetry breaking effect of the open strings apparently destabilizes the local lattice structure and precipitates crystal melting. The crystal defects are thus not static entities under dynamic conditions, such as elevated temperatures or material loading, but rather are active agents exhibiting a rich nonlinear dynamics that is not addressed in conventional “static” defect melting models. PMID:23556789

String-like cooperative motion in homogeneous melting.

PubMed

Zhang, Hao; Khalkhali, Mohammad; Liu, Qingxia; Douglas, Jack F

2013-03-28

Despite the fundamental nature and practical importance of melting, there is still no generally accepted theory of this ubiquitous phenomenon. Even the earliest simulations of melting of hard discs by Alder and Wainwright indicated the active role of collective atomic motion in melting and here we utilize molecular dynamics simulation to determine whether these correlated motions are similar to those found in recent studies of glass-forming (GF) liquids and other condensed, strongly interacting, particle systems. We indeed find string-like collective atomic motion in our simulations of "superheated" Ni crystals, but other observations indicate significant differences from GF liquids. For example, we observe neither stretched exponential structural relaxation, nor any decoupling phenomenon, while we do find a boson peak, findings that have strong implications for understanding the physical origin of these universal properties of GF liquids. Our simulations also provide a novel view of "homogeneous" melting in which a small concentration of interstitial defects exerts a powerful effect on the crystal stability through their initiation and propagation of collective atomic motion. These relatively rare point defects are found to propagate down the strings like solitons, driving the collective motion. Crystal integrity remains preserved when the permutational atomic motions take the form of ring-like atomic exchanges, but a topological transition occurs at higher temperatures where the rings open to form linear chains similar in geometrical form and length distribution to the strings of GF liquids. The local symmetry breaking effect of the open strings apparently destabilizes the local lattice structure and precipitates crystal melting. The crystal defects are thus not static entities under dynamic conditions, such as elevated temperatures or material loading, but rather are active agents exhibiting a rich nonlinear dynamics that is not addressed in conventional "static" defect melting models.

A study of fluid-structure problems

NASA Astrophysics Data System (ADS)

Lam, Dennis Kang-Por

The stability of structures with and without fluid load is investigated. A method is developed for determining the fluid load in terms of added structural mass. Finite element methods are employed to study the buckling of a cylindrical shell under axial compression and liquid storage tanks under hydrodynamic load. Both linear and nonlinear analyses are performed. Diamond modes are found to be the possible postbuckling shapes of the cylindrical shell. Local buckling including elephant-foot buckle and diamond buckle are found for the liquid storage tank models. Comparison between the linear and nonlinear results indicates a substantial difference in buckling mode shapes, though the buckling loads are close to each other. The method for determining the hydrodynamic mass is applied to the impeller stage of a centrifugal pump. The method is based on a linear perturbation technique which assumes that the disturbance in the flow boundaries and velocities caused by the motion of the structure is small. A potential method is used to estimate the velocity flow field. The hydrodynamic mass is then obtained by calculating the total force which results from the pressure induced by a perturbation of the structure.

Local structure order in Pd 78Cu 6Si 16 liquid

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

Yue, G. Q.; Zhang, Y.; Sun, Y.

2015-02-05

The short-range order (SRO) in Pd 78Cu 6Si 16 liquid was studied by high energy x-ray diffraction and ab initio molecular dynamics (MD) simulations. The calculated pair correlation functions at different temperatures agree well with the experimental results. The partial pair correlation functions from ab intio MD simulations indicate that Si atoms prefer to be uniformly distributed while Cu atoms tend to aggregate. By performing structure analysis using Honeycutt-Andersen index, Voronoi tessellation, and atomic cluster alignment method, we show that the icosahedron and face-centered cubic SRO increase upon cooling. The dominant SRO is the Pd-centered Pd 9Si 2 motif, namelymore » the structure of which motif is similar to the structure of Pd-centered clusters in the Pd 9Si 2 crystal. The study further confirms the existence of trigonal prism capped with three half-octahedra that is reported as a structural unit in Pd-based amorphous alloys. The majority of Cu-centered clusters are icosahedra, suggesting that the presence of Cu is benefit to promote the glass forming ability.« less

Local Environment and Interactions of Liquid and Solid Interfaces Revealed by Spectral Line Shape of Surface Selective Nonlinear Vibrational Probe

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

Chen, Shun-Li; Fu, Li; Chase, Zizwe A.

Vibrational spectral lineshape contains important detailed information of molecular vibration and reports its specific interactions and couplings to its local environment. In this work, recently developed sub-1 cm-1 high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) was used to measure the -C≡N stretch vibration in the 4-n-octyl-4’-cyanobiphenyl (8CB) Langmuir or Langmuir-Blodgett (LB) monolayer as a unique vibrational probe, and the spectral lineshape analysis revealed the local environment and interactions at the air/water, air/glass, air/calcium fluoride and air/-quartz interfaces for the first time. The 8CB Langmuir or LB film is uniform and the vibrational spectral lineshape of its -C≡N group hasmore » been well characterized, making it a good choice as the surface vibrational probe. Lineshape analysis of the 8CB -C≡N stretch SFG vibrational spectra suggests the coherent vibrational dynamics and the structural and dynamic inhomogeneity of the -C≡N group at each interface are uniquely different. In addition, it is also found that there are significantly different roles for water molecules in the LB films on different substrate surfaces. These results demonstrated the novel capabilities of the surface nonlinear spectroscopy in characterization and in understanding the specific structures and chemical interactions at the liquid and solid interfaces in general.« less

Thermal conductivity switch: Optimal semiconductor/metal melting transition

NASA Astrophysics Data System (ADS)

Kim, Kwangnam; Kaviany, Massoud

2016-10-01

Scrutinizing distinct solid/liquid (s /l ) and solid/solid (s /s ) phase transitions (passive transitions) for large change in bulk (and homogenous) thermal conductivity, we find the s /l semiconductor/metal (S/M) transition produces the largest dimensionless thermal conductivity switch (TCS) figure of merit ZTCS (change in thermal conductivity divided by smaller conductivity). At melting temperature, the solid phonon and liquid molecular thermal conductivities are comparable and generally small, so the TCS requires localized electron solid and delocalized electron liquid states. For cyclic phase reversibility, the congruent phase transition (no change in composition) is as important as the thermal transport. We identify X Sb and X As (X =Al , Cd, Ga, In, Zn) and describe atomic-structural metrics for large ZTCS, then show the superiority of S/M phonon- to electron-dominated transport melting transition. We use existing experimental results and theoretical and ab initio calculations of the related properties for both phases (including the Kubo-Greenwood and Bridgman formulations of liquid conductivities). The 5 p orbital of Sb contributes to the semiconductor behavior in the solid-phase band gap and upon disorder and bond-length changes in the liquid phase this changes to metallic, creating the large contrast in thermal conductivity. The charge density distribution, electronic localization function, and electron density of states are used to mark this S/M transition. For optimal TCS, we examine the elemental selection from the transition, basic, and semimetals and semiconductor groups. For CdSb, addition of residual Ag suppresses the bipolar conductivity and its ZTCS is over 7, and for Zn3Sb2 it is expected to be over 14, based on the structure and transport properties of the better-known β -Zn4Sb3 . This is the highest ZTCS identified. In addition to the metallic melting, the high ZTCS is due to the electron-poor nature of II-V semiconductors, leading to the significantly low phonon conductivity.

Dynamics and diffusion mechanism of low-density liquid silicon

DOE PAGES

Shen, B.; Wang, Z. Y.; Dong, F.; ...

2015-11-05

A first-order phase transition from a high-density liquid to a low-density liquid has been proposed to explain the various thermodynamic anomies of water. It also has been proposed that such liquid–liquid phase transition would exist in supercooled silicon. Computer simulation studies show that, across the transition, the diffusivity drops roughly 2 orders of magnitude, and the structures exhibit considerable tetrahedral ordering. The resulting phase is a highly viscous, low-density liquid silicon. Investigations on the atomic diffusion of such a novel form of liquid silicon are of high interest. Here we report such diffusion results from molecular dynamics simulations using themore » classical Stillinger–Weber (SW) potential of silicon. We show that the atomic diffusion of the low-density liquid is highly correlated with local tetrahedral geometries. We also show that atoms diffuse through hopping processes within short ranges, which gradually accumulate to an overall random motion for long ranges as in normal liquids. There is a close relationship between dynamical heterogeneity and hopping process. We point out that the above diffusion mechanism is closely related to the strong directional bonding nature of the distorted tetrahedral network. Here, our work offers new insights into the complex behavior of the highly viscous low density liquid silicon, suggesting similar diffusion behaviors in other tetrahedral coordinated liquids that exhibit liquid–liquid phase transition such as carbon and germanium.« less

Comparative study of crystallization process in metallic melts using ab initio molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Debela, Tekalign T.; Wang, X. D.; Cao, Q. P.; Zhang, D. X.; Jiang, J. Z.

2017-05-01

The crystallization process of liquid metals is studied using ab initio molecular dynamics simulations. The evolution of short-range order during quenching in Pb and Zn liquids is compared with body-centered cubic (bcc) Nb and V, and hexagonal closed-packed (hcp) Mg. We found that the fraction and type of the short-range order depends on the system under consideration, in which the icosahedral symmetry seems to dominate in the body-centered cubic metals. Although the local atomic structures in stable liquids are similar, liquid hcp-like Zn, bcc-like Nb and V can be deeply supercooled far below its melting point before crystallization while the supercooled temperature range in liquid Pb is limited. Further investigations into the nucleation process reveal the process of polymorph selection. In the body-centered cubic systems, the polymorph selection occurs in the supercooled state before the nucleation is initiated, while in the closed-packed systems it starts at the time of onset of crystallization. Atoms with bcc-like lattices in all studied supercooled liquids are always detected before the polymorph selection. It is also found that the bond orientational ordering is strongly correlated with the crystallization process in supercooled Zn and Pb liquids.

In situ KPFM imaging of local photovoltaic characteristics of structured organic photovoltaic devices.

PubMed

Watanabe, Satoshi; Fukuchi, Yasumasa; Fukasawa, Masako; Sassa, Takafumi; Kimoto, Atsushi; Tajima, Yusuke; Uchiyama, Masanobu; Yamashita, Takashi; Matsumoto, Mutsuyoshi; Aoyama, Tetsuya

2014-02-12

Here, we discuss the local photovoltaic characteristics of a structured bulk heterojunction, organic photovoltaic devices fabricated with a liquid carbazole, and a fullerene derivative based on analysis by scanning kelvin probe force microscopy (KPFM). Periodic photopolymerization induced by an interference pattern from two laser beams formed surface relief gratings (SRG) in the structured films. The surface potential distribution in the SRGs indicates the formation of donor and acceptor spatial distribution. Under illumination, the surface potential reversibly changed because of the generation of fullerene anions and hole transport from the films to substrates, which indicates that we successfully imaged the local photovoltaic characteristics of the structured photovoltaic devices. Using atomic force microscopy, we confirmed the formation of the SRG because of the material migration to the photopolymerized region of the films, which was induced by light exposure through photomasks. The structuring technique allows for the direct fabrication and the control of donor and acceptor spatial distribution in organic photonic and electronic devices with minimized material consumption. This in situ KPFM technique is indispensable to the fabrication of nanoscale electron donor and electron acceptor spatial distribution in the devices.

A Mechanism for Recent Production of Liquid Water on Mars

NASA Technical Reports Server (NTRS)

Hecht, M. H.; Bridges, N. T.

2003-01-01

Though Mars is a cold, dry planet, with respect to the thermal stability of liquid water at low altitudes it is not terribly different from comparably cold places on Earth. In dry air such water would evaporate faster on Mars, at a rate comparable to a 60 C hot spring on Earth, but the heat loss associated with that evaporation would be mitigated by the poor thermal convection in the thin Martian air. Even at higher altitudes where the atmospheric pressure does not reach the triple point of water, liquid water might theoretically exist in a low-vapor pressure form such as wet soil, in a briny solution, or simply under a layer of dust or snow. The theoretical stability of liquid water does not suggest its occurrence, either on Mars or in Antarctica. In fact, global models have suggested that locations capable of providing sufficient heat for melting are, precisely for that reason, too dry for water to be present. However, the temperature of irregular local structures such as trenches or craters can be markedly warmer than those of the uniform surfaces of global models. The work described here suggests a plausible scenario in which seasonal liquid water might be produced locally, in sheltered locations, through a process of condensation, cold-trapping, buffering, and melting. While the amounts produced in the present climate would be small, copious amounts of meltwater may have been produced at other phases of the orbital cycle, as recently as 20,000 years ago.

Synchrotron x-ray high energy PDF and tomography studies for gallium melts under high-pressure conditions

NASA Astrophysics Data System (ADS)

Liu, H.; Liu, L. L.; Li, R.; Li, L.

2015-12-01

Liquid gallium exhibits unusual and unique physical properties. A rich polymorphism and metastable modifications of solid Ga have been discovered and a number of studies of liquid gallium under high pressure conditions were reported. However, some fundamental properties, such as the equation of state (EoS) of Ga melt under extreme conditions remain unclear. To compare to the previous reports, we performed the pair distribution function (PDF) study using diamond anvil cell, in which synchrotron high-energy x-ray total scattering data, combined with reverse Monte Carlo simulation, was used to study the microstructure and EoS of liquid gallium under high pressure at room temperature conditions. The EoS of Ga melt, which was measured from synchrotron x-ray tomography method at room temperature, was used to avoid the potential relatively big errors for the density estimation from the reverse Monte Carlo simulation with the mathematical fit to the measured structure factor data. The volume change of liquid gallium have been studied as a function of pressure and temperature up to 5 GPa at 370 K using synchrotron x-ray microtomography combined with energy dispersive x-ray diffraction (EDXRD) techniques using Drickamer press. The directly measured P-V-T curves were obtained from 3D tomography reconstruction data. The existence of possible liquid-liquid phase transition regions is proposed based on the abnormal compressibility and local structure change in Ga melts.

Light scattering by a nematic liquid crystal droplet: Wentzel–Kramers–Brillouin approximation

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

Loiko, V. A., E-mail: loiko@dragon.bas-net.by; Konkolovich, A. V.; Miskevich, A. A.

2016-01-15

Light scattering by an optically anisotropic liquid crystal (LC) droplet of a nematic in an isotropic polymer matrix is considered in the Wentzel–Kramers–Brillouin (WKB) approximation. General relations are obtained for elements of the amplitude matrix of light scattering by a droplet of arbitrary shape and for the structure of the director field. Analytic expressions for the amplitude matrices are derived for spherical LC droplets with a uniformly oriented structure of local optical axes for strictly forward and strictly backward scattering. The efficiency factors of extinction and backward scattering for a spherical nonabsorbing LC droplet depending on the LC optical anisotropy,more » refractive index of the polymer, illumination conditions, and orientation of the optical axis of the droplet are analyzed. Verification of the obtained solutions has been performed.« less

Heterogeneity in a room-temperature ionic liquid: persistent local environments and the red-edge effect.

PubMed

Hu, Zhonghan; Margulis, Claudio J

2006-01-24

In this work, we investigate the slow dynamics of 1-butyl-3-methylimidazolium hexafluorophosphate, a very popular room-temperature ionic solvent. Our study predicts the existence of heterogeneity in the liquid and shows that this heterogeneity is the underlying microscopic cause for the recently reported "red-edge effect" (REE) observed in the study of fluorescence of the organic probe 2-amino-7-nitrofluorene. This theoretical work explains in microscopic terms the relation between REE and dynamic heterogeneity in a room-temperature ionic liquid (IL). The REE is typical of micellar or colloidal systems, which are characterized by microscopic environments that are structurally very different. In contrast, in the case of this room-temperature IL, the REE occurs because of the long period during which molecules are trapped in quasistatic local solvent cages. This trapping time, which is longer than the lifetime of the excited-state probe, together with the inability of the surroundings to adiabatically relax, induces a set of site-specific spectroscopic responses. Subensembles of fluorescent molecules associated with particular local environments absorb and emit at different frequencies. We describe in detail the absorption wavelength-dependent emission spectra of 2-amino-7-nitrofluorene and show that this dependence on lambda(ex) is characteristic of the IL and, as is to be expected, is absent in the case of a normal solvent such as methanol.

Influence of an amorphous wall on the distribution of localized excitations in a colloidal glass-forming liquid

NASA Astrophysics Data System (ADS)

Gokhale, Shreyas; Hima Nagamanasa, K.; Sood, A. K.; Ganapathy, Rajesh

2016-07-01

Elucidating the nature of the glass transition has been the holy grail of condensed matter physics and statistical mechanics for several decades. A phenomenological aspect that makes glass formation a conceptually formidable problem is that structural and dynamic correlations in glass-forming liquids are too subtle to be captured at the level of conventional two-point functions. As a consequence, a host of theoretical techniques, such as quenched amorphous configurations of particles, have been devised and employed in simulations and colloid experiments to gain insights into the mechanisms responsible for these elusive correlations. Very often, though, the analysis of spatio-temporal correlations is performed in the context of a single theoretical framework, and critical comparisons of microscopic predictions of competing theories are thereby lacking. Here, we address this issue by analysing the distribution of localized excitations, which are building blocks of relaxation as per the dynamical facilitation (DF) theory, in the presence of an amorphous wall, a construct motivated by the random first-order transition theory (RFOT). We observe that spatial profiles of the concentration of excitations exhibit complex features such as non-monotonicity and oscillations. Moreover, the smoothly varying part of the concentration profile yields a length scale {ξc} , which we compare with a previously computed length scale {ξ\\text{dyn}} . Our results suggest a method to assess the role of dynamical facilitation in governing structural relaxation in glass-forming liquids.

Bending, wrinkling, and folding of thin polymer film/elastomer interfaces

NASA Astrophysics Data System (ADS)

Ebata, Yuri

This work focuses on understanding the buckling deformation mechanisms of bending, wrinkling, and folding that occur on the surfaces and interfaces of polymer systems. We gained fundamental insight into the formation mechanism of these buckled structures for thin glassy films placed on an elastomeric substrate. By taking advantage of geometric confinement, we demonstrated new strategies in controlling wrinkling morphologies. We were able to achieve surfaces with controlled patterned structures which will have a broad impact in optical, adhesive, microelectronics, and microfluidics applications. Wrinkles and strain localized features, such as delaminations and folds, are observed in many natural systems and are useful for a wide range of patterning applications. However, the transition from sinusoidal wrinkles to more complex strain localized structures is not well understood. We investigated the onset of wrinkling and strain localizations under uniaxial strain. We show that careful measurement of feature amplitude allowed not only the determination of wrinkle, fold, or delamination onset, but also allowed clear distinction between each feature. The folds observed in this experiment have an outward morphology from the surface in contrast to folds that form into the plane, as observed in a film floating on a liquid substrate. A critical strain map was constructed, where the critical strain was measured experimentally for wrinkling, folding, and delamination with varying film thickness and modulus. Wrinkle morphologies, i.e. amplitude and wavelength of wrinkles, affect properties such as electron transport in stretchable electronics and adhesion properties of smart surfaces. To gain an understanding of how the wrinkle morphology can be controlled, we introduced a geometrical confinement in the form of rigid boundaries. Upon straining, we found that wrinkles started near the rigid boundaries where maximum local strain occurred and propagated towards the middle as more global strain was applied. In contrast to homogeneous wrinkling with constant amplitude that is observed for an unconfined system, the wrinkling observed here had varying amplitude as a function of distance from the rigid boundaries. We demonstrated that the number of wrinkles can be tuned by controlling the distance between the rigid boundaries. Location of wrinkles was also controlled by introducing local stress distributions via patterning the elastomeric substrate. Two distinct wrinkled regions were achieved on a surface where the film is free-standing over a circular hole pattern and where the film is supported by the substrate. The hoe diameter and applied strain affected the wavelength and amplitude of the free-standing membrane. Using discontinuous dewetting, a one-step fabrication method was developed to selectively deposit a small volume of liquid in patterned microwells and encapsulate it with a polymeric film. The pull-out velocity, a velocity at which the sample is removed from a bath of liquid, was controlled to observe how encapsulation process is affected. The polymeric film was observed to wrinkle at low pull-out velocity due to no encapsulation of liquid; whereas the film bent at medium pull-out velocity due to capillary effect as the liquid evaporated through the film. To quantify the amount of liquid encapsulated, we mixed salt in water and measured the size of the deposited salt crystals. The salt crystal size, and hence the amount of liquid encapsulated, was controlled by varying either the encapsulation velocity or the size of the patterned microwells. In addition, we showed that the deposited salt crystals are protected by the laminated film until the film is removed, providing advantageous control for delivery and release. Yeast cells were also captured in the microwells to show the versatility. This encapsulation method is useful for wide range of applications, such as trapping single cells for biological studies, growing microcrystals for optical and magnetic applications, and single-use sensor technologies.

Effects of the bond polarity on the structural and dynamical properties of silica-like liquids

NASA Astrophysics Data System (ADS)

Pafong Sanjon, E.; Drossel, B.; Vogel, M.

2018-03-01

Silica is a network-forming liquid that shares many properties with water due to its tetrahedral structure. It undergoes a transition from a fragile to a strong liquid as the temperature is decreased, which is accompanied by a structural change to lower density and higher tetrahedral order. In order to disentangle the effects of Coulomb and van der Waals interactions on the structure and dynamics of liquid silica, we modify the bond polarity by changing the partial charges assigned to each atom. Using molecular dynamics simulations, we show that density, tetrahedral order, and structural relaxation times decrease when reducing bond polarity. Moreover, we find that the density maximum and the fragile-to-strong transition move to lower temperatures until they eventually vanish when the partial charges are decreased below approximately 75% of their regular value. Irrespective of whether strong or fragile behavior exists, structural relaxation is governed by hopping motion at sufficiently low temperatures. As long as there is a strong regime, the energy barrier associated with strong dynamics decreases with decreasing partial charges, but the dependence on the bond polarity differs from that of the activation energy in the Arrhenius regime at high temperatures. We show that the fragile-to-strong transition is associated with structural changes occurring between the first and second coordination shells that lead to a decrease in density and an increase in tetrahedral order. In particular, independent of the value of the partial charges, the distribution of the local structures is the same at this dynamic crossover, but we find no evidence that the effect occurs upon crossing the Widom line. In the fragile regime at intermediate temperatures, the relaxation times are well described by a previously proposed model which decomposes the apparent activation energy into a constant single-particle contribution and a temperature-dependent collective contribution. However, our results for silica-like melts do not obey several common relations of the model parameters reported for molecular glass formers.

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

Chainer, Timothy J.; Parida, Pritish R.

Systems and methods for cooling include one or more computing structure, an inter-structure liquid cooling system that includes valves configured to selectively provide liquid coolant to the one or more computing structures; a heat rejection system that includes one or more heat rejection units configured to cool liquid coolant; and one or more liquid-to-liquid heat exchangers that include valves configured to selectively transfer heat from liquid coolant in the inter-structure liquid cooling system to liquid coolant in the heat rejection system. Each computing structure further includes one or more liquid-cooled servers; and an intra-structure liquid cooling system that has valvesmore » configured to selectively provide liquid coolant to the one or more liquid-cooled servers.« less

Provisioning cooling elements for chillerless data centers

DOEpatents

Chainer, Timothy J.; Parida, Pritish R.

2016-12-13

Systems and methods for cooling include one or more computing structure, an inter-structure liquid cooling system that includes valves configured to selectively provide liquid coolant to the one or more computing structures; a heat rejection system that includes one or more heat rejection units configured to cool liquid coolant; and one or more liquid-to-liquid heat exchangers that include valves configured to selectively transfer heat from liquid coolant in the inter-structure liquid cooling system to liquid coolant in the heat rejection system. Each computing structure further includes one or more liquid-cooled servers; and an intra-structure liquid cooling system that has valves configured to selectively provide liquid coolant to the one or more liquid-cooled servers.

Diffusive Transport and Structural Properties of Liquid Iron Alloys at High Pressure

NASA Astrophysics Data System (ADS)

Posner, E.; Rubie, D. C.; Steinle-Neumann, G.; Frost, D. J.

2017-12-01

Diffusive transport properties of liquid iron alloys at high pressures (P) and temperatures (T) place important kinetic constraints on processes related to the origin and evolution of planetary cores. Earth's core composition is largely controlled by the extent of chemical equilibration achieved between liquid metal bodies and a silicate magma ocean during core formation, which can be estimated using chemical diffusion data. In order to estimate the time and length scales of metal-silicate chemical equilibration, we have measured chemical diffusion rates of Si, O and Cr in liquid iron over the P-T range of 1-18 GPa and 1873-2643 K using a multi-anvil apparatus. We have also performed first-principles molecular dynamic simulations of comparable binary liquid compositions, in addition to pure liquid Fe, over a much wider P-T range (1 bar-330 GPa, 2200-5500 K) in order to both validate the simulation results with experimental data at conditions accessible in the laboratory and to extend our dataset to conditions of the Earth's core. Over the entire P-T range studied using both methods, diffusion coefficients are described consistently and well using an exponential function of the homologous temperature relation. Si, Cr and Fe diffusivities of approximately 5 × 10-9 m2 s-1 are constant along the melting curve from ambient to core pressures, while oxygen diffusion is 2-3 times faster. Our results indicate that in order for the composition of the Earth's core to represent chemical equilibrium, impactor cores must have broken up into liquid droplet sizes no larger than a few tens of cm. Structural properties, analyzed using partial radial distribution functions from the molecular dynamics simulations, reveal a pressure-induced structural change in liquid Fe0.96O0.04 at densities of 8 g cm-3, in agreement with previous experimental studies. For densities above 8 g cm-3, the liquid is essentially close packed with a local CsCl-like (B2) packing of Fe around O under conditions of the Earth's core.

Spectroscopic studies of nanomaterials with a liquid-helium-free high-stability cryogenic scanning tunneling microscope

NASA Astrophysics Data System (ADS)

Kislitsyn, Dmitry Anatolevich

This dissertation presents results of a project bringing Scanning Tunneling Microscope (STM) into a regime of unlimited operational time at cryogenic conditions. Freedom from liquid helium consumption was achieved and technical characteristics of the instrument are reported, including record low noise for a scanning probe instrument coupled to a close-cycle cryostat, which allows for atomically resolved imaging, and record low thermal drift. Subsequent studies showed that the new STM opened new prospects in nanoscience research by enabling Scanning Tunneling Spectroscopic (STS) spatial mapping to reveal details of the electronic structure in real space for molecules and low-dimensional nanomaterials, for which this depth of investigation was previously prohibitively expensive. Quantum-confined electronic states were studied in single-walled carbon nanotubes (SWCNTs) deposited on the Au(111) surface. Localization on the nanometer-scale was discovered to produce a local vibronic manifold resulting from the localization-enhanced electron-vibrational coupling. STS showed the vibrational overtones, identified as D-band Kekule vibrational modes and K-point transverse out-of plane phonons. This study experimentally connected the properties of well-defined localized electronic states to the properties of associated vibronic states. Electronic structures of alkyl-substituted oligothiophenes with different backbone lengths were studied and correlated with torsional conformations assumed on the Au(111) surface. The molecules adopted distinct planar conformations with alkyl ligands forming cis- or trans-mutual orientations and at higher coverage self-assembled into ordered structures, binding to each other via interdigitated alkyl ligands. STS maps visualized, in real space, particle-in-a-box-like molecular orbitals. Shorter quaterthiophenes have substantially varying orbital energies because of local variations in surface reactivity. Different conformers of longer oligothiophenes with significant geometrical distortions of the oligothiophene backbones surprisingly exhibited similar electronic structures, indicating insensitivity of interaction with the surface to molecular conformation. Electronic states for annealed ligand-free lead sulfide nanocrystals were investigated, as well as hydrogen-passivated silicon nanocrystals, supported on the Au(111) surface. Delocalized quantum-confined states and localized defect-related states were identified, for the first time, via STS spatial mapping. Physical mechanisms, involving surface reconstruction or single-atom defects, were proposed for surface state formation to explain the observed spatial behavior of the electronic density of states. This dissertation includes previously published co-authored material.

Interfacial layering and capillary roughness in immiscible liquids.

PubMed

Geysermans, P; Pontikis, V

2010-08-21

The capillary roughness and the atomic density profiles of extended interfaces between immiscible liquids are determined as a function of the interface area by using molecular dynamics and Lennard-Jones (12-6) potentials. We found that with increasing area, the interface roughness diverges logarithmically, thus fitting the theoretical mean-field prediction. In systems small enough for the interfacial roughness not to blur the structural details, atomic density profiles across the fluid interface are layered with correlation length in the range of molecular correlations in liquids. On increasing the system size, the amplitude of the thermally excited position fluctuations of the interface increases, thus causing layering to rapidly vanish, if density profiles are computed without special care. In this work, we present and validate a simple method, operating in the direct space, for extracting from molecular dynamics trajectories the "intrinsic" structure of a fluid interface that is the local density profile of the interface cleaned from capillary wave effects. Estimated values of interfacial properties such as the tension, the intrinsic width, and the lower wavelength limit of position fluctuations are in agreement with results collected from the literature.

Computed a multiple band metamaterial absorber and its application based on the figure of merit value

NASA Astrophysics Data System (ADS)

Chen, Chao; Sheng, Yuping; Jun, Wang

2018-01-01

A high performed multiple band metamaterial absorber is designed and computed through the software Ansofts HFSS 10.0, which is constituted with two kinds of separated metal particles sub-structures. The multiple band absorption property of the metamaterial absorber is based on the resonance of localized surface plasmon (LSP) modes excited near edges of metal particles. The damping constant of gold layer is optimized to obtain a near-perfect absorption rate. Four kinds of dielectric layers is computed to achieve the perfect absorption perform. The perfect absorption perform of the metamaterial absorber is enhanced through optimizing the structural parameters (R = 75 nm, w = 80 nm). Moreover, a perfect absorption band is achieved because of the plasmonic hybridization phenomenon between LSP modes. The designed metamaterial absorber shows high sensitive in the changed of the refractive index of the liquid. A liquid refractive index sensor strategy is proposed based on the computed figure of merit (FOM) value of the metamaterial absorber. High FOM values (116, 111, and 108) are achieved with three liquid (Methanol, Carbon tetrachloride, and Carbon disulfide).

Microstructural properties and evolution of nanoclusters in liquid Si during a rapid cooling process

NASA Astrophysics Data System (ADS)

Gao, T.; Hu, X.; Li, Y.; Tian, Z.; Xie, Q.; Chen, Q.; Liang, Y.; Luo, X.; Ren, L.; Luo, J.

2017-11-01

The formation of amorphous structures in Si during the rapid quenching process was studied based on molecular dynamics simulation by using the Stillinger-Weber potential. The evolution characteristics of nanoclusters during the solidification were analyzed by several structural analysis methods. The amorphous Si has been formed with many tetrahedral clusters and few nanoclusters. During the solidification, tetrahedral polyhedrons affect the local structures by their different positions and connection modes. The main kinds of polyhedrons randomly linked with one another to form an amorphous network structures in the system. The structural evolution of crystal nanocluster demonstrates that the nanocluster has difficulty to growth because of the high cooling rate of 1012 K/s.

Provisioning cooling elements for chillerless data centers

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

Chainer, Timothy J.; Parida, Pritish R.

Systems and methods for cooling include one or more computing structure, an inter-structure liquid cooling system that includes valves configured to selectively provide liquid coolant to the one or more computing structures; a heat rejection system that includes one or more heat rejection units configured to cool liquid coolant; and one or more liquid-to-liquid heat exchangers that include valves configured to selectively transfer heat from liquid coolant in the inter-structure liquid cooling system to liquid coolant in the heat rejection system. Each computing structure further includes one or more liquid-cooled servers; and an intra-structure liquid cooling system that has valvesmore » configured to selectively provide liquid coolant to the one or more liquid-cooled servers.« less

The melting point of lithium: an orbital-free first-principles molecular dynamics study

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

Chen, Mohan; Hung, Linda; Huang, Chen

2013-08-25

The melting point of liquid lithium near zero pressure is studied with large-scale orbital-free first-principles molecular dynamics (OF-FPMD) in the isobaric-isothermal ensemble. Here, we adopt the Wang-Govind-Carter (WGC) functional as our kinetic energy density functional (KEDF) and construct a bulk-derived local pseudopotential (BLPS) for Li. Our simulations employ both the ‘heat-until-melts’ method and the coexistence method. We predict 465 K as an upper bound of the melting point of Li from the ‘heat-until-melts’ method, while we predict 434 K as the melting point of Li from the coexistence method. These values compare well with an experimental melting point of 453more » K at zero pressure. Furthermore, we calculate a few important properties of liquid Li including the diffusion coefficients, pair distribution functions, static structure factors, and compressibilities of Li at 470 K and 725 K in the canonical ensemble. This theoretically-obtained results show good agreement with known experimental results, suggesting that OF-FPMD using a non-local KEDF and a BLPS is capable of accurately describing liquid metals.« less

40 CFR 98.403 - Calculating GHG emissions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Natural Gas and Natural Gas Liquids § 98.403... natural gas processing plants from local production, received as a liquid and vaporized for delivery, or... local production, or natural gas that was received as a liquid, vaporized and delivered, and any other...

Structural Evolution of Supercritical CO2 across the Frenkel Line.

PubMed

Bolmatov, Dima; Zav'yalov, D; Gao, M; Zhernenkov, Mikhail

2014-08-21

Here, we study structural properties of the supercritical carbon dioxide and discover the existence of persistent medium-range order correlations, which make supercritical carbon dioxide nonuniform and heterogeneous on an intermediate length scale. We report on the CO2 heterogeneity shell structure where, in the first shell, both carbon and oxygen atoms experience gas-like-type interactions with short-range order correlations while within the second shell, oxygen atoms essentially exhibit a liquid-like type of interactions due to localization of transverse-like phonon packets. Importantly, we highlight a catalytic role of atoms inside of the nearest-neighbor heterogeneity shell in providing a mechanism for diffusion and proving the existence of an additional thermodynamic boundary in the supercritical carbon dioxide on an intermediate length scale. Finally, we discuss important implications for answering the intriguing question whether Venus may have had CO2 oceans and urge for an experimental detection of this persistent local-order heterogeneity.

Carbon diffusion in molten uranium: an ab initio molecular dynamics study

NASA Astrophysics Data System (ADS)

Garrett, Kerry E.; Abrecht, David G.; Kessler, Sean H.; Henson, Neil J.; Devanathan, Ram; Schwantes, Jon M.; Reilly, Dallas D.

2018-04-01

In this work we used ab initio molecular dynamics within the framework of density functional theory and the projector-augmented wave method to study carbon diffusion in liquid uranium at temperatures above 1600 K. The electronic interactions of carbon and uranium were described using the local density approximation (LDA). The self-diffusion of uranium based on this approach is compared with literature computational and experimental results for liquid uranium. The temperature dependence of carbon and uranium diffusion in the melt was evaluated by fitting the resulting diffusion coefficients to an Arrhenius relationship. We found that the LDA calculated activation energy for carbon was nearly twice that of uranium: 0.55 ± 0.03 eV for carbon compared to 0.32 ± 0.04 eV for uranium. Structural analysis of the liquid uranium-carbon system is also discussed.

A Gaussian Approximation Potential for Silicon

NASA Astrophysics Data System (ADS)

Bernstein, Noam; Bartók, Albert; Kermode, James; Csányi, Gábor

We present an interatomic potential for silicon using the Gaussian Approximation Potential (GAP) approach, which uses the Gaussian process regression method to approximate the reference potential energy surface as a sum of atomic energies. Each atomic energy is approximated as a function of the local environment around the atom, which is described with the smooth overlap of atomic environments (SOAP) descriptor. The potential is fit to a database of energies, forces, and stresses calculated using density functional theory (DFT) on a wide range of configurations from zero and finite temperature simulations. These include crystalline phases, liquid, amorphous, and low coordination structures, and diamond-structure point defects, dislocations, surfaces, and cracks. We compare the results of the potential to DFT calculations, as well as to previously published models including Stillinger-Weber, Tersoff, modified embedded atom method (MEAM), and ReaxFF. We show that it is very accurate as compared to the DFT reference results for a wide range of properties, including low energy bulk phases, liquid structure, as well as point, line, and plane defects in the diamond structure.

Nano-material aspects of shock absorption in bone joints.

PubMed

Tributsch, H; Copf, F; Copf, P; Hindenlang, U; Niethard, F U; Schneider, R

2010-01-01

This theoretical study is based on a nano-technological evaluation of the effect of pressure on the composite bone fine structure. It turned out, that the well known macroscopic mechano-elastic performance of bones in combination with muscles and tendons is just one functional aspect which is critically supported by additional micro- and nano- shock damping technology aimed at minimising local bone material damage within the joints and supporting spongy bone material. The identified mechanisms comprise essentially three phenomena localised within the three-dimensional spongy structure with channels and so called perforated flexible tensulae membranes of different dimensions intersecting and linking them. Kinetic energy of a mechanical shock may be dissipated within the solid-liquid composite bone structure into heat via the generation of quasi-chaotic hydromechanic micro-turbulence. It may generate electro-kinetic energy in terms of electric currents and potentials. And the resulting specific structural and surface electrochemical changes may induce the compressible intra-osseal liquid to build up pressure dependent free chemical energy. Innovative bone joint prostheses will have to consider and to be adapted to the nano-material aspects of shock absorption in the operated bones.

Experimental studying of local characteristics of gas-liquid flow in microchannels by optical methods

NASA Astrophysics Data System (ADS)

Bartkus, German V.; Kuznetsov, Vladimir V.

2018-03-01

The local characteristics of the gas-liquid two-phase flow in rectangular microchannels 420 × 280 μm and 395 × 205 μm with T-shaped mixer inlet were experimentally investigated in this work. Visualization of flow regimes and measurement of local characteristics were carried out using a high-speed video camera Optronis CX600x2 and laser-induced fluorescence (LIF) method. Deionized water and ethanol were used as the liquid phase, and nitrogen - as the gas phase. The Rhodamine 6G dye was added to the liquid. The location of the microchannel in space (horizontal, vertical) was changed. The profiles of the liquid film along the long side of the microchannel were obtained, the local film thickness was measured in the channel`s central section for the elongated bubble flow and the transition flow of the deionized water-nitrogen mixture. The unevenness of liquid film thickness at the channel cross-section and along the bubble was experimentally shown. The temporal dynamics of two-phase flow for the ethanol-nitrogen mixture was shown. It was found that most of the liquid flows in the meniscus on the short side of the microchannel for the present gas and liquid flow rates.

The influence of liquid/vapor phase change onto the Nusselt number

NASA Astrophysics Data System (ADS)

Popescu, Elena-Roxana; Colin, Catherine; Tanguy, Sebastien

2017-11-01

In spite of its significant interest in various fields, there is currently a very few information on how an external flow will modify the evaporation or the condensation of a liquid surface. Although most applications involve turbulent flows, the simpler configuration where a laminar superheated or subcooled vapor flow is shearing a saturated liquid interface has still never been solved. Based on a numerical approach, we propose to characterize the interaction between a laminar boundary layer of a superheated or subcooled vapor flow and a static liquid pool at saturation temperature. By performing a full set of simulations sweeping the parameters space, correlations are proposed for the first time on the Nusselt number depending on the dimensionless numbers that characterize both vaporization and condensation. As attended, the Nusselt number decreases or increases in the configurations involving respectively vaporization or condensation. More unexpected is the behaviour of the friction of the vapor flow on the liquid pool, for which we report that it is weakly affected by the phase change, despite the important variation of the local flow structure due to evaporation or condensation.

Effects of high pressure on microstructure evolution and crystallization mechanisms during solidification of nickel

NASA Astrophysics Data System (ADS)

Zhang, Hai-Tao; Mo, Yun-Fei; Liu, Rang-Su; Tian, Ze-An; Liu, Hai-Rong; Hou, Zhao-Yang; Zhou, Li-Li; Liang, Yong-Chao; Peng, Ping

2018-03-01

To deeply understand the effects of high pressure on microstructural evolutions and crystallization mechanisms of liquid metal Ni during solidification process, MD simulation studies have been performed under 7 pressures of 0 ˜ 30 GPa, at cooling rate of 1.0 × 1011 K s-1. Adopting several microstructural analyzing methods, especially the cluster-type index method (CTIM-2) to analyze the local microstructures in the system. It is found that the pressure has important influence on the formation and evolution of microstructures, especially of the main basic clusters in the system. All the simulation systems are directly solidified into crystal structures, and the 1421, 1422, 1441 and 1661 bond-types, as well the FCC (12 0 0 0 12 0), HCP (12 0 0 0 6 6) and BCC (14 6 0 8 0 0) clusters play a key role in the microstructure transitions from liquid to crystal structures. The crystallization temperature T c is enhanced almost linearly with the increase of pressure. Highly interesting, it is found for the first time that there is an important phase transformation point from FCC to BCC structures between 20 ˜ 22.5 GPa during the solidification processes from the same initial liquid system at the same cooling rate. And the effect of increasing pressure is similar to that of decreasing cooling rate for the phase transformation of microstructures during solidification process of liquid metal Ni system, though they have different concrete effecting mechanisms.

The Boson peak in confined water: An experimental investigation of the liquid-liquid phase transition hypothesis

DOE PAGES

Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; ...

2015-12-05

The Boson peak (BP) of deeply cooled confined water is studied by using inelastic neutron scattering (INS) in a large interval of the (P, T) phase plane. By taking into account the different behavior of such a collective vibrational mode in both strong and fragile glasses as well as in glass-forming materials, we were able to determine the Widom line that characterizes supercooled bulk water within the frame of the liquid-liquid phase transition (LLPT) hypothesis. The peak frequency and width of the BP correlated with the water polymorphism of the LLPT scenario, allowing us to distinguish the “low-density liquid” (LDL)more » and “high-density liquid” (HDL) phases in deeply cooled bulk water.Moreover, the BP properties afford a further confirmation of theWidom line temperature T W as the (P, T) locus in which the local structure of water transforms from a predominately LDL form to a predominately HDL form.« less

Parallel and Perpendicular Alignment of Anisotropic Particles in Free Liquid Microjets and Emerging Microdroplets.

PubMed

Schlenk, Mathias; Hofmann, Eddie; Seibt, Susanne; Rosenfeldt, Sabine; Schrack, Lukas; Drechsler, Markus; Rothkirch, Andre; Ohm, Wiebke; Breu, Josef; Gekle, Stephan; Förster, Stephan

2018-04-24

Liquid microjets play a key role in fiber spinning, inkjet printing, and coating processes. In all of these applications, the liquid jets carry dispersed particles whose spatial and orientational distributions within the jet critically influence the properties of the fabricated structures. Despite its importance, there is currently no knowledge about the orientational distribution of particles within microjets and droplets. Here, we demonstrate a microfluidic device that allows to determine the local particle distribution and orientation by X-ray scattering. Using this methodology, we discovered unexpected changes in the particle orientation upon exiting the nozzle to form a free jet, and upon jet break-up into droplets, causing an unusual biaxial particle orientation. We show how flow and aspect ratio determine the flow orientation of anisotropic particles. Furthermore, we demonstrate that the observed phenomena are a general characteristic of anisotropic particles. Our findings greatly enhance our understanding of particle orientation in free jets and droplets and provide a rationale for controlling particle alignment in liquid jet-based fabrication methodologies.

The Boson peak in confined water: An experimental investigation of the liquid-liquid phase transition hypothesis

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

Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico

The Boson peak (BP) of deeply cooled confined water is studied by using inelastic neutron scattering (INS) in a large interval of the (P, T) phase plane. By taking into account the different behavior of such a collective vibrational mode in both strong and fragile glasses as well as in glass-forming materials, we were able to determine the Widom line that characterizes supercooled bulk water within the frame of the liquid-liquid phase transition (LLPT) hypothesis. The peak frequency and width of the BP correlated with the water polymorphism of the LLPT scenario, allowing us to distinguish the “low-density liquid” (LDL)more » and “high-density liquid” (HDL) phases in deeply cooled bulk water.Moreover, the BP properties afford a further confirmation of theWidom line temperature T W as the (P, T) locus in which the local structure of water transforms from a predominately LDL form to a predominately HDL form.« less

Molecular dynamics of palmitic acid and lead palmitate in cross-linked linseed oil films: Implications from deuterium magnetic resonance for lead soap formation in traditional oil paintings.

PubMed

Catalano, Jaclyn; Murphy, Anna; Yao, Yao; Zumbulyadis, Nicholas; Centeno, Silvia A; Dybowski, Cecil

2018-02-01

Many oil paintings, dating from the 15th century to the present, are affected by the formation of heavy-metal carboxylates (soaps) that alter the structural integrity and appearance of the works. Through transport phenomena not yet understood, free fatty acids formed from oils used as binders migrate through the paint film and react with heavy-metal ions that are constituents of pigments and/or driers, forming metal carboxylates. The local molecular dynamics of fatty acids and metal carboxylates are factors influencing material transport in these systems. We report temperature-dependent 2 H NMR spectra of palmitic acid and lead palmitate as pure materials, in cross-linked linseed oil films, and in a lead white linseed oil paint film as part of our broader research into metal soap formation. Local dynamics at the α carbon, at the terminal methyl group, and at the middle of the fatty acid chain were observed in specifically deuterated materials. Changes in the dynamic behavior with temperature were observed by the appearance of two species, a solid-like material and a liquid-like material. The relative amounts of the two phases and their deuterium NMR parameters indicate that the amount of liquid-like material and the local dynamics at that site increase with temperature. At the three locations along the chain and at all temperatures, there is a larger percentage of acyl chains of both palmitic acid and lead palmitate that are "mobile" or liquid-like in linseed oil films than there are in the pure materials. However, the percentage of liquid-like species is decreased in a lead white paint film, as compared to a linseed oil matrix. In addition, these experiments indicate that there is a larger percentage of liquid-like acyl chains of palmitic acid than of lead palmitate under identical conditions in these model paint systems. Copyright © 2017 Elsevier Inc. All rights reserved.

Lead(ii) soaps: crystal structures, polymorphism, and solid and liquid mesophases.

PubMed

Martínez-Casado, F J; Ramos-Riesco, M; Rodríguez-Cheda, J A; Redondo-Yélamos, M I; Garrido, L; Fernández-Martínez, A; García-Barriocanal, J; da Silva, I; Durán-Olivencia, M; Poulain, A

2017-07-05

The long-chain members of the lead(ii) alkanoate series or soaps, from octanoate to octadecanoate, have been thoroughly characterized by means of XRD, PDF analysis, DSC, FTIR, ssNMR and other techniques, in all their phases and mesophases. The crystal structures at room temperature of all of the members of the series are now solved, showing the existence of two polymorphic forms in the room temperature crystal phase, different to short and long-chain members. Only nonanoate and decanoate present both forms, and this polymorphism is proven to be monotropic. At higher temperature, these compounds present a solid mesophase, defined as rotator, a liquid crystal phase and a liquid phase, all of which have a similar local arrangement. Since some lead(ii) soaps appear as degradation compounds in oil paintings, the solved crystal structures of lead(ii) soaps can now be used as fingerprints for their detection using X-ray diffraction. Pair distribution function analysis on these compounds is very similar in the same phases and mesophases for the different members, showing the same short range order. This observation suggests that this technique could also be used in the detection of these compounds in disordered phases or in the initial stages of formation in paintings.

Far-from-equilibrium magnetic granular layers: dynamic patterns, magnetic order and self-assembled swimmers

NASA Astrophysics Data System (ADS)

Snezhko, Alexey

2010-03-01

Ensembles of interacting particles subject to an external periodic forcing often develop nontrivial collective behavior and self-assembled dynamic patterns. We study emergent phenomena in magnetic granular ensembles suspended at a liquid-air and liquid-liquid interfaces and subjected to a transversal alternating magnetic field. Experiments reveal a new type of nontrivially ordered dynamic self-assembled structures (in particular, ``magnetic snakes'', ``asters'', ``clams'') emerging in such systems in a certain range of excitation parameters. These non-equilibrium dynamic structures emerge as a result of the competition between magnetic and hydrodynamic forces and have complex magnetic ordering. Transition between different self-assembled phases with parameters of external driving magnetic field is observed. I will show that above some frequency threshold magnetic snakes spontaneously break the symmetry of the self-induced surface flows (symmetry breaking instability) and turn into swimmers. Self-induced surface flows symmetry can be also broken in a controlled fashion by introduction of a large bead to a magnetic snake (bead-snake hybrid), that transforms it into a robust self-locomoting entity. Some features of the self-localized structures can be understood in the framework of an amplitude equation for parametric waves coupled to the conservation law equation describing the evolution of the magnetic particle density and the Navier-Stokes equation for hydrodynamic flows.

Structural interactions in ionic liquids linked to higher-order Poisson-Boltzmann equations

NASA Astrophysics Data System (ADS)

Blossey, R.; Maggs, A. C.; Podgornik, R.

2017-06-01

We present a derivation of generalized Poisson-Boltzmann equations starting from classical theories of binary fluid mixtures, employing an approach based on the Legendre transform as recently applied to the case of local descriptions of the fluid free energy. Under specific symmetry assumptions, and in the linearized regime, the Poisson-Boltzmann equation reduces to a phenomenological equation introduced by Bazant et al. [Phys. Rev. Lett. 106, 046102 (2011)], 10.1103/PhysRevLett.106.046102, whereby the structuring near the surface is determined by bulk coefficients.

Direct observation of impact propagation and absorption in dense colloidal monolayers

NASA Astrophysics Data System (ADS)

Buttinoni, Ivo; Cha, Jinwoong; Lin, Wei-Hsun; Job, Stéphane; Daraio, Chiara; Isa, Lucio

2017-11-01

Dense colloidal suspensions can propagate and absorb large mechanical stresses, including impacts and shocks. The wave transport stems from the delicate interplay between the spatial arrangement of the structural units and solvent-mediated effects. For dynamic microscopic systems, elastic deformations of the colloids are usually disregarded due to the damping imposed by the surrounding fluid. Here, we study the propagation of localized mechanical pulses in aqueous monolayers of micron-sized particles of controlled microstructure. We generate extreme localized deformation rates by exciting a target particle via pulsed-laser ablation. In crystalline monolayers, stress propagation fronts take place, where fast-moving particles (V approximately a few meters per second) are aligned along the symmetry axes of the lattice. Conversely, more viscous solvents and disordered structures lead to faster and isotropic energy absorption. Our results demonstrate the accessibility of a regime where elastic collisions also become relevant for suspensions of microscopic particles, behaving as “billiard balls” in a liquid, in analogy with regular packings of macroscopic spheres. We furthermore quantify the scattering of an impact as a function of the local structural disorder.

Direct observation of impact propagation and absorption in dense colloidal monolayers

PubMed Central

Cha, Jinwoong; Lin, Wei-Hsun; Job, Stéphane; Daraio, Chiara

2017-01-01

Dense colloidal suspensions can propagate and absorb large mechanical stresses, including impacts and shocks. The wave transport stems from the delicate interplay between the spatial arrangement of the structural units and solvent-mediated effects. For dynamic microscopic systems, elastic deformations of the colloids are usually disregarded due to the damping imposed by the surrounding fluid. Here, we study the propagation of localized mechanical pulses in aqueous monolayers of micron-sized particles of controlled microstructure. We generate extreme localized deformation rates by exciting a target particle via pulsed-laser ablation. In crystalline monolayers, stress propagation fronts take place, where fast-moving particles (V approximately a few meters per second) are aligned along the symmetry axes of the lattice. Conversely, more viscous solvents and disordered structures lead to faster and isotropic energy absorption. Our results demonstrate the accessibility of a regime where elastic collisions also become relevant for suspensions of microscopic particles, behaving as “billiard balls” in a liquid, in analogy with regular packings of macroscopic spheres. We furthermore quantify the scattering of an impact as a function of the local structural disorder. PMID:29087329

Controlling the Localization of Liquid Droplets in Polymer Matrices by Evaporative Lithography.

PubMed

Zhao, Huaixia; Xu, Jiajia; Jing, Guangyin; Prieto-López, Lizbeth Ofelia; Deng, Xu; Cui, Jiaxi

2016-08-26

Localized inclusions of liquids provide solid materials with many functions, such as self-healing, secretion, and tunable mechanical properties, in a spatially controlled mode. However, a strategy to control the distribution of liquid droplets in solid matrices directly obtained from a homogeneous solution has not been reported thus far. Herein, we describe an approach to selectively localize liquid droplets in a supramolecular gel directly obtained from its solution by using evaporative lithography. In this process, the formation of droplet-embedded domains occurs in regions of free evaporation where the non-volatile liquid is concentrated and undergoes a phase separation to create liquid droplets prior to gelation, while a homogeneous gel matrix is formed in the regions of hindered evaporation. The different regions of a coating with droplet embedment patterns display different secretion abilities, enabling the control of the directional movement of water droplets. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamic crossover in deeply cooled water confined in MCM-41 at 4 kbar and its relation to the liquid-liquid transition hypothesis

NASA Astrophysics Data System (ADS)

Wang, Zhe; Le, Peisi; Ito, Kanae; Leão, Juscelino B.; Tyagi, Madhusudan; Chen, Sow-Hsin

2015-09-01

With quasi-elastic neutron scattering, we study the single-particle dynamics of the water confined in a hydrophilic silica material, MCM-41, at 4 kbar. A dynamic crossover phenomenon is observed at 219 K. We compare this dynamic crossover with the one observed at ambient pressure and find that (a) above the crossover temperature, the temperature dependence of the characteristic relaxation time at ambient pressure exhibits a more evident super-Arrhenius behavior than that at 4 kbar. Especially, at temperatures below about 230 K, the relaxation time at 4 kbar is even smaller than that at ambient pressure. This feature is different from many other liquids. (b) Below the crossover temperature, the Arrhenius behavior found at ambient pressure has a larger activation energy compared to the one found at 4 kbar. We ascribe the former to the difference between the local structure of the low-density liquid (LDL) phase and that of the high-density liquid (HDL) phase, and the latter to the difference between the strength of the hydrogen bond of the LDL and that of the HDL. Therefore, we conclude that the phenomena observed in this paper are consistent with the LDL-to-HDL liquid-liquid transition hypothesis.

Dynamic crossover in deeply cooled water confined in MCM-41 at 4 kbar and its relation to the liquid-liquid transition hypothesis

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

Wang, Zhe; Le, Peisi; Ito, Kanae

With quasi-elastic neutron scattering, we study the single-particle dynamics of the water confined in a hydrophilic silica material, MCM-41, at 4 kbar. A dynamic crossover phenomenon is observed at 219 K. We compare this dynamic crossover with the one observed at ambient pressure and find that (a) above the crossover temperature, the temperature dependence of the characteristic relaxation time at ambient pressure exhibits a more evident super-Arrhenius behavior than that at 4 kbar. Especially, at temperatures below about 230 K, the relaxation time at 4 kbar is even smaller than that at ambient pressure. This feature is different from manymore » other liquids. (b) Below the crossover temperature, the Arrhenius behavior found at ambient pressure has a larger activation energy compared to the one found at 4 kbar. We ascribe the former to the difference between the local structure of the low-density liquid (LDL) phase and that of the high-density liquid (HDL) phase, and the latter to the difference between the strength of the hydrogen bond of the LDL and that of the HDL. Therefore, we conclude that the phenomena observed in this paper are consistent with the LDL-to-HDL liquid-liquid transition hypothesis.« less

Supercooled and glassy water: Metastable liquid(s), amorphous solid(s), and a no-man's land

NASA Astrophysics Data System (ADS)

Handle, Philip H.; Loerting, Thomas; Sciortino, Francesco

2017-12-01

We review the recent research on supercooled and glassy water, focusing on the possible origins of its complex behavior. We stress the central role played by the strong directionality of the water-water interaction and by the competition between local energy, local entropy, and local density. In this context we discuss the phenomenon of polyamorphism (i.e., the existence of more than one disordered solid state), emphasizing both the role of the preparation protocols and the transformation between the different disordered ices. Finally, we present the ongoing debate on the possibility of linking polyamorphism with a liquid-liquid transition that could take place in the no-man's land, the temperature-pressure window in which homogeneous nucleation prevents the investigation of water in its metastable liquid form.

Near-field optical technique applied for investigation of the characteristics of polymer fiber and waveguide structures.

PubMed

Ming, Hai; Tang, Lin; Sun, Xiaohong; Zhang, Jiangying; Wang, Pei; Lu, Yonghua; Bai, Ming; Guo, Yang; Xie, Aifang; Zhang, Zebo

2004-01-01

This article summarizes the near-field optical technique applied for investigating the characteristics of polymer fiber and waveguide structures. The near-field optical technique is used to analyze multimode interference structures of fiber. The localized fluctuation of the transmission caused by fractal cluster is carried out in Nd3+- and Eu3+-doped polymer fiber and film by means of a scanning near-field optical microscopy. The near-field optical spectrum of Nd3+-doped polymer fiber is investigated. The topography and near-field intensity images of Azo-polymer liquid crystal film for waveguide are obtained simultaneously.

Defect interactions in anisotropic two-dimensional fluids

NASA Astrophysics Data System (ADS)

Stannarius, Ralf; Harth, Kirsten

Disclinations in liquid crystals bear striking analogies to defect structures in a wide variety of physical systems, they are excellent models to study fundamental properties of defect interactions. Freely suspended smectic C films behave like quasi 2D polar nematics. An experimental procedure is introduced to capture high-strength disclinations in localized spots. After they are released in a controlled way, the motion of the mutually repelling topological charges is studied. We demonstrate that the classical models, based on elastic one-constant approximation, fail to describe their dynamics correctly. In realistic liquid crystals, the models work only in ideal configurations. In general, additional director walls modify interactions substantially. Funded by DFG within project STA 425/28-1.

High-pressure x-ray diffraction studies on the structure of liquid silicate using a Paris-Edinburgh type large volume press.

PubMed

Yamada, Akihiro; Wang, Yanbin; Inoue, Toru; Yang, Wenge; Park, Changyong; Yu, Tony; Shen, Guoyin

2011-01-01

An experimental setup for high-pressure liquid structure studies with synchrotron x-ray diffraction using the Paris-Edinburgh press has been installed at station 16-BM-B (HPCAT) of the Advanced Photon Source, Argonne National Laboratory. By collecting energy-dispersive data with a synchrotron white beam at various 2θ angles, the present device allows us to obtain the structure factor, S(Q), over a wide range of Q ( = 4πsinθ∕λ) owing to the excellent angular accessibility up to 37° in 2θ and high energy photons well beyond 100 keV. We have successfully collected XRD data on silicate (albite, NaAlSi(3)O(8)) liquids with Q up to ∼22 Å(-1) and pressure up to 5.3 GPa and temperature 1873 K, and obtained the radial distribution function, G(r), with a reasonable resolution. The T-O bond length (where T = Al, Si), which is a fundamental measure of local structure for aluminous silicate consisting of SiO(n) and AlO(n) polyhedra (tetrahedra at 1 atm condition), was found to be slightly shortened to 1.626 Å compared to that of glass at 1 atm. The T-O-T bound angle, which is the linkage of the above polyhedra, is the most responsible for densification. The T-O-T peak in G(r) splits into two peaks, suggesting a differentiation of the bond angle at high-pressure. The present technical development demonstrates that the Paris-Edinburgh press is suitable for studies of silicate liquids under high-pressure conditions.

Influence of a depletion interaction on dynamical heterogeneity in a dense quasi-two-dimensional colloid liquid.

PubMed

Ho, Hau My; Cui, Bianxiao; Repel, Stephen; Lin, Binhua; Rice, Stuart A

2004-11-01

We report the results of digital video microscopy studies of the large particle displacements in a quasi-two-dimensional binary mixture of large (L) and small (S) colloid particles with diameter ratio sigma(L)/sigma(S)=4.65, as a function of the large and small colloid particle densities. As in the case of the one-component quasi-two-dimensional colloid system, the binary mixtures exhibit structural and dynamical heterogeneity. The distribution of large particle displacements over the time scale examined provides evidence for (at least) two different mechanisms of motion, one associated with particles in locally ordered regions and the other associated with particles in locally disordered regions. When rhoL*=Npisigma(L) (2)/4A< or =0.35, the addition of small colloid particles leads to a monotonic decrease in the large particle diffusion coefficient with increasing small particle volume fraction. When rhoL* > or =0.35 the addition of small colloid particles to a dense system of large colloid particles at first leads to an increase in the large particle diffusion coefficient, which is then followed by the expected decrease of the large particle diffusion coefficient with increasing small colloid particle volume fraction. The mode coupling theory of the ideal glass transition in three-dimensional systems makes a qualitative prediction that agrees with the initial increase in the large particle diffusion coefficient with increasing small particle density. Nevertheless, because the structural and dynamical heterogeneities of the quasi-two-dimensional colloid liquid occur within the field of equilibrium states, and the fluctuations generate locally ordered domains rather than just disordered regions of higher and lower density, it is suggested that mode coupling theory does not account for all classes of relevant fluctuations in a quasi-two-dimensional liquid. (c) 2004 American Institute of Physics.

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

Mokshin, A. V., E-mail: anatolii.mokshin@mail.ru; Khusnutdinoff, R. M., E-mail: khrm@mail.ru; Novikov, A. G.

The features of the microscopic structure, as well as one-particle and collective dynamics of liquid gallium in the temperature range from T = 313 to 1273 K, are studied on the p = 1.0 atm isobar. Detailed analysis of the data on diffraction of neutrons and X-rays, as well as the results of atomic dynamics simulation, lead to some conclusions about the structure. In particular, for preset conditions, gallium is in the equilibrium liquid phase showing no features of any stable local crystalline clusters. The pronounced asymmetry of the principle peak of the static structure factor and the characteristic “shoulder”more » in its right-hand part appearing at temperatures close to the melting point, which are clearly observed in the diffraction data, are due to the fact that the arrangement of the nearest neighbors of an arbitrary atom in the system is estimated statistically from the range of correlation length values and not by a single value as in the case of simple liquids. Compactly located dimers with a very short bond make a significant contribution to the statistics of nearest neighbors. The temperature dependence of the self-diffusion coefficient calculated from atomic dynamics simulation agrees well with the results obtained from experimental spectra of the incoherent scattering function. Interpolation of the temperature dependence of the self-diffusion coefficient on a logarithmic scale reveals two linear regions with a transition temperature of about 600 K. The spectra of the dynamic structure factor and spectral densities of the local current calculated by simulating the atomic dynamics indicate the existence of acoustic vibrations with longitudinal and transverse polarizations in liquid gallium, which is confirmed by experimental data on inelastic scattering of neutrons and X-rays. It is found that the vibrational density of states is completely reproduced by the generalized Debye model, which makes it possible to decompose the total vibrational motion into individual contributions associated with the formation of acoustic waves with longitudinal and transverse polarizations. Comparison of the heights of the low-frequency component and of the high-frequency peak in the spectral density of vibrational states also indicates a temperature of T ≈ 600 K, at which the diffusion type of one-particle dynamics changes to the vibrational type upon a decrease in temperature. It is demonstrated that the modified Einstein–Stokes relation can be derived using the generalized Debye model.« less

Amorphous ices explained in terms of nonequilibrium phase transitions in supercooled water

NASA Astrophysics Data System (ADS)

Limmer, David; Chandler, David

2013-03-01

We analyze the phase diagram of supercooled water out-of-equilibrium using concepts from space-time thermodynamics and the dynamic facilitation theory of the glass transition, together with molecular dynamics simulations. We find that when water is driven out-of-equilibrium, it can exist in multiple amorphous states. In contrast, we find that when water is at equilibrium, it can exist in only one liquid state. The amorphous non-equilibrium states are solids, distinguished from the liquid by their lack of mobility, and distinguished from each other by their different densities and local structure. This finding explains the experimentally observed polyamorphism of water as a class of nonequilibrium phenomena involving glasses of different densities. While the amorphous solids can be long lived, they are thermodynamically unstable. When allowed to relax to equilibrium, they crystallize with pathways that pass first through liquid state configurations and then to ordered ice.

Unraveling the Stepwise Melting of an Ionic Liquid.

PubMed

Lima, Thamires A; Paschoal, Vitor H; Faria, Luiz F O; Ribeiro, Mauro C C

2017-05-04

Differential scanning calorimetry, X-ray diffraction, and Raman spectroscopy were used to reveal the premelting events precursors of melting of the ionic liquid triethylsulfonium bis(trifluoromethanesufonyl)imide, [S 222 ][NTf 2 ]. On heating the crystalline phase of [S 222 ][NTf 2 ], melting occurs along a sequence of at least three steps. First, the crystalline long-range order breaks down, but local order is retained. The second step is characterized by conformational freedom of the ethyl chains of cations related to premelting of nonpolar domains, and the complete melting finally occurs when anions acquire conformational freedom. This work provides a microscopic view on the mechanism of melting of [S 222 ][NTf 2 ] in line with the picture of melting taking place as a sequence of structural changes. The results of this work shed light on the understanding of the complex melting process of ionic liquids.

Ferromagnetic Switching of Knotted Vector Fields in Liquid Crystal Colloids.

PubMed

Zhang, Qiaoxuan; Ackerman, Paul J; Liu, Qingkun; Smalyukh, Ivan I

2015-08-28

We experimentally realize polydomain and monodomain chiral ferromagnetic liquid crystal colloids that exhibit solitonic and knotted vector field configurations. Formed by dispersions of ferromagnetic nanoplatelets in chiral nematic liquid crystals, these colloidal ferromagnets exhibit spontaneous long-range alignment of magnetic dipole moments of individual platelets, giving rise to a continuum of the magnetization field M(r). Competing effects of surface confinement and chirality prompt spontaneous formation and enable the optical generation of localized twisted solitonic structures with double-twist tubes and torus knots of M(r), which exhibit a strong sensitivity to the direction of weak magnetic fields ∼1  mT. Numerical modeling, implemented through free energy minimization to arrive at a field-dependent three-dimensional M(r), shows a good agreement with experiments and provides insights into the torus knot topology of observed field configurations and the corresponding physical underpinnings.

Carbon diffusion in molten uranium: an ab initio molecular dynamics study

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

Garrett, Kerry E.; Abrecht, David G.; Kessler, Sean H.

In this work we used ab initio molecular dynamics (AIMD) within the framework of density functional theory (DFT) and the projector-augmented wave (PAW) method to study carbon diffusion in liquid uranium at temperatures above 1600 K. The electronic interactions of carbon and uranium were described using the local density approximation (LDA). The self-diffusion of uranium based on this approach is compared with literature computational and experimental results for liquid uranium. The temperature dependence of carbon and uranium diffusion in the melt was evaluated by fitting the resulting diffusion coefficients to an Arrhenius relationship. We found that the LDA calculated activationmore » energy for carbon was nearly twice that of uranium: 0.55±0.03 eV for carbon compared to 0.32±0.04 eV for uranium. Structural analysis of the liquid uranium-carbon system is also discussed.« less

NIMROD: The Near and InterMediate Range Order Diffractometer of the ISIS second target station.

PubMed

Bowron, D T; Soper, A K; Jones, K; Ansell, S; Birch, S; Norris, J; Perrott, L; Riedel, D; Rhodes, N J; Wakefield, S R; Botti, A; Ricci, M-A; Grazzi, F; Zoppi, M

2010-03-01

NIMROD is the Near and InterMediate Range Order Diffractometer of the ISIS second target station. Its design is optimized for structural studies of disordered materials and liquids on a continuous length scale that extends from the atomic, upward of 30 nm, while maintaining subatomic distance resolution. This capability is achieved by matching a low and wider angle array of high efficiency neutron scintillation detectors to the broad band-pass radiation delivered by a hybrid liquid water and liquid hydrogen neutron moderator assembly. The capabilities of the instrument bridge the gap between conventional small angle neutron scattering and wide angle diffraction through the use of a common calibration procedure for the entire length scale. This allows the instrument to obtain information on nanoscale systems and processes that are quantitatively linked to the local atomic and molecular order of the materials under investigation.

Computational Simulation of Vibrational Overtone Spectral Regions: Sarin

DTIC Science & Technology

2006-12-01

level have been used to determine the vapour phase local mode parameters, [ and Dx, for each oscillator in the two spectrally significant conformers...approach to spectral simulation reported herein should be undertaken by acquiring the experimental spectral regions of several CWAs in the vapour and liquid...33 viii DRDC Suffield TR 2006-220 List of figures Figure 1: The vapour phase structures of the three lowest energy conformers of sarin, calculated

Harnessing Electrostatic Forces to Grow Bio-inspired Hierarchical Vascular Networks

NASA Astrophysics Data System (ADS)

Behler, Kristopher; Melrose, Zachary; Schott, Andrew; Wetzel, Eric

2012-02-01

Vascular networks provide a system for fluid distribution. Artificial vascular materials with enhanced properties are currently being developed that could ultimately be integrated into systems reliant upon fluid transport while retaining their structural properties. An uninterrupted and controllable supply of liquid is optimal for many applications such as continual self-healing materials, in-situ delivery of index matched fluids, thermal management and drug delivery systems could benefit from a bio-inspired vascular approach that combines complex network geometries with minimal processing parameters. Two such approaches to induce vascular networks are electrohydrodynamic viscous fingering (EHVF) and electrical treeing (ET). EHVF is a phenomenon that occurs when a low viscosity liquid is forced through a high viscosity fluid or matrix, resulting in branches due to capillary and viscous forces in the high viscosity material. By applying voltages of 0 -- 60 kV, finger diameter is reduced. ET is the result of partial discharges in a dielectric material. In the vicinity of a small diameter electrode, the local electric field is greater than the global dielectric strength, causing a localized, step-wise, breakdown to occur forming a highly branched interconnected structure. ET is a viable method to produce networks on a smaller, micron, scale than the products of the EHVF method.

Determination of local values of gas and liquid mass flux in highly loaded two-phase flow

NASA Technical Reports Server (NTRS)

Burick, R. J.; Scheuerman, C. H.; Falk, A. Y.

1974-01-01

A measurement system using a deceleration probe was designed for determining the local values of gas and liquid mass flux in various gas/liquid droplet sprayfields. The system was used to characterize two-phase flowfields generated by gas/liquid rocket-motor injectors. Measurements were made at static pressures up to 500 psia and injected mass flow ratios up to 20. The measurement system can also be used at higher pressures and in gas/solid flowfields.

United polarizable multipole water model for molecular mechanics simulation

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

Qi, Rui; Wang, Qiantao; Ren, Pengyu, E-mail: pren@mail.utexas.edu

2015-07-07

We report the development of a united AMOEBA (uAMOEBA) polarizable water model, which is computationally 3–5 times more efficient than the three-site AMOEBA03 model in molecular dynamics simulations while providing comparable accuracy for gas-phase and liquid properties. In this coarse-grained polarizable water model, both electrostatic (permanent and induced) and van der Waals representations have been reduced to a single site located at the oxygen atom. The permanent charge distribution is described via the molecular dipole and quadrupole moments and the many-body polarization via an isotropic molecular polarizability, all located at the oxygen center. Similarly, a single van der Waals interactionmore » site is used for each water molecule. Hydrogen atoms are retained only for the purpose of defining local frames for the molecular multipole moments and intramolecular vibrational modes. The parameters have been derived based on a combination of ab initio quantum mechanical and experimental data set containing gas-phase cluster structures and energies, and liquid thermodynamic properties. For validation, additional properties including dimer interaction energy, liquid structures, self-diffusion coefficient, and shear viscosity have been evaluated. The results demonstrate good transferability from the gas to the liquid phase over a wide range of temperatures, and from nonpolar to polar environments, due to the presence of molecular polarizability. The water coordination, hydrogen-bonding structure, and dynamic properties given by uAMOEBA are similar to those derived from the all-atom AMOEBA03 model and experiments. Thus, the current model is an accurate and efficient alternative for modeling water.« less

Theoretical Studies of Nonuniform Orientational Order in Liquid Crystals and Active Particles

NASA Astrophysics Data System (ADS)

Duzgun, Ayhan

I investigate three systems that exhibit complex patterns in orientational order, which are controlled by geometry interacting with the dynamics of phase transitions, metastability, and activity. 1. Liquid Crystal Elastomers: Liquid-crystal elastomers are remarkable materials that combine the elastic properties of cross-linked polymer networks with the anisotropy of liquid crystals. Any distortion of the polymer network affects the nematic order of the liquid crystal, and, likewise, any change in the magnitude or direction of the nematic order influences the shape of the elastomer. When elastomers are prepared without any alignment, they develop disordered polydomain structures as they are cooled into the nematic phase. To model these polydomain structures, I develop a dynamic theory for the isotropic-nematic transition in elastomers. 2. Active Brownian Particles: Unlike equilibrium systems, active matter is not governed by the conventional laws of thermodynamics. I perform Langevin dynamics simulations and analytic calculations to explore how systems cross over from equilibrium to active behavior as the activity is increased. Based on these results, I calculate how the pressure depends on wall curvature, and hence make analytic predictions for the motion of curved tracers and other effects of confinement in active matter systems. 3. Skyrmions in Liquid Crystals: Skyrmions are localized topological defects in the orientation of an order parameter field, without a singularity in the magnitude of the field. For many years, such defects have been studied in the context of chiral liquid crystals--for example, as bubbles in a confined cholesteric phase or as double-twist tubes in a blue phase. More recently, skyrmions have been investigated extensively in the context of chiral magnets. In this project, I compare skyrmions in chiral liquid crystals with the analogous magnetic defects. Through simulations based on the nematic order tensor, I model both isolated skyrmions and periodic defect lattices.

Revealing Hidden Structural Order Controlling Both Fast and Slow Glassy Dynamics in Supercooled Liquids

NASA Astrophysics Data System (ADS)

Tong, Hua; Tanaka, Hajime

2018-01-01

The dynamics of a supercooled liquid near the glass transition is characterized by two-step relaxation, fast β and slow α relaxations. Because of the apparently disordered nature of glassy structures, there have been long debates over whether the origin of drastic slowing-down of the α relaxation accompanied by heterogeneous dynamics is thermodynamic or dynamic. Furthermore, it has been elusive whether there is any deep connection between fast β and slow α modes. To settle these issues, here we introduce a set of new structural order parameters characterizing sterically favored structures with high local packing capability, and then access structure-dynamics correlation by a novel nonlocal approach. We find that the particle mobility is under control of the static order parameter field. The fast β process is controlled by the instantaneous order parameter field locally, resulting in short-time particle-scale dynamics. Then the mobility field progressively develops with time t , following the initial order parameter field from disorder to more ordered regions. As is well known, the heterogeneity in the mobility field (dynamic heterogeneity) is maximized with a characteristic length ξ4, when t reaches the relaxation time τα. We discover that this mobility pattern can be predicted solely by a spatial coarse graining of the initial order parameter field at t =0 over a length ξ without any dynamical information. Furthermore, we find a relation ξ ˜ξ4, indicating that the static length ξ grows coherently with the dynamic one ξ4 upon cooling. This further suggests an intrinsic link between τα and ξ : the growth of the static length ξ is the origin of dynamical slowing-down. These we confirm for the first time in binary glass formers both in two and three spatial dimensions. Thus, a static structure has two intrinsic characteristic lengths, particle size and ξ , which control dynamics in local and nonlocal manners, resulting in the emergence of the two key relaxation modes, fast β and slow α processes, respectively. Because the two processes share a common structural origin, we can even predict a dynamic propensity pattern at long timescale from the fast β pattern. The presence of such intrinsic structure-dynamics correlation strongly indicates a thermodynamic nature of glass transition.

Solvation structures of water in trihexyltetradecylphosphonium-orthoborate ionic liquids

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

Wang, Yong-Lei, E-mail: wangyonl@gmail.com; System and Component Design, Department of Machine Design, KTH Royal Institute of Technology, SE-100 44 Stockholm; Sarman, Sten

2016-08-14

Atomistic molecular dynamics simulations have been performed to investigate effective interactions of isolated water molecules dispersed in trihexyltetradecylphosphonium-orthoborate ionic liquids (ILs). The intrinsic free energy changes in solvating one water molecule from gas phase into bulk IL matrices were estimated as a function of temperature, and thereafter, the calculations of potential of mean force between two dispersed water molecules within different IL matrices were performed using umbrella sampling simulations. The systematic analyses of local ionic microstructures, orientational preferences, probability and spatial distributions of dispersed water molecules around neighboring ionic species indicate their preferential coordinations to central polar segments in orthoboratemore » anions. The effective interactions between two dispersed water molecules are partially or totally screened as their separation distance increases due to interference of ionic species in between. These computational results connect microscopic anionic structures with macroscopically and experimentally observed difficulty in completely removing water from synthesized IL samples and suggest that the introduction of hydrophobic groups to central polar segments and the formation of conjugated ionic structures in orthoborate anions can effectively reduce residual water content in the corresponding IL samples.« less

Fermionic spin liquid analysis of the paramagnetic state in volborthite

NASA Astrophysics Data System (ADS)

Chern, Li Ern; Schaffer, Robert; Sorn, Sopheak; Kim, Yong Baek

2017-10-01

Recently, thermal Hall effect has been observed in the paramagnetic state of volborthite, which consists of distorted kagome layers with S =1 /2 local moments. Despite the appearance of magnetic order below 1 K , the response to external magnetic field and unusual properties of the paramagnetic state above 1 K suggest possible realization of exotic quantum phases. Motivated by these discoveries, we investigate possible spin liquid phases with fermionic spinon excitations in a nonsymmorphic version of the kagome lattice, which belongs to the two-dimensional crystallographic group p 2 g g . This nonsymmorphic structure is consistent with the spin model obtained in the density functional theory calculation. Using projective symmetry group analysis and fermionic parton mean field theory, we identify twelve distinct Z2 spin liquid states, four of which are found to have correspondence in the eight Schwinger boson spin liquid states we classified earlier. We focus on the four fermionic states with bosonic counterpart and find that the spectrum of their corresponding root U (1 ) states features spinon Fermi surface. The existence of spinon Fermi surface in candidate spin liquid states may offer a possible explanation of the finite thermal Hall conductivity observed in volborthite.

A computational study of diffusion in a glass-forming metallic liquid

DOE PAGES

Wang, T.; Zhang, F.; Yang, L.; ...

2015-06-09

In this study, liquid phase diffusion plays a critical role in phase transformations (e.g. glass transformation and devitrification) observed in marginal glass forming systems such as Al-Sm. Controlling transformation pathways in such cases requires a comprehensive description of diffusivity, including the associated composition and temperature dependencies. In our computational study, we examine atomic diffusion in Al-Sm liquids using ab initio molecular dynamics (AIMD) and determine the diffusivities of Al and Sm for selected alloy compositions. Non-Arrhenius diffusion behavior is observed in the undercooled liquids with an enhanced local structural ordering. Through assessment of our AIMD result, we construct a generalmore » formulation for Al-Sm liquid, involving a diffusion mobility database that includes composition and temperature dependence. A Volmer-Fulcher-Tammann (VFT) equation is adopted for describing the non-Arrhenius behavior observed in the undercooled liquid. Furthermore, the composition dependence of diffusivity is found quite strong, even for the Al-rich region contrary to the sole previous report on this binary system. The model is used in combination with the available thermodynamic database to predict specific diffusivities and compares well with reported experimental data for 0.6 at.% and 5.6 at.% Sm in Al-Sm alloys.« less

Faraday wave lattice as an elastic metamaterial.

PubMed

Domino, L; Tarpin, M; Patinet, S; Eddi, A

2016-05-01

Metamaterials enable the emergence of novel physical properties due to the existence of an underlying subwavelength structure. Here, we use the Faraday instability to shape the fluid-air interface with a regular pattern. This pattern undergoes an oscillating secondary instability and exhibits spontaneous vibrations that are analogous to transverse elastic waves. By locally forcing these waves, we fully characterize their dispersion relation and show that a Faraday pattern presents an effective shear elasticity. We propose a physical mechanism combining surface tension with the Faraday structured interface that quantitatively predicts the elastic wave phase speed, revealing that the liquid interface behaves as an elastic metamaterial.

Nano-Material Aspects of Shock Absorption in Bone Joints

PubMed Central

Tributsch, H; Copf, F; Copf, p; Hindenlang, U; Niethard, F.U; Schneider, R

2010-01-01

This theoretical study is based on a nano-technological evaluation of the effect of pressure on the composite bone fine structure. It turned out, that the well known macroscopic mechano-elastic performance of bones in combination with muscles and tendons is just one functional aspect which is critically supported by additional micro- and nano- shock damping technology aimed at minimising local bone material damage within the joints and supporting spongy bone material. The identified mechanisms comprise essentially three phenomena localised within the three–dimensional spongy structure with channels and so called perforated flexible tensulae membranes of different dimensions intersecting and linking them. Kinetic energy of a mechanical shock may be dissipated within the solid-liquid composite bone structure into heat via the generation of quasi-chaotic hydromechanic micro-turbulence. It may generate electro-kinetic energy in terms of electric currents and potentials. And the resulting specific structural and surface electrochemical changes may induce the compressible intra-osseal liquid to build up pressure dependent free chemical energy. Innovative bone joint prostheses will have to consider and to be adapted to the nano-material aspects of shock absorption in the operated bones. PMID:21625375

Structural transition in sputter-deposited amorphous germanium films by aging at ambient temperature

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

Okugawa, M.; Nakamura, R., E-mail: nakamura@mtr.osakafu-u.ac.jp; Numakura, H.

The structure of amorphous Ge (a-Ge) films prepared by sputter-deposition and the effects of aging at ambient temperature and pressure were studied by pair-distribution-function (PDF) analysis from electron scattering and molecular dynamics simulations. The PDFs of the as-deposited and aged samples for 3–13 months showed that the major peaks for Ge-Ge bonds decrease in intensity and broaden with aging for up to 7 months. In the PDFs of a-Ge of molecular dynamics simulation obtained by quenching liquid at different rates, the major peak intensities of a slowly cooled model are higher than those of a rapidly cooled model. Analyses onmore » short- and medium-range configurations show that the slowly cooled model includes a certain amount of medium-range ordered (MRO) clusters, while the rapidly cooled model includes liquid-like configurations rather than MRO clusters. The similarity between experimental and computational PDFs implies that as-deposited films are similar in structure to the slowly cooled model, whereas the fully aged films are similar to the rapidly cooled model. It is assumed that as they undergo room-temperature aging, the MRO clusters disintegrate and transform into liquid-like regions in the same matrix. This transition in local configurations is discussed in terms of instability and the non-equilibrium of nanoclusters produced by a vapor-deposition process.« less

Molecular orientation in a dielectric liquid-vapor interphase

NASA Astrophysics Data System (ADS)

Chacón, E.; Mederos, L.; Navascués, G.; Tarazona, P.

1985-04-01

The density functional theory of Chacón et al. is used to study the molecular orientation in an interphase of a weak dipolar fluid. Explicit expressions are obtained using standard perturbation techniques. Molecular orientation, local susceptibility, and the Gibbsean surface susceptibility are evaluated for a Stockmayer model of dipolar fluid. The effect of the surface structure on the bulk ferroelectric transition is discussed in the light of the present theory and the numerical results.

Unveiling the structural arrangements responsible for the atomic dynamics in metallic glasses during physical aging

NASA Astrophysics Data System (ADS)

Giordano, V. M.; Ruta, B.

2016-01-01

Understanding and controlling physical aging, that is, the spontaneous temporal evolution of out-of-equilibrium systems, represents one of the greatest tasks in material science. Recent studies have revealed the existence of a complex atomic motion in metallic glasses, with different aging regimes in contrast with the typical continuous aging observed in macroscopic quantities. By combining dynamical and structural synchrotron techniques, here for the first time we directly connect previously identified microscopic structural mechanisms with the peculiar atomic motion, providing a broader unique view of their complexity. We show that the atomic scale is dominated by the interplay between two processes: rearrangements releasing residual stresses related to a cascade mechanism of relaxation, and medium range ordering processes, which do not affect the local density, likely due to localized relaxations of liquid-like regions. As temperature increases, a surprising additional secondary relaxation process sets in, together with a faster medium range ordering, likely precursors of crystallization.

Pressure/temperature fluid cell apparatus for the neutron powder diffractometer instrument: probing atomic structure in situ.

PubMed

Wang, Hsiu-Wen; Fanelli, Victor R; Reiche, Helmut M; Larson, Eric; Taylor, Mark A; Xu, Hongwu; Zhu, Jinlong; Siewenie, Joan; Page, Katharine

2014-12-01

This contribution describes a new local structure compatible gas/liquid cell apparatus for probing disordered materials at high pressures and variable temperatures in the Neutron Powder Diffraction instrument at the Lujan Neutron Scattering Center, Los Alamos National Laboratory. The new sample environment offers choices for sample canister thickness and canister material type. Finite element modeling is utilized to establish maximum allowable working pressures of 414 MPa at 15 K and 121 MPa at 600 K. High quality atomic pair distribution function data extraction and modeling have been demonstrated for a calibration standard (Si powder) and for supercritical and subcritical CO2 measurements. The new sample environment was designed to specifically target experimental studies of the local atomic structures involved in geologic CO2 sequestration, but will be equally applicable to a wide variety of energy applications, including sorption of fluids on nano/meso-porous solids, clathrate hydrate formation, catalysis, carbon capture, and H2 and natural gas uptake/storage.

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

Braun, Efrem; Chen, Joseph J.; Schnell, Sondre K.

Molecular simulations and NMR relaxometry experiments demonstrate that pure benzene or xylene confined in isoreticular metal–organic frameworks (IRMOFs) exhibit true vapor–liquid phase equilibria where the effective critical point may be reduced by tuning the structure of the MOF. Our results are consistent with vapor and liquid phases extending over many MOF unit cells. These results are counterintuitive since the MOF pore diameters are approximately the same length scale as the adsorbate molecules. As applications of these materials in catalysis, separations, and gas storage rely on the ability to tune the properties of adsorbed molecules, we anticipate that the ability tomore » systematically control the critical point, thereby preparing spatially inhomogeneous local adsorbate densities, could add a new design tool for MOF applications.« less

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

Braun, Efrem; Chen, Joseph J.; Schnell, Sondre K.

Molecular simulations and NMR relaxometry experiments demonstrate that pure benzene or xylene confined in isoreticular metal–organic frameworks (IRMOFs) exhibit true vapor–liquid phase equilibria where the effective critical point may be reduced by tuning the structure of the MOF. Our results are consistent with vapor and liquid phases extending over many MOF unit cells. These results are counterintuitive since the MOF pore diameters are approximately the same length scale as the adsorbate molecules. Lastly, as applications of these materials in catalysis, separations, and gas storage rely on the ability to tune the properties of adsorbed molecules, we anticipate that the abilitymore » to systematically control the critical point, thereby preparing spatially inhomogeneous local adsorbate densities, could add a new design tool for MOF applications.« less

Electrical Transport Properties of Liquid Al-Cu Alloys

NASA Astrophysics Data System (ADS)

Thakore, B. Y.; Khambholja, S. G.; Suthar, P. H.; Jani, A. R.

2010-06-01

Electrical transport properties viz. electrical resistivity, thermoelectric power and thermal conductivity of liquid Al-Cu alloys as a function of Cu concentration have been studied in the present paper. Ashcroft empty core model potential has been used to incorporate the ion-electron interaction. To incorporate the exchange and correlation effects, five different forms of local field correction functions viz. Hartree, Taylor, Ichimaru et al., Farid et al. and Sarkar et al. have been used. The transport properties of binary system have been studied using Faber-Ziman formulation combined with Ashcroft-Langreth (AL) partial structure factor. The computed values of electrical resistivity are compared with experimental data and for low Cu concentration, good agreement has been observed. Further, thermoelectric power and thermal conductivity have also been predicted.

Linear and nonlinear properties of photonic crystal fibers filled with nematic liquid crystals

NASA Astrophysics Data System (ADS)

Brzdąkiewicz, K. A.; Laudyn, U. A.; Karpierz, M. A.; Woliński, T. R.; Wójcik, J.

2006-12-01

We investigate linear and nonlinear light propagation in the photonic crystal fibers infiltrated with nematic liquid crystals. Such a photonic structure, with periodic modulation of refractive index, which could be additionally controlled by the temperature and by the optical power, allows for the study of discrete optical phenomena. Our theoretical investigations, carried out with the near infrared wavelength of 830 nm, for both focusing and defocusing Kerr-type nonlinearity, show the possibility of the transverse light localization, which can result in the discrete soliton generation. In addition, we present the preliminary experimental results on the linear light propagation in the photonic crystal fiber with the glycerin-water solution and 6CHBT nematics, as the guest materials.

Growth Kinetics of Intracellular RNA/Protein Droplets: Signature of a Liquid-Liquid Phase Transition?

NASA Astrophysics Data System (ADS)

Berry, Joel; Weber, Stephanie C.; Vaidya, Nilesh; Zhu, Lian; Haataja, Mikko; Brangwynne, Clifford P.

2015-03-01

Nonmembrane-bound organelles are functional, dynamic assemblies of RNA and/or protein that can self-assemble and disassemble within the cytoplasm or nucleoplasm. The possibility that underlying intracellular phase transitions may drive and mediate the morphological evolution of some membrane-less organelles has been supported by several recent studies. In this talk, results from a collaborative experimental-theoretical study of the growth and dissolution kinetics of nucleoli and extranucleolar droplets (ENDs) in C. elegans embryos will be presented. We have employed Flory-Huggins solution theory, reaction-diffusion kinetics, and quantitative statistical dynamic scaling analysis to characterize the specific growth mechanisms at work. Our findings indicate that both in vivo and in vitro droplet scaling and growth kinetics are consistent with those resulting from an equilibrium liquid-liquid phase transition mediated by passive nonequilibrium growth mechanisms - simultaneous Brownian coalescence and Ostwald ripening. This supports a view in which cells can employ phase transitions to drive structural organization, while utilizing active processes, such as local transcriptional activity, to fine tune the kinetics of these phase transitions in response to given conditions.

Highly Swellable, Dual-Responsive Hydrogels Based on PNIPAM and Redox Active Poly(ferrocenylsilane) Poly(ionic liquid)s: Synthesis, Structure, and Properties.

PubMed

Feng, Xueling; Zhang, Kaihuan; Chen, Peng; Sui, Xiaofeng; Hempenius, Mark A; Liedberg, Bo; Vancso, G Julius

2016-12-01

Highly swellable, dual-responsive hydrogels, consisting of thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) and redox-responsive poly(ferrocenylsilane) (PFS) based poly(ionic liquid)s (PILs) are formed by photo-polymerization. PFS chains bearing cross-linkable vinylimidazolium (VIm) side groups are copolymerized with NIPAM in aqueous solutions under ultraviolet light (λ = 365 nm) in the presence of a photoinitiator. The PFS-PILs serve as a macro-cross-linker and also provide redox responsiveness. The swelling ratio, morphology, and lower critical solution temperature (LCST) of the hydrogels are studied as a function of the PNIPAM/PFS ratio. The value of the LCST is dependent on the choice of the counterion of the PIL and the PNIPAM/PFS ratio. The hydrogel is employed as a reducing environment for the in situ fabrication of gold nanoparticles (AuNPs), forming AuNP-hydrogel composites. The localized surface plasmon resonance peak of the as-synthesized Au nanoparticles inside the hydrogel could be tuned by altering the temperature. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Principles and applications of laser-induced liquid-phase jet-chemical etching

NASA Astrophysics Data System (ADS)

Stephen, Andreas; Metev, Simeon; Vollertsen, Frank

2003-11-01

In this treatment method laser radiation, which is guided from a coaxially expanding liquid jet-stream, locally initiates a thermochemical etching reaction on a metal surface, which leads to selective material removal at high resolution and quality of the treated surface as well as low thermal influence on the workpiece. Electrochemical investigations were performed under focused laser irradiation using a cw-Nd:YAG laser with a maximum power of 15 W and a simultaneous impact of the liquid jet-stream consisting of phosphoric acid with a maximum flow rate of 20 m/s. The time resolved measurements of the electrical potential difference against an electrochemical reference electrode were correlated with the specific processing parameters and corresponding etch rates to identify processing conditions for temporally stable and enhanced chemical etching reactions. Applications of laser-induced liquid-phase jet-chemical etching in the field of sensor technology, micromechanics and micrmoulding technology are presented. This includes the microstructuring of thin film systems, cutting of foils of shape memory alloys or the generation of structures with defined shape in bulk material.

Preliminary experiments to quantify liquid movement under mimetic vocal fold vibrational forces.

PubMed

Titze, Ingo R; Klemuk, Sarah; Lu, Xiaoying

2014-07-01

Hydration of vocal fold tissues is essential for self-sustained oscillation. Normal regulatory processes of liquid transport to and from the vocal folds would be expected through the autonomic systems, but the possibility exists that liquid movement may occur locally due to vibrational pressures. Such movement may cause regions of lower or higher concentrations of liquid viscosity and therewith changes in phonation threshold pressure. Hyaluronic acid, a glycosaminoglycan that attracts large quantities of free water, may be a key molecule for transporting or localizing liquids. Some preliminary experiments are reported in which attempts were made to move low-concentration HA liquids with vibration. None of the experiments was conclusive, but collectively they lay some groundwork for future explorations.

Structure and function of seed storage proteins in faba bean (Vicia faba L.).

PubMed

Liu, Yujiao; Wu, Xuexia; Hou, Wanwei; Li, Ping; Sha, Weichao; Tian, Yingying

2017-05-01

The protein subunit is the most important basic unit of protein, and its study can unravel the structure and function of seed storage proteins in faba bean. In this study, we identified six specific protein subunits in Faba bean (cv. Qinghai 13) combining liquid chromatography (LC), liquid chromatography-electronic spray ionization mass (LC-ESI-MS/MS) and bio-information technology. The results suggested a diversity of seed storage proteins in faba bean, and a total of 16 proteins (four GroEL molecular chaperones and 12 plant-specific proteins) were identified from 97-, 96-, 64-, 47-, 42-, and 38-kD-specific protein subunits in faba bean based on the peptide sequence. We also analyzed the composition and abundance of the amino acids, the physicochemical characteristics, secondary structure, three-dimensional structure, transmembrane domain, and possible subcellular localization of these identified proteins in faba bean seed, and finally predicted function and structure. The three-dimensional structures were generated based on homologous modeling, and the protein function was analyzed based on the annotation from the non-redundant protein database (NR database, NCBI) and function analysis of optimal modeling. The objective of this study was to identify the seed storage proteins in faba bean and confirm the structure and function of these proteins. Our results can be useful for the study of protein nutrition and achieve breeding goals for optimal protein quality in faba bean.

Structural characteristics of liquid nitromethane at the nanoscale confinement in carbon nanotubes.

PubMed

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

2014-10-01

The stability of energetic materials confined in the carbon nanotubes can be improved at ambient pressure and room temperature, leading to potential energy storage and controlled energy release. However, the microscopic structure of confined energetic materials and the role played by the confinement size are still fragmentary. In this study, molecular dynamics simulations have been performed to explore the structural characteristics of liquid nitromethane (NM), one of the simplest energetic materials, confined in a series of armchair single-walled carbon nanotubes (SWNTs) changing from (5,5) to (16,16) at ambient conditions. The simulation results show that the size-dependent ordered structures of NM with preferred orientations are formed inside the tubular cavities driven by the van der Waals attractions between NM and SWNT together with the dipole-dipole interactions of NM, giving rise to a higher local mass density than that of bulk NM. The NM dipoles prefer to align parallel along the SWNT axis in an end-to-end fashion inside all the nanotubes except the (7,7) SWNT where a unique staggered orientation of NM dipoles perpendicular to the SWNT axis is observed. As the SWNT radius increases, the structural arrangements and dipole orientations of NM become disordered as a result of the weakening of van der Waals interactions between NM and SWNT.

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

Li, Rong; Wu, Yongquan, E-mail: yqwu@shu.edu.cn; Xiao, Junjiang

We observed homogeneous nucleation process of supercooled liquid Fe by molecular dynamics simulations. Using bond-orientational order parameters together with Voronoi polyhedron method, we characterized local structure, calculated the volume of Voronoi polyhedra of atoms and identified the structure and density fluctuations. We monitored the formation of nucleus and analyzed its inner structure. The birth and growth of the pre-nucleus and nucleus are accompanied with aggregating and disaggregating processes in the time scale of femtosecond. Only the initial solid-like clusters (ISLC), ranging from 1 to 7 atoms, pop up directly from liquid. The relation between the logarithm of number of clustersmore » and the cluster size was found to be linear for ISLCs and was observed to be parabolic for all solid-like clusters (SLC) due to aggregating and disaggregating effects. The nucleus and pre-nuclei mainly consist of body centered cubic (BCC) and hexagonal close packed atoms, while the BCC atoms tend to be located at the surface. Medium-range structure fluctuations induce the birth of ISLCs, benefit the aggregation of embryos and remarkably promote the nucleation. But density fluctuations contribute little to nucleation. The lifetime of most icosahedral-like atoms (ICO) is shorter than 0.7 ps. No obvious relationship was found between structure/density fluctuations and the appearance of ICO atoms.« less

Elastic stress transmission and transformation (ESTT) by confined liquid: A new mechanics for fracture in elastic lithosphere of the earth

USGS Publications Warehouse

Xu, Xing-Wang; Peters, Stephen; Liang, Guang-He; Zhang, Bao-Lin

2016-01-01

Tectonic stress alters local stress fields in the surrounding country rocks and therefore synchronously varies the local effective tensile tangential stress and the nature and geometry of the liquid-driven fractures.

Final Report for DE-FG02-93ER14376,Ionic Transport in Electrochemical Media

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

J. W. Halley

This project was a molecular dynamics study of the relevant issues associated with the structure and transport of lithium in polymer electrolytes such as polyethylene oxide(PEO). In close collaboration with quantum chemist Larry Curtiss and neutron scatterers David Lee Price and Marie-Louise Saboungi at Argonne, we used molecular dynamics to study the local structure and dynamics and ion transport in the polymer. The studies elucidated the mechanism of Li transport in PEO, revealing that the rate limiting step is extremely sensitive to the magnitude of the torsion forces in the backbone of the polymer. Because the torsion forces are difficultmore » to manipulate chemically, this makes it easier to understand why improving the conductivity of PEO based electrolytes has proven to be very difficult. We studied the transport properties of cations in ionic liquids as possible additives to polymer membranes for batteries and fuel cells and found preliminary indications that the transport is enhanced near phase separation in acid-ionic liquid mixtures.« less

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

Helfferich, Julian; Lyubimov, Ivan; Reid, Daniel

Glasses produced via physical vapor deposition can display greater kinetic stability and lower enthalpy than glasses prepared by liquid cooling. While the reduced enthalpy has often been used as a measure of the stability, it is not obvious whether dynamic measures of stability provide the same view. Here, we study dynamics in vapor-deposited and liquid-cooled glass films using molecular simulations of a bead-spring polymer model as well as a Lennard-Jones binary mixture in two and three dimensions. We confirm that the dynamics in vapor-deposited glasses is indeed slower than in ordinary glasses. We further show that the inherent structure energymore » is a good reporter of local dynamics, and that aged systems and glasses prepared by cooling at progressively slower rates exhibit the same behavior as vapor-deposited materials when they both have the same inherent structure energy. These findings suggest that the stability inferred from measurements of the energy is also manifested in dynamic observables, and they strengthen the view that vapor deposition processes provide an effective strategy for creation of stable glasses.« less

Fragile-to-strong transition in liquid silica

NASA Astrophysics Data System (ADS)

Geske, Julian; Drossel, Barbara; Vogel, Michael

2016-03-01

We investigate anomalies in liquid silica with molecular dynamics simulations and present evidence for a fragile-to-strong transition at around 3100 K-3300 K. To this purpose, we studied the structure and dynamical properties of silica over a wide temperature range, finding four indicators of a fragile-to-strong transition. First, there is a density minimum at around 3000 K and a density maximum at 4700 K. The turning point is at 3400 K. Second, the local structure characterized by the tetrahedral order parameter changes dramatically around 3000 K from a higher-ordered, lower-density phase to a less ordered, higher-density phase. Third, the correlation time τ changes from an Arrhenius behavior below 3300 K to a Vogel-Fulcher-Tammann behavior at higher temperatures. Fourth, the Stokes-Einstein relation holds for temperatures below 3000 K, but is replaced by a fractional relation above this temperature. Furthermore, our data indicate that dynamics become again simple above 5000 K, with Arrhenius behavior and a classical Stokes-Einstein relation.

IR spectral assignments for the hydrated excess proton in liquid water.

PubMed

Biswas, Rajib; Carpenter, William; Fournier, Joseph A; Voth, Gregory A; Tokmakoff, Andrei

2017-04-21

The local environmental sensitivity of infrared (IR) spectroscopy to a hydrogen-bonding structure makes it a powerful tool for investigating the structure and dynamics of excess protons in water. Although of significant interest, the line broadening that results from the ultrafast evolution of different solvated proton-water structures makes the assignment of liquid-phase IR spectra a challenging task. In this work, we apply a normal mode analysis using density functional theory of thousands of proton-water clusters taken from reactive molecular dynamics trajectories of the latest generation multistate empirical valence bond proton model (MS-EVB 3.2). These calculations are used to obtain a vibrational density of states and IR spectral density, which are decomposed on the basis of solvated proton structure and the frequency dependent mode character. Decompositions are presented on the basis of the proton sharing parameter δ, often used to distinguish Eigen and Zundel species, the stretch and bend character of the modes, the mode delocalization, and the vibrational mode symmetry. We find there is a wide distribution of vibrational frequencies spanning 1200-3000 cm -1 for every local proton configuration, with the region 2000-2600 cm -1 being mostly governed by the distorted Eigen-like configuration. We find a continuous red shift of the special-pair O⋯H + ⋯O stretching frequency, and an increase in the flanking water bending intensity with decreasing δ. Also, we find that the flanking water stretch mode of the Zundel-like species is strongly mixed with the flanking water bend, and the special pair proton oscillation band is strongly coupled with the bend modes of the central H 5 O2+moiety.

IR spectral assignments for the hydrated excess proton in liquid water

NASA Astrophysics Data System (ADS)

Biswas, Rajib; Carpenter, William; Fournier, Joseph A.; Voth, Gregory A.; Tokmakoff, Andrei

2017-04-01

The local environmental sensitivity of infrared (IR) spectroscopy to a hydrogen-bonding structure makes it a powerful tool for investigating the structure and dynamics of excess protons in water. Although of significant interest, the line broadening that results from the ultrafast evolution of different solvated proton-water structures makes the assignment of liquid-phase IR spectra a challenging task. In this work, we apply a normal mode analysis using density functional theory of thousands of proton-water clusters taken from reactive molecular dynamics trajectories of the latest generation multistate empirical valence bond proton model (MS-EVB 3.2). These calculations are used to obtain a vibrational density of states and IR spectral density, which are decomposed on the basis of solvated proton structure and the frequency dependent mode character. Decompositions are presented on the basis of the proton sharing parameter δ, often used to distinguish Eigen and Zundel species, the stretch and bend character of the modes, the mode delocalization, and the vibrational mode symmetry. We find there is a wide distribution of vibrational frequencies spanning 1200-3000 cm-1 for every local proton configuration, with the region 2000-2600 cm-1 being mostly governed by the distorted Eigen-like configuration. We find a continuous red shift of the special-pair O⋯H+⋯O stretching frequency, and an increase in the flanking water bending intensity with decreasing δ. Also, we find that the flanking water stretch mode of the Zundel-like species is strongly mixed with the flanking water bend, and the special pair proton oscillation band is strongly coupled with the bend modes of the central H5+O2 moiety.

Radical re-appraisal of water structure in hydrophilic confinement.

PubMed

Soper, Alan K

2013-12-18

The structure of water confined in MCM41 silica cylindrical pores is studied to determine whether confined water is simply a version of the bulk liquid which can be substantially supercooled without crystallisation. A combination of total neutron scattering from the porous silica, both wet and dry, and computer simulation using a realistic model of the scattering substrate is used. The water in the pore is divided into three regions: core, interfacial and overlap. The average local densities of water in these simulations are found to be about 20% lower than bulk water density, while the density in the core region is below, but closer to, the bulk density. There is a decrease in both local and core densities when the temperature is lowered from 298 K to 210 K. The radical proposal is made here that water in hydrophilic confinement is under significant tension, around -100 MPa, inside the pore.

Localized synthesis, assembly and integration of silicon nanowires

NASA Astrophysics Data System (ADS)

Englander, Ongi

Localized synthesis, assembly and integration of one-dimensional silicon nanowires with MEMS structures is demonstrated and characterized in terms of local synthesis processes, electric-field assisted self-assembly, and a proof-of-concept nanoelectromechanical system (HEMS) demonstration. Emphasis is placed on the ease of integration, process control strategies, characterization techniques and the pursuit of integrated devices. A top-down followed by a bottom-up integration approach is utilized. Simple MEMS heater structures are utilized as the microscale platforms for the localized, bottom-up synthesis of one-dimensional nanostructures. Localized heating confines the high temperature region permitting only localized nanostructure synthesis and allowing the surroundings to remain at room temperature thus enabling CMOS compatible post-processing. The vapor-liquid-solid (VLS) process in the presence of a catalytic nanoparticle, a vapor phase reactant, and a specific temperature environment is successfully employed locally. Experimentally, a 5nm thick gold-palladium layer is used as the catalyst while silane is the vapor phase reactant. The current-voltage behavior of the MEMS structures can be correlated to the approximate temperature range required for the VLS reaction to take place. Silicon nanowires averaging 45nm in diameter and up to 29mum in length synthesized at growth rates of up to 1.5mum/min result. By placing two MEMS structures in close proximity, 4--10mum apart, localized silicon nanowire growth can be used to link together MEMS structures to yield a two-terminal, self-assembled micro-to-nano system. Here, one MEMS structure is designated as the hot growth structure while a nearby structure is designated as the cold secondary structure, whose role is to provide a natural stopping point for the VLS reaction. The application of a localized electric-field, 5 to 13V/mum in strength, during the synthesis process, has been shown to improve nanowire organization, alignment, and assembly. The integrated nanoelectrormechanical system was found to be mechanically resilient as it proved to successfully withstand a wide variety of post-processing steps, including manipulations and examinations under scanning and transmission electron microscopes and aqueous processing, although a super critical drying step is necessary to preserve the integrated system during the drying process. Electrical characterization of the system proved challenging due to low carrier concentration and possible transport issues at the nano-micro interface. Nonetheless, in a proof-of-concept demonstration, the system was functionalized and tested for a hydrogen sensing application.

Measurement of gas diffusion coefficient in liquid-saturated porous media using magnetic resonance imaging

NASA Astrophysics Data System (ADS)

Song, Yongchen; Hao, Min; Zhao, Yuechao; Zhang, Liang

2014-12-01

In this study, the dual-chamber pressure decay method and magnetic resonance imaging (MRI) were used to dynamically visualize the gas diffusion process in liquid-saturated porous media, and the relationship of concentration-distance for gas diffusing into liquid-saturated porous media at different times were obtained by MR images quantitative analysis. A non-iterative finite volume method was successfully applied to calculate the local gas diffusion coefficient in liquid-saturated porous media. The results agreed very well with the conventional pressure decay method, thus it demonstrates that the method was feasible of determining the local diffusion coefficient of gas in liquid-saturated porous media at different times during diffusion process.

Local Area Water Removal Analysis of a Proton Exchange Membrane Fuel Cell under Gas Purge Conditions

PubMed Central

Lee, Chi-Yuan; Lee, Yu-Ming; Lee, Shuo-Jen

2012-01-01

In this study, local area water content distribution under various gas purging conditions are experimentally analyzed for the first time. The local high frequency resistance (HFR) is measured using novel micro sensors. The results reveal that the liquid water removal rate in a membrane electrode assembly (MEA) is non-uniform. In the under-the-channel area, the removal of liquid water is governed by both convective and diffusive flux of the through-plane drying. Thus, almost all of the liquid water is removed within 30 s of purging with gas. However, liquid water that is stored in the under-the-rib area is not easy to remove during 1 min of gas purging. Therefore, the re-hydration of the membrane by internal diffusive flux is faster than that in the under-the-channel area. Consequently, local fuel starvation and membrane degradation can degrade the performance of a fuel cell that is started from cold. PMID:22368495

Local area water removal analysis of a proton exchange membrane fuel cell under gas purge conditions.

PubMed

Lee, Chi-Yuan; Lee, Yu-Ming; Lee, Shuo-Jen

2012-01-01

In this study, local area water content distribution under various gas purging conditions are experimentally analyzed for the first time. The local high frequency resistance (HFR) is measured using novel micro sensors. The results reveal that the liquid water removal rate in a membrane electrode assembly (MEA) is non-uniform. In the under-the-channel area, the removal of liquid water is governed by both convective and diffusive flux of the through-plane drying. Thus, almost all of the liquid water is removed within 30 s of purging with gas. However, liquid water that is stored in the under-the-rib area is not easy to remove during 1 min of gas purging. Therefore, the re-hydration of the membrane by internal diffusive flux is faster than that in the under-the-channel area. Consequently, local fuel starvation and membrane degradation can degrade the performance of a fuel cell that is started from cold.

Generalized localization model of relaxation in glass-forming liquids

PubMed Central

Cicerone, Marcus T.; Zhong, Qin; Tyagi, Madhusudan

2012-01-01

Glassy solidification is characterized by two essential phenomena: localization of the solidifying material’s constituent particles and a precipitous increase in its structural relaxation time τ. Determining how these two phenomena relate is key to understanding glass formation. Leporini and coworkers have recently argued that τ universally depends on a localization length-scale (the Debye-Waller factor) in a way that depends only upon the value of at the glass transition. Here we find that this ‘universal’ model does not accurately describe τ in several simulated and experimental glass-forming materials. We develop a new localization model of solidification, building upon the classical Hall-Wolynes and free volume models of glass formation, that accurately relates τ to in all systems considered. This new relationship is based on a consideration of the the anisotropic nature of particle localization. The model also indicates the presence of a particle delocalization transition at high temperatures associated with the onset of glass formation. PMID:23393495

Crossover of Microscopic Dynamics in Metallic Supercooled Liquid Observed by NMR

NASA Astrophysics Data System (ADS)

Wu, Yue; Li, Lilong

2004-03-01

Nuclear magnetic resonance (NMR) is used to characterize local atomic motions in the glassy and supercooled liquid states of the bulk metallic glass system Pd_43Ni_10Cu_27P_20. It is shown that NMR is very effective in detecting local motions such as vibrations in metallic systems. The temperature dependence of the Knight shift reveals that certain local atomic motion decreases rapidly below a crossover temperature T_c. Above Tc as well as below the glass transition temperature Tg the mean-squared amplitude of local motions is shown to depend linearly on the temperature. The observed rapid decrease below Tc cannot be explained by heterogeneity effects. It reveals that qualitative changes of microscopic properties in the supercooled liquid take place at temperatures significantly above T_g. The observed phenomenon can be explained in terms of a rapid disappearance of certain local motions below Tc as suggested by the mode-coupling theory.

Structural, electronic, and vibrational properties of high-density amorphous silicon: a first-principles molecular-dynamics study.

PubMed

Morishita, Tetsuya

2009-05-21

We report a first-principles study of the structural, electronic, and dynamical properties of high-density amorphous (HDA) silicon, which was found to be formed by pressurizing low-density amorphous (LDA) silicon (a normal amorphous Si) [T. Morishita, Phys. Rev. Lett. 93, 055503 (2004); P. F. McMillan, M. Wilson, D. Daisenberger, and D. Machon, Nature Mater. 4, 680 (2005)]. Striking structural differences between HDA and LDA are revealed. The LDA structure holds a tetrahedral network, while the HDA structure contains a highly distorted tetrahedral network. The fifth neighboring atom in HDA tends to be located at an interstitial position of a distorted tetrahedron composed of the first four neighboring atoms. Consequently, the coordination number of HDA is calculated to be approximately 5 unlike that of LDA. The electronic density of state (EDOS) shows that HDA is metallic, which is consistent with a recent experimental measurement of the electronic resistance of HDA Si. We find from local EDOS that highly distorted tetrahedral configurations enhance the metallic nature of HDA. The vibrational density of state (VDOS) also reflects the structural differences between HDA and LDA. Some of the characteristic vibrational modes of LDA are dematerialized in HDA, indicating the degradation of covalent bonds. The overall profile of the VDOS for HDA is found to be an intermediate between that for LDA and liquid Si under pressure (high-density liquid Si).

The structure of MgO-SiO2 glasses at elevated pressure.

PubMed

Wilding, Martin; Guthrie, Malcolm; Kohara, Shinji; Bull, Craig L; Akola, Jaakko; Tucker, Matt G

2012-06-06

The magnesium silicate system is an important geophysical analogue and neutron diffraction data from glasses formed in this system may also provide an initial framework for understanding the structure-dependent properties of related liquids that are important during planetary formation. Neutron diffraction data collected in situ for a single composition (38 mol% SiO(2)) magnesium silicate glass sample shows local changes in structure as pressure is increased from ambient conditions to 8.6 GPa at ambient temperature. A method for obtaining the fully corrected, total structure factor, S(Q), has been developed that allows accurate structural characterization as this weakly scattering glass sample is compressed. The measured S(Q) data indicate changes in chemical ordering with pressure and the real-space transforms show an increase in Mg-O coordination number and a distortion of the local environment around magnesium ions. We have used reverse Monte Carlo methods to compare the high pressure and ambient pressure structures and also compare the high pressure form with a more silica-poor glass (Mg(2)SiO(4)) that represents the approach to a more dense, void-free and topologically ordered structure. The Mg-O coordination number increases with pressure and we also find that the degree of continuous connectivity of Si-O bonds increases via a collapse of interstices.

Thermoelectric-enhanced, liquid-based cooling of a multi-component electronic system

DOEpatents

Chainer, Timothy J; Graybill, David P; Iyengar, Madhusudan K; Kamath, Vinod; Kochuparambil, Bejoy J; Schmidt, Roger R; Steinke, Mark E

2015-11-10

Methods are provided for facilitating cooling of an electronic component. The methods include providing: a liquid-cooled structure, a thermal conduction path coupling the electronic component and the liquid-cooled structure, a coolant loop in fluid communication with a coolant-carrying channel of the liquid-cooled structure, and an outdoor-air-cooled heat exchange unit coupled to facilitate heat transfer from the liquid-cooled structure via, at least in part, the coolant loop. The thermoelectric array facilitates transfer of heat from the electronic component to the liquid-cooled structure, and the heat exchange unit cools coolant passing through the coolant loop by dissipating heat from the coolant to outdoor ambient air. In one implementation, temperature of coolant entering the liquid-cooled structure is greater than temperature of the outdoor ambient air to which heat is dissipated.

Thermoelectric-enhanced, liquid-based cooling of a multi-component electronic system

DOEpatents

Chainer, Timothy J; Graybill, David P; Iyengar, Madhusudan K; Kamath, Vinod; Kochuparambil, Bejoy J; Schmidt, Roger R; Steinke, Mark E

2015-05-12

Apparatus and method are provided for facilitating cooling of an electronic component. The apparatus includes a liquid-cooled structure, a thermal conduction path coupling the electronic component and the liquid-cooled structure, a coolant loop in fluid communication with a coolant-carrying channel of the liquid-cooled structure, and an outdoor-air-cooled heat exchange unit coupled to facilitate heat transfer from the liquid-cooled structure via, at least in part, the coolant loop. The thermoelectric array facilitates transfer of heat from the electronic component to the liquid-cooled structure, and the heat exchange unit cools coolant passing through the coolant loop by dissipating heat from the coolant to outdoor ambient air. In one implementation, temperature of coolant entering the liquid-cooled structure is greater than temperature of the outdoor ambient air to which heat is dissipated.

Supercooled and glassy water: Metastable liquid(s), amorphous solid(s), and a no-man’s land

PubMed Central

Handle, Philip H.; Sciortino, Francesco

2017-01-01

We review the recent research on supercooled and glassy water, focusing on the possible origins of its complex behavior. We stress the central role played by the strong directionality of the water–water interaction and by the competition between local energy, local entropy, and local density. In this context we discuss the phenomenon of polyamorphism (i.e., the existence of more than one disordered solid state), emphasizing both the role of the preparation protocols and the transformation between the different disordered ices. Finally, we present the ongoing debate on the possibility of linking polyamorphism with a liquid–liquid transition that could take place in the no-man’s land, the temperature–pressure window in which homogeneous nucleation prevents the investigation of water in its metastable liquid form. PMID:29133419

Long range order and two-fluid behavior in heavy electron materials

DOE PAGES

Shirer, Kent R.; Shockley, Abigail C.; Dioguardi, Adam P.; ...

2012-09-24

The heavy electron Kondo liquid is an emergent state of condensed matter that displays universal behavior independent of material details. Properties of the heavy electron liquid are best probed by NMR Knight shift measurements, which provide a direct measure of the behavior of the heavy electron liquid that emerges below the Kondo lattice coherence temperature as the lattice of local moments hybridizes with the background conduction electrons. Because the transfer of spectral weight between the localized and itinerant electronic degrees of freedom is gradual, the Kondo liquid typically coexists with the local moment component until the material orders at lowmore » temperatures. The two-fluid formula captures this behavior in a broad range of materials in the paramagnetic state. In order to investigate two-fluid behavior and the onset and physical origin of different long range ordered ground states in heavy electron materials, we have extended Knight shift measurements to URu 2Si 2, CeIrIn 5, and CeRhIn 5. In CeRhIn 5 we find that the antiferromagnetic order is preceded by a relocalization of the Kondo liquid, providing independent evidence for a local moment origin of antiferromagnetism. In URu 2Si 2 the hidden order is shown to emerge directly from the Kondo liquid and so is not associated with local moment physics. Lastly, our results imply that the nature of the ground state is strongly coupled with the hybridization in the Kondo lattice in agreement with phase diagram proposed by Yang and Pines.« less

Fluid-structure finite-element vibrational analysis

NASA Technical Reports Server (NTRS)

Feng, G. C.; Kiefling, L.

1974-01-01

A fluid finite element has been developed for a quasi-compressible fluid. Both kinetic and potential energy are expressed as functions of nodal displacements. Thus, the formulation is similar to that used for structural elements, with the only differences being that the fluid can possess gravitational potential, and the constitutive equations for fluid contain no shear coefficients. Using this approach, structural and fluid elements can be used interchangeably in existing efficient sparse-matrix structural computer programs such as SPAR. The theoretical development of the element formulations and the relationships of the local and global coordinates are shown. Solutions of fluid slosh, liquid compressibility, and coupled fluid-shell oscillation problems which were completed using a temporary digital computer program are shown. The frequency correlation of the solutions with classical theory is excellent.

Molecular dynamics simulations of the structure and single-particle dynamics of mixtures of divalent salts and ionic liquids

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

Gómez-González, Víctor; Docampo-Álvarez, Borja; Gallego, Luis J.

2015-09-28

We report a molecular dynamics study of the structure and single-particle dynamics of mixtures of a protic (ethylammonium nitrate) and an aprotic (1-butyl-3-methylimidazolium hexaflurophosphate [BMIM][PF{sub 6}]) room-temperature ionic liquids doped with magnesium and calcium salts with a common anion at 298.15 K and 1 atm. The solvation of these divalent cations in dense ionic environments is analyzed by means of apparent molar volumes of the mixtures, radial distribution functions, and coordination numbers. For the protic mixtures, the effect of salt concentration on the network of hydrogen bonds is also considered. Moreover, single-particle dynamics of the salt cations is studied by means ofmore » their velocity autocorrelation functions and vibrational densities of states, explicitly analyzing the influence of salt concentration, and cation charge and mass on these magnitudes. The effect of the valency of the salt cation on these properties is considered comparing the results with those for the corresponding mixtures with lithium salts. We found that the main structural and dynamic features of the local solvation of divalent cations in ionic liquids are similar to those of monovalent salts, with cations being localized in the polar nanoregions of the bulk mixture coordinated in monodentate and bidentate coordination modes by the [NO{sub 3}]{sup −} and [PF{sub 6}]{sup −} anions. However, stronger electrostatic correlations of these polar nanoregions than in mixtures with salts with monovalent cations are found. The vibrational modes of the ionic liquid (IL) are seen to be scarcely affected by the addition of the salt, and the effect of mass and charge on the vibrational densities of states of the dissolved cations is reported. Cation mass is seen to exert a deeper influence than charge on the low-frequency vibrational spectra, giving a red shift of the vibrational modes and a virtual suppression of the higher energy vibrational modes for the heavier Ca{sup 2+} cations. No qualitative difference with monovalent cations was found in what solvation is concerned, which suggests that no enhanced reduction of the mobility of these cations and their complexes in ILs respective to those of monovalent cations is to be expected.« less

Studying localized corrosion using liquid cell transmission electron microscopy

DOE PAGES

Chee, See Wee; Pratt, Sarah H.; Hattar, Khalid; ...

2014-11-07

Using liquid cell transmission electron microscopy (LCTEM), localized corrosion of Cu and Al thin films immersed in aqueous NaCl solutions was studied. We demonstrate that potentiostatic control can be used to initiate pitting and that local compositional changes, due to focused ion beam implantation of Au + ions, can modify the corrosion susceptibility of Al films. Likewise, a discussion on strategies to control the onset of pitting is also presented.

Electron paramagnetic resonance studies of slowly tumbling vanadyl spin probes in nematic liquid crystals

NASA Technical Reports Server (NTRS)

Bruno, G. V.; Harrington, J. K.; Eastman, M. P.

1978-01-01

An analysis of EPR line shapes by the method of Polnaszek, Bruno, and Freed is made for slowly tumbling vanadyl spin probes in viscous nematic liquid crystals. The use of typical vanadyl complexes as spin probes for nematic liquid crystals is shown to simplify the theoretical analysis and the subsequent interpretation. Rotational correlation times tau and orientational ordering parameters S sub Z where slow tumbling effects are expected to be observed in vanadyl EPR spectra are indicated in a plot. Analysis of the inertial effects on the probe reorientation, which are induced by slowly fluctuating torque components of the local solvent structure, yield quantitative values for tau and S sub Z. The weakly ordered probe VOAA is in the slow tumbling region and displays these inertial effects throughout the nematic range of BEPC and Phase V. VOAA exhibits different reorientation behavior near the isotropic-nematic transition temperature than that displayed far below this transition temperature.

Theory of molecular crowding in Brownian hard-sphere liquids.

PubMed

Zaccone, Alessio; Terentjev, Eugene M

2012-06-01

We derive an analytical pair potential of mean force for Brownian molecules in the liquid state. Our approach accounts for many-particle correlations of crowding particles of the liquid and for diffusive transport across the spatially modulated local density of crowders in the dense environment. Focusing on the limit of equal-size particles, we show that this diffusive transport leads to additional density- and structure-dependent terms in the interaction potential and to a much stronger attraction (by a factor of ≈4 at average volume fraction of crowders φ{0}=0.25) than in the standard depletion interaction where the diffusive effects are neglected. As an illustration of the theory, we use it to study the size of a polymer chain in a solution of inert crowders. Even in the case of an athermal background solvent, when a classical chain should be fully swollen, we find a sharp coil-globule transition of the ideal chain collapsing at a critical value of the crowder volume fraction φ{c}≈0.145.

Interaction and dynamics of ionic liquids based on choline and amino acid anions

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

Campetella, M.; Bodo, E., E-mail: enrico.bodo@uniroma1.it; Caminiti, R., E-mail: ruggero.caminiti@uniroma1.it

2015-06-21

The combination of amino acid anions with the choline cation gives origin to a new and potentially important class of organic ionic liquids that might represent a viable and bio-compatible alternative with respect to the traditional ones. We present here a detailed study of the bulk phase of the prototype system composed of the simplest amino acid (alanine) anion and the choline cation, based on ab initio and classical molecular dynamics. Theoretical findings have been validated by comparing with accurate experimental X-ray diffraction data and infrared spectra. We find that hydrogen bonding (HB) features in these systems are crucial inmore » establishing their local geometric structure. We have also found that these HBs once formed are persistent and that the proton resides exclusively on the choline cation. In addition, we show that a classical force field description for this particular ionic liquid can be accurately performed by using a slightly modified version of the generalized AMBER force field.« less

Interaction and dynamics of ionic liquids based on choline and amino acid anions

NASA Astrophysics Data System (ADS)

Campetella, M.; Bodo, E.; Caminiti, R.; Martino, A.; D'Apuzzo, F.; Lupi, S.; Gontrani, L.

2015-06-01

The combination of amino acid anions with the choline cation gives origin to a new and potentially important class of organic ionic liquids that might represent a viable and bio-compatible alternative with respect to the traditional ones. We present here a detailed study of the bulk phase of the prototype system composed of the simplest amino acid (alanine) anion and the choline cation, based on ab initio and classical molecular dynamics. Theoretical findings have been validated by comparing with accurate experimental X-ray diffraction data and infrared spectra. We find that hydrogen bonding (HB) features in these systems are crucial in establishing their local geometric structure. We have also found that these HBs once formed are persistent and that the proton resides exclusively on the choline cation. In addition, we show that a classical force field description for this particular ionic liquid can be accurately performed by using a slightly modified version of the generalized AMBER force field.

Study of Thermodynamics of Liquid Noble-Metals Alloys Through a Pseudopotential Theory

NASA Astrophysics Data System (ADS)

Vora, Aditya M.

2010-09-01

The Gibbs-Bogoliubov (GB) inequality is applied to investigate the thermodynamic properties of some equiatomic noble metal alloys in liquid phase such as Au-Cu, Ag-Cu, and Ag-Au using well recognized pseudopotential formalism. For description of the structure, well known Percus-Yevick (PY) hard sphere model is used as a reference system. By applying a variation method the best hard core diameters have been found which correspond to minimum free energy. With this procedure the thermodynamic properties such as entropy and heat of mixing have been computed. The influence of local field correction function viz; Hartree (H), Taylor (T), Ichimaru-Utsumi (IU), Farid et al. (F), and Sarkar et al. (S) is also investigated. The computed results of the excess entropy compares favourably in the case of liquid alloys while the agreement with experiment is poor in the case of heats of mixing. This may be due to the sensitivity of the heats of mixing with the potential parameters and the dielectric function.

A laser tomographic investigation of liquid fuel sprays

NASA Technical Reports Server (NTRS)

Yule, A. J.; Ahseng, C.; Felton, P.; Ungut, A.; Chigier, N. A.

1980-01-01

A light scattering technique is combined with a tomographic transformation to convert line of sight integrated data, measured in sprays, to measurements of droplet size and concentration in volume elements within the spray. The technique is developed and assessed by systematic experiments in axisymmetric sprays generated by twin-fluid atomisers. The good agreement found shows that, provided certain conditions are satisfied by the local spray structure, the technique provides information on spray structure, similar in detail and extent to that derived by photography, but with reduced experimental time. The technique is applied to an investigation of a kerosene spray vaporizing in a hot gas stream.

Evaluation of parallel milliliter-scale stirred-tank bioreactors for the study of biphasic whole-cell biocatalysis with ionic liquids.

PubMed

Dennewald, Danielle; Hortsch, Ralf; Weuster-Botz, Dirk

2012-01-01

As clear structure-activity relationships are still rare for ionic liquids, preliminary experiments are necessary for the process development of biphasic whole-cell processes involving these solvents. To reduce the time investment and the material costs, the process development of such biphasic reaction systems would profit from a small-scale high-throughput platform. Exemplarily, the reduction of 2-octanone to (R)-2-octanol by a recombinant Escherichia coli in a biphasic ionic liquid/water system was studied in a miniaturized stirred-tank bioreactor system allowing the parallel operation of up to 48 reactors at the mL-scale. The results were compared to those obtained in a 20-fold larger stirred-tank reactor. The maximum local energy dissipation was evaluated at the larger scale and compared to the data available for the small-scale reactors, to verify if similar mass transfer could be obtained at both scales. Thereafter, the reaction kinetics and final conversions reached in different reactions setups were analysed. The results were in good agreement between both scales for varying ionic liquids and for ionic liquid volume fractions up to 40%. The parallel bioreactor system can thus be used for the process development of the majority of biphasic reaction systems involving ionic liquids, reducing the time and resource investment during the process development of this type of applications. Copyright © 2011. Published by Elsevier B.V.

Chain Breakage in the Supercooled Liquid - Liquid Transition and Re-entry of the λ-transition in Sulfur.

PubMed

Zhang, Linji; Ren, Yang; Liu, Xiuru; Han, Fei; Evans-Lutterodt, Kenneth; Wang, Hongyan; He, Yali; Wang, Junlong; Zhao, Yong; Yang, Wenge

2018-03-14

Amorphous sulfur was prepared by rapid compression of liquid sulfur at temperatures above the λ-transition for to preserve the high-temperature liquid structure. We conducted synchrotron high-energy X-ray diffraction and Raman spectroscopy to diagnose the structural evolution of amorphous sulfur from room temperature to post-λ-transition temperature. Discontinuous changes of the first and second peaks in atomic pair-distribution-function, g(r), were observed during the transition from amorphous to liquid sulfur. The average first-neighbor coordination numbers showed an abrupt drop from 1.92 to 1.81. The evolution of the chain length clearly shows that the transition was accompanied by polymeric chains breaking. Furthermore, a re-entry of the λ-transition structure was involved in the heating process. The amorphous sulfur, which inherits the post-λ-transition structure from its parent melts, transformed to the pre-λ-transition liquid structure at around 391 K. Upon further heating, the pre-λ-transition liquid transformed to a post-λ-transition structure through the well-known λ-transition process. This discovery offers a new perspective on amorphous sulfur's structural inheritance from its parent liquid and has implications for understanding the structure, evolution and properties of amorphous sulfur and its liquids.

Experimental investigation of liquid-liquid system drop size distribution in Taylor-Couette flow and its application in the CFD simulation

NASA Astrophysics Data System (ADS)

Farzad, Reza; Puttinger, Stefan; Pirker, Stefan; Schneiderbauer, Simon

Liquid-liquid systems are widely used in the several industries such as food, pharmaceutical, cosmetic, chemical and petroleum. Drop size distribution (DSD) plays a key role as it strongly affects the overall mass and heat transfer in the liquid-liquid systems. To understand the underlying mechanisms single drop breakup experiments have been done by several researchers in the Taylor-Couette flow; however, most of those studies concentrate on the laminar flow regime and therefore, there is no sufficient amount of data in the case of in turbulent flows. The well-defined pattern of the Taylor-Couette flow enables the possibility to investigate DSD as a function of the local fluid dynamic properties, such as shear rate, which is in contrast to more complex devices such as stirred tank reactors. This paper deals with the experimental investigation of liquid-liquid DSD in Taylor-Couette flow. From high speed camera images we found a simple correlation for the Sauter mean diameter as a function of the local shear employing image processing. It is shown that this correlation holds for different oil-in-water emulsions. Finally, this empirical correlation for the DSD is used as an input data for a CFD simulation to compute the local breakup of individual droplets in a stirred tank reactor.

Nanoporous Materials Can Tune the Critical Point of a Pure Substance

DOE PAGES

Braun, Efrem; Chen, Joseph J.; Schnell, Sondre K.; ...

2015-09-30

Molecular simulations and NMR relaxometry experiments demonstrate that pure benzene or xylene confined in isoreticular metal–organic frameworks (IRMOFs) exhibit true vapor–liquid phase equilibria where the effective critical point may be reduced by tuning the structure of the MOF. Our results are consistent with vapor and liquid phases extending over many MOF unit cells. These results are counterintuitive since the MOF pore diameters are approximately the same length scale as the adsorbate molecules. Lastly, as applications of these materials in catalysis, separations, and gas storage rely on the ability to tune the properties of adsorbed molecules, we anticipate that the abilitymore » to systematically control the critical point, thereby preparing spatially inhomogeneous local adsorbate densities, could add a new design tool for MOF applications.« less

As-Cast Icosashedral Quasicrystals in Ti-Zr-Ni Alloys

NASA Astrophysics Data System (ADS)

Lee, Geun Woo; Gangopadhyay, Anup K.; Kelton, Kenneth F.

2002-03-01

Most Ti-based icosahedral quasicrystals (i-phase) obtained by rapid quenching from the melt are metastable and disordered. In contrast, the Ti-Zr-Ni i-phase prepared by low temperature annealing is stable and better ordered. This i-phase is formed by a solid-state transformation from C14 Laves phase and α (Ti/Zr) solid-solution phase. It has not been possible previously to grow this i-phase directly from the liquid. Here, the nucleation and growth of the i-phase from the liquid in as-cast Ti-Zr-Ni alloys is reported. Pentagonal growth ledges in as-cast Ti-Zr-Ni ingots are clearly observed. Transmission electron microscopy and x-ray diffraction studies confirm the phase identity. Differential scanning calorimetry measurements show an endothermic transformation from the i-phase to a phase mixture of the C14 Laves and solid-solution phases, demonstrating that this i-phase is also stable. The short time that the liquid remains in the Laves phase-forming-field and the higher nucleation rate of the i-phase, owing to the presumed similarity between the local atomic structures of the i-phase and liquid, allows the i-phase to nucleate and grow directly from the liquid. Container-less solidification studies using electrostatic levitation (ESL) techniques support this conclusion.

Liquid uranium alloy-helium fission reactor

DOEpatents

Minkov, Vladimir

1986-01-01

This invention teaches a nuclear fission reactor having a core vessel and at least one tandem heat exchanger vessel coupled therewith across upper and lower passages to define a closed flow loop. Nuclear fuel such as a uranium alloy in its liquid phase fills these vessels and flow passages. Solid control elements in the reactor core vessel are adapted to be adjusted relative to one another to control fission reaction of the liquid fuel therein. Moderator elements in the other vessel and flow passages preclude fission reaction therein. An inert gas such as helium is bubbled upwardly through the heat exchanger vessel operable to move the liquid fuel upwardly therein and unidirectionally around the closed loop and downwardly through the core vessel. This helium gas is further directed to heat conversion means outside of the reactor vessels to utilize the heat from the fission reaction to generate useful output. The nuclear fuel operates in the 1200.degree.-1800.degree. C. range, and even higher to 2500.degree. C., limited only by the thermal effectiveness of the structural materials, increasing the efficiency of power generation from the normal 30-35% with 300.degree.-500.degree. C. upper limit temperature to 50-65%. Irradiation of the circulating liquid fuel, as contrasted to only localized irradiation of a solid fuel, provides improved fuel utilization.

Real-space imaging of fractional quantum Hall liquids

NASA Astrophysics Data System (ADS)

Hayakawa, Junichiro; Muraki, Koji; Yusa, Go

2013-01-01

Electrons in semiconductors usually behave like a gas--as independent particles. However, when confined to two dimensions under a perpendicular magnetic field at low temperatures, they condense into an incompressible quantum liquid. This phenomenon, known as the fractional quantum Hall (FQH) effect, is a quantum-mechanical manifestation of the macroscopic behaviour of correlated electrons that arises when the Landau-level filling factor is a rational fraction. However, the diverse microscopic interactions responsible for its emergence have been hidden by its universality and macroscopic nature. Here, we report real-space imaging of FQH liquids, achieved with polarization-sensitive scanning optical microscopy using trions (charged excitons) as a local probe for electron spin polarization. When the FQH ground state is spin-polarized, the triplet/singlet intensity map exhibits a spatial pattern that mirrors the intrinsic disorder potential, which is interpreted as a mapping of compressible and incompressible electron liquids. In contrast, when FQH ground states with different spin polarization coexist, domain structures with spontaneous quasi-long-range order emerge, which can be reproduced remarkably well from the disorder patterns using a two-dimensional random-field Ising model. Our results constitute the first reported real-space observation of quantum liquids in a class of broken symmetry state known as the quantum Hall ferromagnet.

Amorphous tantala and its relationship with the molten state

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

Alderman, Oliver L.G.; Benmore, C. J.; Neuefeind, Joerg C.

The structure factors of molten Ta 2O 5 and Nb 2O 5 have been measured by high-energy x-ray and pulsed neutron diffraction. These are compared to transmission-mode x-ray diffraction through a self-supported 15-μm ion-beam sputtered amorphous tantala film. Atomistic models derived from the diffraction data by means of empirical potential structure refinement reveal that tantala and niobia liquids are very close to isomorphous, as confirmed by measurement of a molten mixture, Ta 0.8Nb 1.2O 5. Nonetheless, peak Nb-O bond lengths are about 1% shorter than those for Ta-O, at temperatures, T*=T/T melt, scaled to the melting points. Mean coordination numbersmore » are n MO≃5.6(1),n OM≃2.23(4) in the liquid state, and n TaO≃6.6(2),n OTa≃2.63(8) in the solid. The liquids are built from five- and six-fold M-O polyhedra which connect principally by corner sharing, with a minority of edge sharing; a-Ta 2O 5 on the other hand has a local structure more akin to the crystalline polymorphs, built primarily from six- and seven-fold polyhedra, with a larger degree of edge sharing. The structural differences between liquid and amorphous Ta 2O 5, coupled with observations of increasing peak bond lengths upon cooling, are consistent with the interpretation that the amorphous film reaches a supercooled liquidlike metastable equilibrium during deposition. In other words, the amorphous film shares a common progenitor state with a hypothetical glass quenched from a fragile melt. In addition, we show that recent classical interatomic potentials do not fully reproduce the diffraction data, and infer that inclusion of attractive (non-Coulombic) Ta-Ta interactions is important, particularly for obtaining the correct degree of edge sharing, coordination numbers, and densities. In conclusion, nanoscale inhomogeneity of the amorphous film is confirmed by the observation of small-angle x-ray scattering.« less

Amorphous tantala and its relationship with the molten state

NASA Astrophysics Data System (ADS)

Alderman, O. L. G.; Benmore, C. J.; Neuefeind, J.; Coillet, E.; Mermet, A.; Martinez, V.; Tamalonis, A.; Weber, R.

2018-04-01

The structure factors of molten T a2O5 and N b2O5 have been measured by high-energy x-ray and pulsed neutron diffraction. These are compared to transmission-mode x-ray diffraction through a self-supported 15-μm ion-beam sputtered amorphous tantala film. Atomistic models derived from the diffraction data by means of empirical potential structure refinement reveal that tantala and niobia liquids are very close to isomorphous, as confirmed by measurement of a molten mixture, T a0.8N b1.2O5 . Nonetheless, peak Nb-O bond lengths are about 1 % shorter than those for Ta-O, at temperatures, T*=T /Tmelt , scaled to the melting points. Mean coordination numbers are nM O≃5.6 (1 ) ,nO M≃2.23 (4 ) in the liquid state, and nTaO≃6.6 (2 ) ,nOTa≃2.63 (8 ) in the solid. The liquids are built from five- and six-fold M -O polyhedra which connect principally by corner sharing, with a minority of edge sharing; a-T a2O5 on the other hand has a local structure more akin to the crystalline polymorphs, built primarily from six- and seven-fold polyhedra, with a larger degree of edge sharing. The structural differences between liquid and amorphous T a2O5 , coupled with observations of increasing peak bond lengths upon cooling, are consistent with the interpretation that the amorphous film reaches a supercooled liquidlike metastable equilibrium during deposition. In other words, the amorphous film shares a common progenitor state with a hypothetical glass quenched from a fragile melt. In addition, we show that recent classical interatomic potentials do not fully reproduce the diffraction data, and infer that inclusion of attractive (non-Coulombic) Ta-Ta interactions is important, particularly for obtaining the correct degree of edge sharing, coordination numbers, and densities. Nanoscale inhomogeneity of the amorphous film is confirmed by the observation of small-angle x-ray scattering.

Amorphous tantala and its relationship with the molten state

DOE PAGES

Alderman, Oliver L.G.; Benmore, C. J.; Neuefeind, Joerg C.; ...

2018-04-01

The structure factors of molten Ta 2O 5 and Nb 2O 5 have been measured by high-energy x-ray and pulsed neutron diffraction. These are compared to transmission-mode x-ray diffraction through a self-supported 15-μm ion-beam sputtered amorphous tantala film. Atomistic models derived from the diffraction data by means of empirical potential structure refinement reveal that tantala and niobia liquids are very close to isomorphous, as confirmed by measurement of a molten mixture, Ta 0.8Nb 1.2O 5. Nonetheless, peak Nb-O bond lengths are about 1% shorter than those for Ta-O, at temperatures, T*=T/T melt, scaled to the melting points. Mean coordination numbersmore » are n MO≃5.6(1),n OM≃2.23(4) in the liquid state, and n TaO≃6.6(2),n OTa≃2.63(8) in the solid. The liquids are built from five- and six-fold M-O polyhedra which connect principally by corner sharing, with a minority of edge sharing; a-Ta 2O 5 on the other hand has a local structure more akin to the crystalline polymorphs, built primarily from six- and seven-fold polyhedra, with a larger degree of edge sharing. The structural differences between liquid and amorphous Ta 2O 5, coupled with observations of increasing peak bond lengths upon cooling, are consistent with the interpretation that the amorphous film reaches a supercooled liquidlike metastable equilibrium during deposition. In other words, the amorphous film shares a common progenitor state with a hypothetical glass quenched from a fragile melt. In addition, we show that recent classical interatomic potentials do not fully reproduce the diffraction data, and infer that inclusion of attractive (non-Coulombic) Ta-Ta interactions is important, particularly for obtaining the correct degree of edge sharing, coordination numbers, and densities. In conclusion, nanoscale inhomogeneity of the amorphous film is confirmed by the observation of small-angle x-ray scattering.« less

Role of density modulation in the spatially resolved dynamics of strongly confined liquids

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

Saw, Shibu, E-mail: shibu.saw@sydney.edu.au; Dasgupta, Chandan, E-mail: cdgupta@physics.iisc.ernet.in

Confinement by walls usually produces a strong modulation in the density of dense liquids near the walls. Using molecular dynamics simulations, we examine the effects of the density modulation on the spatially resolved dynamics of a liquid confined between two parallel walls, using a resolution of a fraction of the interparticle distance in the liquid. The local dynamics is quantified by the relaxation time associated with the temporal autocorrelation function of the local density. We find that this local relaxation time varies in phase with the density modulation. The amplitude of the spatial modulation of the relaxation time can bemore » quite large, depending on the characteristics of the wall and thermodynamic parameters of the liquid. To disentangle the effects of confinement and density modulation on the spatially resolved dynamics, we compare the dynamics of a confined liquid with that of an unconfined one in which a similar density modulation is induced by an external potential. We find several differences indicating that density modulation alone cannot account for all the features seen in the spatially resolved dynamics of confined liquids. We also examine how the dynamics near a wall depends on the separation between the two walls and show that the features seen in our simulations persist in the limit of large wall separation.« less

Prediction of the retention of s-triazines in reversed-phase high-performance liquid chromatography under linear gradient-elution conditions.

PubMed

D'Archivio, Angelo Antonio; Maggi, Maria Anna; Ruggieri, Fabrizio

2014-08-01

In this paper, a multilayer artificial neural network is used to model simultaneously the effect of solute structure and eluent concentration profile on the retention of s-triazines in reversed-phase high-performance liquid chromatography under linear gradient elution. The retention data of 24 triazines, including common herbicides and their metabolites, are collected under 13 different elution modes, covering the following experimental domain: starting acetonitrile volume fraction ranging between 40 and 60% and gradient slope ranging between 0 and 1% acetonitrile/min. The gradient parameters together with five selected molecular descriptors, identified by quantitative structure-retention relationship modelling applied to individual separation conditions, are the network inputs. Predictive performance of this model is evaluated on six external triazines and four unseen separation conditions. For comparison, retention of triazines is modelled by both quantitative structure-retention relationships and response surface methodology, which describe separately the effect of molecular structure and gradient parameters on the retention. Although applied to a wider variable domain, the network provides a performance comparable to that of the above "local" models and retention times of triazines are modelled with accuracy generally better than 7%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanolayered Features of Collagen-like Peptides

NASA Technical Reports Server (NTRS)

Valluzzi, Regina; Bini, Elisabetta; Haas, Terry; Cebe, Peggy; Kaplan, David L.

2003-01-01

We have been investigating collagen-like model oligopeptides as molecular bases for complex ordered biomimetic materials. The collagen-like molecules incorporate aspects of native collagen sequence and secondary structure. Designed modifications to native primary and secondary structure have been incorporated to control the nanostructure and microstructure of the collagen-like materials produced. We find that the collagen-like molecules form a number of lyotropic rod liquid crystalline phases, which because of their strong temperature dependence in the liquid state can also be viewed as solvent intercalated thermotropic liquid crystals. The liquid crystalline phases formed by the molecules can be captured in the solid state by drying off solvent, resulting in solid nanopatterned (chemically and physically) thermally stable (to greater than 100 C) materials. Designed sequences which stabilize smectic phases have allowed a variety of nanoscale multilayered biopolymeric materials to be developed. Preliminary investigations suggest that chemical patterns running perpendicular to the smectic layer plane can be functionalized and used to localize a variety of organic, inorganic, and organometallic moieties in very simple multilayered nanocomposites. The phase behavior of collagen-like oligopeptide materials is described, emphasizing the correlation between mesophase, molecular orientation, and chemical patterning at the microscale and nanoscale. In many cases, the textures observed for smectic and hexatic phase collagens are remarkably similar to the complex (and not fully understood) helicoids observed in biological collagen-based tissues. Comparisons between biological morphologies and collagen model liquid crystalline (and solidified materials) textures may help us understand the molecular features which impart order and function to the extracellular matrix and to collagen-based mineralized tissues. Initial studies have utilized synthetic collagen-like peptides while future work will also focus on similar sequences generated via genetic engineering methods.

Analysis of spatial correlations in a model two-dimensional liquid through eigenvalues and eigenvectors of atomic-level stress matrices.

PubMed

Levashov, V A; Stepanov, M G

2016-01-01

Considerations of local atomic-level stresses associated with each atom represent a particular approach to address structures of disordered materials at the atomic level. We studied structural correlations in a two-dimensional model liquid using molecular dynamics simulations in the following way. We diagonalized the atomic-level stress tensor of every atom and investigated correlations between the eigenvalues and orientations of the eigenvectors of different atoms as a function of distance between them. It is demonstrated that the suggested approach can be used to characterize structural correlations in disordered materials. In particular, we found that changes in the stress correlation functions on decrease of temperature are the most pronounced for the pairs of atoms with separation distance that corresponds to the first minimum in the pair density function. We also show that the angular dependencies of the stress correlation functions previously reported by Wu et al. [Phys. Rev. E 91, 032301 (2015)10.1103/PhysRevE.91.032301] do not represent the anisotropic Eshelby's stress fields, as it is suggested, but originate in the rotational properties of the stress tensors.

X-ray digital industrial radiography (DIR) for local liquid velocity (VLL) measurement in trickle bed reactors (TBRs): Validation of the technique

NASA Astrophysics Data System (ADS)

Mohd Salleh, Khairul Anuar; Rahman, Mohd Fitri Abdul; Lee, Hyoung Koo; Al Dahhan, Muthanna H.

2014-06-01

Local liquid velocity measurements in Trickle Bed Reactors (TBRs) are one of the essential components in its hydrodynamic studies. These measurements are used to effectively determine a reactor's operating condition. This study was conducted to validate a newly developed technique that combines Digital Industrial Radiography (DIR) with Particle Tracking Velocimetry (PTV) to measure the Local Liquid Velocity (VLL) inside TBRs. Three millimeter-sized Expanded Polystyrene (EPS) beads were used as packing material. Three validation procedures were designed to test the newly developed technique. All procedures and statistical approaches provided strong evidence that the technique can be used to measure the VLL within TBRs.

X-ray digital industrial radiography (DIR) for local liquid velocity (V(LL)) measurement in trickle bed reactors (TBRs): validation of the technique.

PubMed

Mohd Salleh, Khairul Anuar; Rahman, Mohd Fitri Abdul; Lee, Hyoung Koo; Al Dahhan, Muthanna H

2014-06-01

Local liquid velocity measurements in Trickle Bed Reactors (TBRs) are one of the essential components in its hydrodynamic studies. These measurements are used to effectively determine a reactor's operating condition. This study was conducted to validate a newly developed technique that combines Digital Industrial Radiography (DIR) with Particle Tracking Velocimetry (PTV) to measure the Local Liquid Velocity (V(LL)) inside TBRs. Three millimeter-sized Expanded Polystyrene (EPS) beads were used as packing material. Three validation procedures were designed to test the newly developed technique. All procedures and statistical approaches provided strong evidence that the technique can be used to measure the V(LL) within TBRs.

Crystalline structures of particles interacting through the harmonic-repulsive pair potential

NASA Astrophysics Data System (ADS)

Levashov, V. A.

2017-09-01

The behavior of identical particles interacting through the harmonic-repulsive pair potential has been studied in 3D using molecular dynamics simulations at a number of different densities. We found that at many densities, as the temperature of the systems decreases, the particles crystallize into complex structures whose formation has not been anticipated in previous studies on the harmonic-repulsive pair potential. In particular, at certain densities, crystallization into the structure I a 3 ¯ d (space group #230) with 16 particles in the unit cell occupying Wyckoff special positions (16b) was observed. This crystal structure has not been observed previously in experiments or in computer simulations of single component atomic or soft matter systems. At another density, we observed a liquid which is rather stable against crystallization. Yet, we observed crystallization of this liquid into the monoclinic C2/c (space group #15) structure with 32 particles in the unit cell occupying four different non-special Wyckoff (8f) sites. In this structure particles located at different Wyckoff sites have different energies. From the perspective of the local atomic environment, the organization of particles in this structure resembles the structure of some columnar quasicrystals. At a different value of the density, we did not observe crystallization at all despite rather long molecular dynamics runs. At two other densities, we observed the formation of the β S n distorted diamond structures instead of the expected diamond structure. Possibly, we also observed the formation of the R 3 ¯ c hexagonal lattice with 24 particles per unit cell occupying non-equivalent positions.

Local mass and energy transports in evaporation processes from a vapor-liquid interface in a slit pore based on molecular dynamics

NASA Astrophysics Data System (ADS)

Fujiwara, K.; Shibahara, M.

2018-02-01

Molecular evaporation processes from a vapor-liquid interface formed in a slit-like pore were examined based on the classical molecular dynamics method, in order to elucidate a molecular mechanism of local mass and energy transports in a slit. The calculation system consisted of monatomic molecules and atoms which interact through the 12-6 Lennard-Jones potential. At first, a liquid was situated in a slit with a vapor-liquid interface, and instantaneous amounts of the mass and energy fluxes defined locally in the slit were obtained in two dimensions to reveal local fluctuation properties of the fluid in equilibrium states. Then, imposing a temperature gradient in the calculation system, non-equilibrium evaporation processes in the slit were investigated in details based on the local mass and energy fluxes. In this study, we focused on the fluid which is in the vicinity of the solid surface and in contact with the vapor phase. In the non-equilibrium evaporation processes, the results revealed that the local energy transport mechanism in the vicinity of the solid surface is different from that of the vapor phase, especially in the case of the relatively strong fluid-solid interaction. The results also revealed that the local mass transport in the vicinity of the solid surface can be interpreted based on the mechanism of the local energy transport, and the mechanism provides valuable information about pictures of the evaporation phenomena especially in the vicinity of the hydrophilic surfaces. It suggests that evaluating and changing this mechanism of the local energy transport are necessary to control the local mass flux more precisely in the vicinity of the solid surface.

Multi-phase-fluid discrimination with local fibre-optical probes: III. Three-phase flows

NASA Astrophysics Data System (ADS)

Fordham, E. J.; Ramos, R. T.; Holmes, A.; Simonian, S.; Huang, S.-M.; Lenn, C. P.

1999-12-01

Local fibre-optical sensors (or `local probes') for immiscible-fluid discrimination are demonstrated in three-phase (oil/water/gas) flows. The probes are made from standard silica fibres with plane oblique facets polished at the fibre tip, with surface treatment for wettability control. They use total internal reflection to distinguish among drops, bubbles and other regions of fluid in multi-phase flows, on the basis of refractive-index contrast. Dual probes, using two sensors each with a quasi-binary output, are used to determine profiles of three-phase volume fraction in a flow of kerosene, water and air in a pipe. The individual sensors used discriminate oil from `not-oil' and gas from liquid; their logical combination discriminates among the three phases. Companion papers deal with the sensor designs used and quantitative results achieved in the simpler two-phase cases of liquid/liquid flows and gas/liquid flows.

Analysis of propellant feedline dynamics

NASA Technical Reports Server (NTRS)

Holster, J. L.; Astleford, W. J.; Gerlach, C. R.

1973-01-01

An analytical model and corresponding computer program for studying disturbances of liquid propellants in typical engine feedline systems were developed. The model includes the effects of steady turbulent mean flow, the influence of distributed compliances, the effects of local compliances, and various factors causing structural-hydraulic coupling. The computer program was set up such that the amplitude and phase of the terminal pressure/input excitation is calculated over any desired frequency range for an arbitrary assembly of various feedline components. A user's manual is included.

Crystalline, Glassy and Polymeric Electrolytes:. Similarities and Differences in Ionic Transport Mechanisms

NASA Astrophysics Data System (ADS)

Souquet, Jean Louis

2006-06-01

Ionocovalent crystals or glasses as well as molten salts or salt polymer complexes are currently studied as electrolytes for high energy density batteries. Their large Red/Ox stability range results from their thermodynamic or kinetic characteristics. For all these electrolytes, charge carriers are the consequence of local deviations from electroneutrality, identified as point defects for ionic crystals or partial dissociation in disordered structures. The charge carriers formation derives from a similar activated process. The main difference comes from the migration process, which depends on the dynamic properties of the surrounding medium. When the structural relaxation time is large, an activated process, mainly enthalpic, prevails for charge carriers migration. It is the usual case for ionic crystals or glasses. In the liquid or overcooled liquid states, the structural relaxation time of the medium is shorter that the time required for the activated migration process to occur and a local reorganization of the medium vanishes the energy barrier and provides the free volume necessary to ionic migration. In that case, the migration is mainly an entropic process. The configurational entropy necessary to this process decreases with temperature and vanishes at the so called ideal glass transition temperature which can be estimated by extrapolation of the transport properties or of the thermodynamic characteristics of the medium. However, at the experiment time scale, this configurational entropy disappears at a somewhat higher temperature, the glass transition temperature at which the structural relaxation time corresponds to the measurement time. Some glass forming ionic melts studied in a large temperature scale, over and below the glass transition temperature, evidence the two, enthalpic and entropic, migration mechanisms, allowing the determination of the thermodynamic characteristics of the charge carriers formation and migration. Some recent results indicate that entropic process, associated to long scale deformations, may also exist in crystalline structures.

Transverse liquid fuel jet breakup, burning, and ignition

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

Li, Hsi-shang

1990-01-01

An analytical/numerical study of the breakup, burning, and ignition of liquid fuels injected transversely into a hot air stream is conducted. The non-reacting liquid jet breakup location is determined by the local sonic point criterion first proposed by Schetz, et al. (1980). Two models, one employing analysis of an elliptical jet cross-section and the other employing a two-dimensional blunt body to represent the transverse jet, have been used for sonic point calculations. An auxiliary criterion based on surface tension stability is used as a separate means of determining the breakup location. For the reacting liquid jet problem, a diffusion flamemore » supported by a one-step chemical reaction within the gaseous boundary layer is solved along the ellipse surface in subsonic crossflow. Typical flame structures and concentration profiles have been calculated for various locations along the jet cross-section as a function of upstream Mach numbers. The integrated reaction rate along the jet cross-section is used to predict ignition position, which is found to be situated near the stagnation point. While a multi-step reaction is needed to represent the ignition process more accurately, the present calculation does yield reasonable predictions concerning ignition along a curved surface.« less

Numerical simulation and experimental validation of the dynamics of multiple bubble merger during pool boiling under microgravity conditions.

PubMed

Abarajith, H S; Dhir, V K; Warrier, G; Son, G

2004-11-01

Numerical simulation and experimental validation of the growth and departure of multiple merging bubbles and associated heat transfer on a horizontal heated surface during pool boiling under variable gravity conditions have been performed. A finite difference scheme is used to solve the equations governing mass, momentum, and energy in the vapor liquid phases. The vapor-liquid interface is captured by a level set method that is modified to include the influence of phase change at the liquid-vapor interface. Water is used as test liquid. The effects of reduced gravity condition and orientation of the bubbles on the bubble diameter, interfacial structure, bubble merger time, and departure time, as well as local heat fluxes, are studied. In the experiments, multiple vapor bubbles are produced on artificial cavities in the 2-10 micrometer diameter range, microfabricated on the polished silicon wafer with given spacing. The wafer was heated electrically from the back with miniature strain gage type heating elements in order to control the nucleation superheat. The experiments conducted in normal Earth gravity and in the low gravity environment of KC-135 aircraft are used to validate the numerical simulations.

Microphysics of liquid complex plasmas in equilibrium and non-equilibrium systems

NASA Astrophysics Data System (ADS)

Piel, Alexander; Block, Dietmar; Melzer, André; Mulsow, Matthias; Schablinski, Jan; Schella, André; Wieben, Frank; Wilms, Jochen

2018-05-01

The dynamic evolution of the microscopic structure of solid and liquid phases of complex plasmas is studied experimentally and by means of molecular dynamics (MD) simulations. In small finite systems, the cooperative motion can be described in terms of discrete modes. These modes are studied with different experimental approaches. Using diffuse scattered laser light, applying laser tweezer forces to individual particles, and periodic laser pulses, the excitation of modes is investigated. The instantaneous normal mode analysis of experimental data from two-dimensional liquid clusters gives access to the local dynamics of the liquid phase. Our investigations shed light on the role of compressional and shear modes as well as the determination of diffusion constants and melting temperatures in finite systems. Special attention is paid to hydrodynamic situations with a stationary inhomogeneous dust flow. MD simulations allow to study the collective motion in the shell of nearest neighbors, which can be linked to smooth and sudden changes of the macroscopic flow. Finally, the observed micro-motion in all situations above allows to shed light on the preference of shear-like over compressional motion in terms of a minimized potential energy and a dynamic incompressibility.

Transverse liquid fuel jet breakup, burning, and ignition. M.S. Thesis

NASA Technical Reports Server (NTRS)

Li, Hsi-Shang

1990-01-01

An analytical study of the breakup, burning, and ignition of liquid fuels injected transversely into a hot air stream is conducted. The non-reacting liquid jet breakup location is determined by the local sonic point criterion. Two models, one employing analysis of an elliptical jet cross-section and the other employing a two-dimensional blunt body to represent the transverse jet, were used for sonic point calculations. An auxiliary criterion based on surface tension stability is used as a separate means of determining the breakup location. For the reacting liquid jet problem, a diffusion flame supported by a one-step chemical reaction within the gaseous boundary layer is solved along the ellipse surface in subsonic cross flow. Typical flame structures and concentration profiles were calculated for various locations along the jet cross-section as a function of upstream Mach numbers. The integration reaction rate along the jet cross-section is used to predict ignition position, which is found to be situated near the stagnation point. While a multi-step reaction is needed to represent the ignition process more accurately, the present calculation does yield reasonable predictions concerning ignition along a curved surface.

Effect of temperature and thermal history on borosilicate glass structure

NASA Astrophysics Data System (ADS)

Angeli, Frédéric; Villain, Olivier; Schuller, Sophie; Charpentier, Thibault; de Ligny, Dominique; Bressel, Lena; Wondraczek, Lothar

2012-02-01

The influence of the temperature and quenching rate on the structure of a borosilicate glass was studied by high-resolution solid-state 11B, 23Na, 29Si nuclear magnetic resonance (NMR) and high-temperature Raman spectroscopy. Data were obtained for glass in the solid state after annealing and quenching at cooling rates covering four orders of magnitude as well as in the liquid state from Raman experiments and from calorimetry and rheological data. Nuclear magnetic resonance measurements were used to calibrate the Raman spectra in order to quantify the change in boron coordination with temperature. This result can then be used to determine the fictive temperature of the glass directly from the boron coordination. The fictive temperature, heat capacity, and configurational entropy are extracted from calorimetry and viscosity measurements. Changes in the boron coordination account for only 25% of the configurational heat capacity of the liquid. The structural parameters capable of accounting for the remaining quantity are discussed on the basis of structural data, both local (inhomogeneity of the sodium distribution) and medium-range (from NMR parameter distribution). It has thus been shown that, although the B-O-B angular distributions of the boroxol rings (and probably the Si-O-Si distributions) are not affected by temperature, a structural disorder is identified through the angular distributions of the bonds linking borate and silicate groups.

Fluid inclusion study of some Sarrabus fluorite deposits, Sardinia, Italy.

USGS Publications Warehouse

Belkin, H.E.; de Vivo, B.; Valera, R.

1984-01-01

Fluid inclusions in six deposits of fluorite fracture fillings associated with Hercynian (Carboniferous) cycle magmatism were studied by microthermometric techniques. All the inclusions were liquid dominated, aqueous, and homogenized in the liquid phase. One-phase (liquid), two-phase (liquid + vapour) and three-phase (liquid, vapour, and solid NaCl daughter mineral) fluid inclusions were noted. This study indicates that five of the fluorite deposits formed from 95o-125oC fluids with approx 15 wt.% NaCl. One other deposit appears to have been formed by very dilute solutions at approx 125oC. It is suggested that the local fluorite-forming process was the formation of fracture-localized hydrothermal systems in which magmatic water interaction with some other fluid-connate, meteoric, or marine.-G.J.N.

Spin-orbit excitations and electronic structure of the putative Kitaev magnet α -RuCl3

NASA Astrophysics Data System (ADS)

Sandilands, Luke J.; Tian, Yao; Reijnders, Anjan A.; Kim, Heung-Sik; Plumb, K. W.; Kim, Young-June; Kee, Hae-Young; Burch, Kenneth S.

2016-02-01

Mott insulators with strong spin-orbit coupling have been proposed to host unconventional magnetic states, including the Kitaev quantum spin liquid. The 4 d system α -RuCl3 has recently come into view as a candidate Kitaev system, with evidence for unusual spin excitations in magnetic scattering experiments. We apply a combination of optical spectroscopy and Raman scattering to study the electronic structure of this material. Our measurements reveal a series of orbital excitations involving localized total angular momentum states of the Ru ion, implying that strong spin-orbit coupling and electron-electron interactions coexist in this material. Analysis of these features allows us to estimate the spin-orbit coupling strength, as well as other parameters describing the local electronic structure, revealing a well-defined hierarchy of energy scales within the Ru d states. By comparing our experimental results with density functional theory calculations, we also clarify the overall features of the optical response. Our results demonstrate that α -RuCl3 is an ideal material system to study spin-orbit coupled magnetism on the honeycomb lattice.

Pressure/temperature fluid cell apparatus for the neutron powder diffractometer instrument: Probing atomic structure in situ

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

Wang, Hsiu-Wen; Fanelli, Victor R.; Reiche, Helmut M.

This contribution describes a new local structure compatible gas/liquid cell apparatus for probing disordered materials at high pressures and variable temperatures in the Neutron Powder Diffraction instrument at the Lujan Neutron Scattering Center, Los Alamos National Laboratory. The new sample environment offers choices for sample canister thickness and canister material type. Finite element modeling is utilized to establish maximum allowable working pressures of 414 MPa at 15 K and 121 MPa at 600 K. High quality atomic pair distribution function data extraction and modeling have been demonstrated for a calibration standard (Si powder) and for supercritical and subcritical CO{sub 2}more » measurements. The new sample environment was designed to specifically target experimental studies of the local atomic structures involved in geologic CO{sub 2} sequestration, but will be equally applicable to a wide variety of energy applications, including sorption of fluids on nano/meso-porous solids, clathrate hydrate formation, catalysis, carbon capture, and H{sub 2} and natural gas uptake/storage.« less

Pressure/temperature fluid cell apparatus for the neutron powder diffractometer instrument: Probing atomic structure in situ

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

Wang, Hsiu -Wen; Fanelli, Victor R.; Reiche, Helmut M.

This contribution describes a new local structure compatible gas/liquid cell apparatus for probing disordered materials at high pressures and variable temperatures in the Neutron Powder Diffraction instrument at the Lujan Neutron Scattering Center, Los Alamos National Laboratory. The new sample environment offers choices for sample canister thickness and canister material type. Finite element modeling is utilized to establish maximum allowable working pressures of 414 MPa at 15 K and 121 MPa at 600 K. High quality atomic pair distribution function data extraction and modeling have been demonstrated for a calibration standard (Si powder) and for supercritical and subcritical CO 2measurements.more » As a result, the new sample environment was designed to specifically target experimental studies of the local atomic structures involved in geologic CO 2 sequestration, but will be equally applicable to a wide variety of energy applications, including sorption of fluids on nano/meso-porous solids, clathrate hydrate formation, catalysis, carbon capture, and H 2 and natural gas uptake/storage.« less

Pressure/temperature fluid cell apparatus for the neutron powder diffractometer instrument: Probing atomic structure in situ

DOE PAGES

Wang, Hsiu -Wen; Fanelli, Victor R.; Reiche, Helmut M.; ...

2014-12-24

This contribution describes a new local structure compatible gas/liquid cell apparatus for probing disordered materials at high pressures and variable temperatures in the Neutron Powder Diffraction instrument at the Lujan Neutron Scattering Center, Los Alamos National Laboratory. The new sample environment offers choices for sample canister thickness and canister material type. Finite element modeling is utilized to establish maximum allowable working pressures of 414 MPa at 15 K and 121 MPa at 600 K. High quality atomic pair distribution function data extraction and modeling have been demonstrated for a calibration standard (Si powder) and for supercritical and subcritical CO 2measurements.more » As a result, the new sample environment was designed to specifically target experimental studies of the local atomic structures involved in geologic CO 2 sequestration, but will be equally applicable to a wide variety of energy applications, including sorption of fluids on nano/meso-porous solids, clathrate hydrate formation, catalysis, carbon capture, and H 2 and natural gas uptake/storage.« less

Impact of anisotropy on the structure and dynamics of ionic liquids: A computational study of 1-butyl-3-methyl-imidazolium trifluoroacetate

NASA Astrophysics Data System (ADS)

Schröder, C.; Rudas, T.; Neumayr, G.; Gansterer, W.; Steinhauser, O.

2007-07-01

The complex ionic network of 1-butyl-3-methyl-imidazolium trifluoroacetate was simulated by means of the molecular dynamics methods over a time period of 100ns. The influence of the anisotropy of the shape and charge distribution of both the cations and the anions on the local (molecular) and global (collective) structure and dynamics is analyzed. The distance-dependent g coefficients of the orientational probability function g(r,Ω) were found to be an excellent way to interpret local structure. Thereby, the combination and interrelation of individual g coefficients elucidate the mutual orientation. Dynamics at the molecular level is characterized by the time correlation function of the center-of-mass corrected molecular dipole moment μcm. Upon uniting the set of molecular dipoles to a single collective rotational dipole moment, MD, dynamics on a global level is studied. Decomposing into subsets of cations and anions respective self terms as well as the prominent cross term can be extracted. This decomposition also enables a detailed peak assignment in dielectric spectra.

Impact of anisotropy on the structure and dynamics of ionic liquids: a computational study of 1-butyl-3-methyl-imidazolium trifluoroacetate.

PubMed

Schröder, C; Rudas, T; Neumayr, G; Gansterer, W; Steinhauser, O

2007-07-28

The complex ionic network of 1-butyl-3-methyl-imidazolium trifluoroacetate was simulated by means of the molecular dynamics methods over a time period of 100 ns. The influence of the anisotropy of the shape and charge distribution of both the cations and the anions on the local (molecular) and global (collective) structure and dynamics is analyzed. The distance-dependent g coefficients of the orientational probability function g(r,Omega) were found to be an excellent way to interpret local structure. Thereby, the combination and interrelation of individual g coefficients elucidate the mutual orientation. Dynamics at the molecular level is characterized by the time correlation function of the center-of-mass corrected molecular dipole moment mucm. Upon uniting the set of molecular dipoles to a single collective rotational dipole moment, MD, dynamics on a global level is studied. Decomposing into subsets of cations and anions respective self terms as well as the prominent cross term can be extracted. This decomposition also enables a detailed peak assignment in dielectric spectra.

Coolant-side heat-transfer rates for a hydrogen-oxygen rocket and a new technique for data correlation

NASA Technical Reports Server (NTRS)

Schacht, R. L.; Quentmeyer, R. J.

1973-01-01

An experimental investigation was conducted to determine the coolant-side, heat transfer coefficients for a liquid cooled, hydrogen-oxygen rocket thrust chamber. Heat transfer rates were determined from measurements of local hot gas wall temperature, local coolant temperature, and local coolant pressure. A correlation incorporating an integration technique for the transport properties needed near the pseudocritical temperature of liquid hydrogen gives a satisfactory prediction of hot gas wall temperatures.

Boundary conditions at the gas sectors of superhydrophobic grooves

NASA Astrophysics Data System (ADS)

Dubov, Alexander L.; Nizkaya, Tatiana V.; Asmolov, Evgeny S.; Vinogradova, Olga I.

2018-01-01

The hydrodynamics of liquid flowing past gas sectors of unidirectional superhydrophobic surfaces is revisited. Attention is focused on the local slip boundary condition at the liquid-gas interface, which is equivalent to the effect of a gas cavity on liquid flow. The system is characterized by a large viscosity contrast between liquid and gas μ /μg≫1 . We interpret earlier results, namely, the dependence of the local slip length on the flow direction, in terms of a tensorial local slip boundary condition and relate the eigenvalues of the local local slip tensor to the texture parameters, such as the width of the groove δ and the local depth of the groove e (y ,α ) . The latter varies in the direction y , orthogonal to the orientation of stripes, and depends on the bevel angle of the groove's edges, π /2 -α , at the point where three phases meet. Our theory demonstrates that when grooves are sufficiently deep their eigenvalues of the local slip length tensor depend only on μ /μg ,δ , and α , but not on the depth. The eigenvalues of the local slip length of shallow grooves depend on μ /μg and e (y ,α ) , although the contribution of the bevel angle is moderate. In order to assess the validity of our theory we propose an approach to solve the two-phase hydrodynamic problem, which significantly facilitates and accelerates calculations compared to conventional numerical schemes. The numerical results show that our simple analytical description obtained for limiting cases of deep and shallow grooves remains valid for various unidirectional textures.

Electronic functions of solid-to-liquid interfaces of organic semiconductor crystals and ionic liquid

NASA Astrophysics Data System (ADS)

Takeya, J.

2008-10-01

The environment of surface electrons at 'solid-to-liquid' interfaces is somewhat extreme, subjected to intense local electric fields or harsh chemical pressures that high-density ionic charge or polarization of mobile molecules create. In this proceedings, we argue functions of electronic carriers generated at the surface of organic semiconductor crystals in response to the local electric fields in the very vicinity of the interface to ionic liquid. The ionic liquids (ILs), or room temperature molten salts, are gaining considerable interest in the recent decade at the prospect of nonvolatile 'green solvents', with the development of chemically stable and nontoxic compounds. Moreover, such materials are also applied to electrolytes for lithium ion batteries and electric double-layer (EDL) capacitors. Our present solid-to-liquid interfaces of rubrene single crystals and ionic liquids work as fast-switching organic field-effect transistors (OFETs) with the highest transconductance, i.e. the most efficient response of the output current to the input voltage, among the OFETs ever built.

Local structural mechanism for frozen-in dynamics in metallic glasses

NASA Astrophysics Data System (ADS)

Liu, X. J.; Wang, S. D.; Wang, H.; Wu, Y.; Liu, C. T.; Li, M.; Lu, Z. P.

2018-04-01

The nature of the glass transition is a fundamental and long-standing intriguing issue in the condensed-matter physics and materials science community. In particular, the structural response by which a liquid is arrested dynamically to form a glass or amorphous solid upon approaching its freezing temperature [the glass transition temperature (Tg)] remains unclear. Various structural scenarios in terms of the percolation theory have been proposed recently to understand such a phenomenon; however, there is still no consensus on what the general percolation entity is and how the entity responds to the sudden slowdown dynamics during the glass transition. In this paper, we demonstrate that one-dimensional local linear ordering (LLO) is a universal structural motif associated with the glass transition for various metallic glasses. The quantitative evolution of LLO with temperature indicates that a percolating LLO network forms to serve as the backbone of the rigid glass solid when the temperature approaches the freezing point, resulting in the frozen-in dynamics accompanying the glass transition. The percolation transition occurs by pinning different LLO networks together, which only needs the introduction of a small number of "joint" atoms between them, and therefore the energy expenditure is very low.

Understanding the breakdown of classic two-phase theory and spray atomization at engine-relevant conditions

NASA Astrophysics Data System (ADS)

Dahms, Rainer N.

2016-04-01

A generalized framework for multi-component liquid injections is presented to understand and predict the breakdown of classic two-phase theory and spray atomization at engine-relevant conditions. The analysis focuses on the thermodynamic structure and the immiscibility state of representative gas-liquid interfaces. The most modern form of Helmholtz energy mixture state equation is utilized which exhibits a unique and physically consistent behavior over the entire two-phase regime of fluid densities. It is combined with generalized models for non-linear gradient theory and for liquid injections to quantify multi-component two-phase interface structures in global thermal equilibrium. Then, the Helmholtz free energy is minimized which determines the interfacial species distribution as a consequence. This minimal free energy state is demonstrated to validate the underlying assumptions of classic two-phase theory and spray atomization. However, under certain engine-relevant conditions for which corroborating experimental data are presented, this requirement for interfacial thermal equilibrium becomes unsustainable. A rigorously derived probability density function quantifies the ability of the interface to develop internal spatial temperature gradients in the presence of significant temperature differences between injected liquid and ambient gas. Then, the interface can no longer be viewed as an isolated system at minimal free energy. Instead, the interfacial dynamics become intimately connected to those of the separated homogeneous phases. Hence, the interface transitions toward a state in local equilibrium whereupon it becomes a dense-fluid mixing layer. A new conceptual view of a transitional liquid injection process emerges from a transition time scale analysis. Close to the nozzle exit, the two-phase interface still remains largely intact and more classic two-phase processes prevail as a consequence. Further downstream, however, the transition to dense-fluid mixing generally occurs before the liquid length is reached. The significance of the presented modeling expressions is established by a direct comparison to a reduced model, which utilizes widely applied approximations but fundamentally fails to capture the physical complexity discussed in this paper.

Propagation-based phase-contrast tomography for high-resolution lung imaging with laboratory sources

NASA Astrophysics Data System (ADS)

Krenkel, Martin; Töpperwien, Mareike; Dullin, Christian; Alves, Frauke; Salditt, Tim

2016-03-01

We have performed high-resolution phase-contrast tomography on whole mice with a laboratory setup. Enabled by a high-brilliance liquid-metal-jet source, we show the feasibility of propagation-based phase contrast in local tomography even in the presence of strongly absorbing surrounding tissue as it is the case in small animal imaging of the lung. We demonstrate the technique by reconstructions of the mouse lung for two different fields of view, covering the whole organ, and a zoom to the local finer structure of terminal airways and alveoli. With a resolution of a few micrometers and the wide availability of the technique, studies of larger biological samples at the cellular level become possible.

Fabrication of hemispherical liquid encapsulated structures based on droplet molding

NASA Astrophysics Data System (ADS)

Ishizuka, Hiroki; Miki, Norihisa

2015-12-01

We have developed and demonstrated a method for forming spherical structures of a thin polydimethylsiloxane (PDMS) membrane encapsulating a liquid. Liquid encapsulation can enhance the performance of microelectromechanical systems (MEMS) devices by providing deformability and improved dielectric properties. Parylene deposition and wafer bonding are applied to encapsulate liquid into a MEMS device. In parylene deposition, a parylene membrane is directly formed onto a liquid droplet. However, since the parylene membrane is stiff, the membrane is fragile. Although wafer bonding can encapsulate liquid between two substrates, the surface of the fabricated structure is normally flat. We propose a new liquid encapsulation method by dispensing liquid droplets. At first, a 20 μl PDMS droplet is dispensed on ethylene glycol. A 70 μl glycerin droplet is dispensed into a PDMS casting solution layer. The droplet forms a layer on heated ethylene glycol. Glycerin and ethylene glycol are chosen for their high boiling points. Additionally, a glycerin droplet is dispensed on the layer and surrounded by a thin PDMS casting solution film. The film is baked for 1 h at 75 °C. As the result, a structure encapsulating a liquid in a flexible PDMS membrane is obtained. We investigate the effects of the volume, surface tension, and guide thickness on the shape of the formed structures. We also evaluated the effect of the structure diameter on miniaturization. The structure can be adapted for various functions by changing the encapsulated liquid. We fabricated a stiffness-tunable structure by dispensing a magnetorheoligical fluid droplet with a stiffness that can be changed by an external magnetic field. We also confirmed that the proposed structure can produce stiffness differences that are distinguishable by humans.

Non-equilibrium magnetic colloidal dispersions at liquid-air interfaces: dynamic patterns, magnetic order and self-assembled swimmers.

PubMed

Snezhko, Alexey

2011-04-20

Colloidal dispersions of interacting particles subjected to an external periodic forcing often develop nontrivial self-assembled patterns and complex collective behavior. A fundamental issue is how collective ordering in such non-equilibrium systems arises from the dynamics of discrete interacting components. In addition, from a practical viewpoint, by working in regimes far from equilibrium new self-organized structures which are generally not available through equilibrium thermodynamics can be created. In this review spontaneous self-assembly phenomena in magnetic colloidal dispersions suspended at liquid-air interfaces and driven out of equilibrium by an alternating magnetic field are presented. Experiments reveal a new type of nontrivially ordered self-assembled structures emerging in such systems in a certain range of excitation parameters. These dynamic structures emerge as a result of the competition between magnetic and hydrodynamic forces and have complex unconventional magnetic ordering. Nontrivial self-induced hydrodynamic fields accompany each out-of-equilibrium pattern. Spontaneous symmetry breaking of the self-induced surface flows leading to a formation of self-propelled microstructures has been discovered. Some features of the self-localized structures can be understood in the framework of the amplitude equation (Ginzburg-Landau type equation) for parametric waves coupled to the conservation law equation describing the evolution of the magnetic particle density and the Navier-Stokes equation for hydrodynamic flows. To understand the fundamental microscopic mechanisms governing self-assembly processes in magnetic colloidal dispersions at liquid-air interfaces a first-principle model for a non-equilibrium self-assembly is presented. The latter model allows us to capture in detail the entire process of out-of-equilibrium self-assembly in the system and reproduces most of the observed phenomenology.

Molecular Design for Preparation of Hexagonal-Ordered Porous Films Based on Side-chain Type Liquid-Crystalline Star Polymer.

PubMed

Naka, Yumiko; Takayama, Hiromu; Koyama, Teruhisa; Le, Khoa V; Sasaki, Takeo

2018-05-02

Fabrication of regularly porous films by the breath-figure method has attracted much attention. The simple, low-cost technique uses the condensation of water droplets to produce these structures, but the phenomenon itself is complex, requiring control over many interacting parameters that change throughout the process. Developing a unified understanding for the molecular design of polymers to prepare ordered porous films is challenging, but required for further advancements. In this article, the effects of the chemical structure of polymers in the breath-figure technique were systematically explored using side-chain type liquid-crystalline (LC) star polymers. The formation of porous films was affected by the structure of the polymers. Although the entire film surface of poly(11-[4-(4-cyanobiphenyl)oxy]undecyl methacrylate) (P11CB) had a hexagonal ordered porous structure over a certain Mn value, regularly arranged holes did not easily form in poly(methyl methacrylate) (PMMA), even though the main chain of PMMA is similar to that of P11CB. Comparing P11CB and poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11B) (P11CB without cyano groups) showed that the local polar groups in hydrophobic polymers promoted the formation of ordered porous films. No holes formed in poly(4-cyanobiphenyl methacrylate) (P0CB) (P11CB without alkyl spacers) films due to its hydrophilicity. The introduction of alkyl chains in P0CB allowed the preparation of honeycomb-structured films by increasing the internal tension. However, alkyl chains in the side chain alone did not result in a porous structure, as in the case of poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11). Aromatic rings are also required to increase the Tg and improve film formability. In the present study, suitable molecular designs of polymers were found, specifically hydrophobic polymers with local polar groups, to form a regularly porous structure. Development of clear guidelines for the molecular design of polymers is the subject of our current research, which will enable the fabrication of porous films using various functional polymers.

Quantitative Proteomic Profiling of Low-Dose Ionizing Radiation Effects in a Human Skin Model

PubMed Central

Hengel, Shawna M.; Aldrich, Joshua T.; Waters, Katrina M.; Pasa-Tolic, Ljiljana; Stenoien, David L.

2014-01-01

To assess responses to low-dose ionizing radiation (LD-IR) exposures potentially encountered during medical diagnostic procedures, nuclear accidents or terrorist acts, a quantitative proteomic approach was used to identify changes in protein abundance in a reconstituted human skin tissue model treated with 0.1 Gy of ionizing radiation. To improve the dynamic range of the assay, subcellular fractionation was employed to remove highly abundant structural proteins and to provide insight into radiation-induced alterations in protein localization. Relative peptide quantification across cellular fractions, control and irradiated samples was performing using 8-plex iTRAQ labeling followed by online two-dimensional nano-scale liquid chromatography and high resolution MS/MS analysis. A total of 107 proteins were detected with statistically significant radiation-induced change in abundance (>1.5 fold) and/or subcellular localization compared to controls. The top biological pathways identified using bioinformatics include organ development, anatomical structure formation and the regulation of actin cytoskeleton. From the proteomic data, a change in proteolytic processing and subcellular localization of the skin barrier protein, filaggrin, was identified, and the results were confirmed by western blotting. This data indicate post-transcriptional regulation of protein abundance, localization and proteolytic processing playing an important role in regulating radiation response in human tissues. PMID:28250387

Local magnetic moments in iron and nickel at ambient and Earth's core conditions.

PubMed

Hausoel, A; Karolak, M; Şaşιoğlu, E; Lichtenstein, A; Held, K; Katanin, A; Toschi, A; Sangiovanni, G

2017-07-12

Some Bravais lattices have a particular geometry that can slow down the motion of Bloch electrons by pre-localization due to the band-structure properties. Another known source of electronic localization in solids is the Coulomb repulsion in partially filled d or f orbitals, which leads to the formation of local magnetic moments. The combination of these two effects is usually considered of little relevance to strongly correlated materials. Here we show that it represents, instead, the underlying physical mechanism in two of the most important ferromagnets: nickel and iron. In nickel, the van Hove singularity has an unexpected impact on the magnetism. As a result, the electron-electron scattering rate is linear in temperature, in violation of the conventional Landau theory of metals. This is true even at Earth's core pressures, at which iron is instead a good Fermi liquid. The importance of nickel in models of geomagnetism may have therefore to be reconsidered.

Local magnetic moments in iron and nickel at ambient and Earth’s core conditions

PubMed Central

Hausoel, A.; Karolak, M.; Şaşιoğlu, E.; Lichtenstein, A.; Held, K.; Katanin, A.; Toschi, A.; Sangiovanni, G.

2017-01-01

Some Bravais lattices have a particular geometry that can slow down the motion of Bloch electrons by pre-localization due to the band-structure properties. Another known source of electronic localization in solids is the Coulomb repulsion in partially filled d or f orbitals, which leads to the formation of local magnetic moments. The combination of these two effects is usually considered of little relevance to strongly correlated materials. Here we show that it represents, instead, the underlying physical mechanism in two of the most important ferromagnets: nickel and iron. In nickel, the van Hove singularity has an unexpected impact on the magnetism. As a result, the electron–electron scattering rate is linear in temperature, in violation of the conventional Landau theory of metals. This is true even at Earth’s core pressures, at which iron is instead a good Fermi liquid. The importance of nickel in models of geomagnetism may have therefore to be reconsidered. PMID:28799538

Effects of local infusions of apomorphine on the extracellular citrulline level in the striatum: Involvement of D1 and D2 dopamine receptors.

PubMed

Savel'ev, S A

2006-11-01

Studies using vital microdialysis and high-performance liquid chromatography showed that local infusion of the NO synthase inhibitor N-nitro-L-arginine (1 mM) into the striatum decreased, while infusion of the dopamine receptor agonist apomorphine (100 microM) increased the level of citrulline (a side product of nitric oxide synthesis) in the intercellular space of this structure in Sprague-Dawley rats. The increase in the citrulline level induced by infusions of apomorphine was completely prevented by local infusions of N-nitro-L-arginine (1 mM) and raclopride (10 microm), a dopamine D2 receptor blocker, but not by infusion of SCH-23390 (50 microm), a dopamine D1 receptor blocker. These data suggest that the increase in extracellular citrulline in the striatum induced by dopaminergic stimulation results from local increases in NO synthase activity and that this effect involves D2, but not D1 dopamine receptors.

Apparatus for measuring the local void fraction in a flowing liquid containing a gas

DOEpatents

Dunn, P.F.

1979-07-17

The local void fraction in liquid containing a gas is measured by placing an impedance-variation probe in the liquid, applying a controlled voltage or current to the probe, and measuring the probe current or voltage. A circuit for applying the one electrical parameter and measuring the other includes a feedback amplifier that minimizes the effect of probe capacitance and a digitizer to provide a clean signal. Time integration of the signal provides a measure of the void fraction, and an oscilloscope display also shows bubble size and distribution.

Apparatus for measuring the local void fraction in a flowing liquid containing a gas

DOEpatents

Dunn, Patrick F.

1981-01-01

The local void fraction in liquid containing a gas is measured by placing an impedance-variation probe in the liquid, applying a controlled voltage or current to the probe, and measuring the probe current or voltage. A circuit for applying the one electrical parameter and measuring the other includes a feedback amplifier that minimizes the effect of probe capacitance and a digitizer to provide a clean signal. Time integration of the signal provides a measure of the void fraction, and an oscilloscope display also shows bubble size and distribution.

Shear viscosity coefficient of liquid lanthanides

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

Patel, H. P., E-mail: patel.harshal2@gmail.com; Thakor, P. B., E-mail: pbthakore@rediffmail.com; Prajapati, A. V., E-mail: anand0prajapati@gmail.com

2015-05-15

Present paper deals with the computation of shear viscosity coefficient (η) of liquid lanthanides. The effective pair potential v(r) is calculated through our newly constructed model potential. The Pair distribution function g(r) is calculated from PYHS reference system. To see the influence of local field correction function, Hartree (H), Tailor (T) and Sarkar et al (S) local field correction function are used. Present results are compared with available experimental as well as theoretical data. Lastly, we found that our newly constructed model potential successfully explains the shear viscosity coefficient (η) of liquid lanthanides.

Shear viscosity coefficient of liquid lanthanides

NASA Astrophysics Data System (ADS)

Patel, H. P.; Sonvane, Y. A.; Thakor, P. B.; Prajapati, A. V.

2015-05-01

Present paper deals with the computation of shear viscosity coefficient (η) of liquid lanthanides. The effective pair potential v(r) is calculated through our newly constructed model potential. The Pair distribution function g(r) is calculated from PYHS reference system. To see the influence of local field correction function, Hartree (H), Tailor (T) and Sarkar et al (S) local field correction function are used. Present results are compared with available experimental as well as theoretical data. Lastly, we found that our newly constructed model potential successfully explains the shear viscosity coefficient (η) of liquid lanthanides.

Relationship between local structure and relaxation in out-of-equilibrium glassy systems

DOE PAGES

Schoenholz, Samuel S.; Cubuk, Ekin D.; Kaxiras, Efthimios; ...

2016-12-27

The dynamical glass transition is typically taken to be the temperature at which a glassy liquid is no longer able to equilibrate on experimental timescales. Consequently, the physical properties of these systems just above or below the dynamical glass transition, such as viscosity, can change by many orders of magnitude over long periods of time following external perturbation. During this progress toward equilibrium, glassy systems exhibit a history dependence that has complicated their study. In previous work, we bridged the gap between structure and dynamics in glassy liquids above their dynamical glass transition temperatures by introducing a scalar field calledmore » “softness,” a quantity obtained using machine-learning methods. Softness is designed to capture the hidden patterns in relative particle positions that correlate strongly with dynamical rearrangements of particle positions. Here we show that the out-of-equilibrium behavior of a model glass-forming system can be understood in terms of softness. We first demonstrate that the evolution of behavior following a temperature quench is a primarily structural phenomenon: The structure changes considerably, but the relationship between structure and dynamics remains invariant. We then show that the relaxation time can be robustly computed from structure as quantified by softness, with the same relation holding both in equilibrium and as the system ages. Together, these results show that the history dependence of the relaxation time in glasses requires knowledge only of the softness in addition to the usual state variables.« less

Relationship between local structure and relaxation in out-of-equilibrium glassy systems.

PubMed

Schoenholz, Samuel S; Cubuk, Ekin D; Kaxiras, Efthimios; Liu, Andrea J

2017-01-10

The dynamical glass transition is typically taken to be the temperature at which a glassy liquid is no longer able to equilibrate on experimental timescales. Consequently, the physical properties of these systems just above or below the dynamical glass transition, such as viscosity, can change by many orders of magnitude over long periods of time following external perturbation. During this progress toward equilibrium, glassy systems exhibit a history dependence that has complicated their study. In previous work, we bridged the gap between structure and dynamics in glassy liquids above their dynamical glass transition temperatures by introducing a scalar field called "softness," a quantity obtained using machine-learning methods. Softness is designed to capture the hidden patterns in relative particle positions that correlate strongly with dynamical rearrangements of particle positions. Here we show that the out-of-equilibrium behavior of a model glass-forming system can be understood in terms of softness. To do this we first demonstrate that the evolution of behavior following a temperature quench is a primarily structural phenomenon: The structure changes considerably, but the relationship between structure and dynamics remains invariant. We then show that the relaxation time can be robustly computed from structure as quantified by softness, with the same relation holding both in equilibrium and as the system ages. Together, these results show that the history dependence of the relaxation time in glasses requires knowledge only of the softness in addition to the usual state variables.

Nanoparticles in ionic liquids: interactions and organization.

PubMed

He, Zhiqi; Alexandridis, Paschalis

2015-07-28

Ionic liquids (ILs), defined as low-melting organic salts, are a novel class of compounds with unique properties and a combinatorially great chemical diversity. Ionic liquids are utilized as synthesis and dispersion media for nanoparticles as well as for surface functionalization. Ionic liquid and nanoparticle hybrid systems are governed by a combined effect of several intermolecular interactions between their constituents. For each interaction, including van der Waals, electrostatic, structural, solvophobic, steric, and hydrogen bonding, the characterization and quantitative calculation methods together with factors affecting these interactions are reviewed here. Various self-organized structures based on nanoparticles in ionic liquids are generated as a result of a balance of these intermolecular interactions. These structures, including colloidal glasses and gels, lyotropic liquid crystals, nanoparticle-stabilized ionic liquid-containing emulsions, ionic liquid surface-functionalized nanoparticles, and nanoscale ionic materials, possess properties of both ionic liquids and nanoparticles, which render them useful as novel materials especially in electrochemical and catalysis applications. This review of the interactions within nanoparticle dispersions in ionic liquids and of the structure of nanoparticle and ionic liquid hybrids provides guidance on the rational design of novel ionic liquid-based materials, enabling applications in broad areas.

Mechanical Properties and Morphologies of Carboxyl-Terminated Butadiene Acrylonitrile Liquid Rubber/Epoxy Blends Compatibilized by Pre-Crosslinking.

PubMed

Xu, Shiai; Song, Xiaoxue; Cai, Yangben

2016-07-29

In order to enhance the compatibilization and interfacial adhesion between epoxy and liquid carboxyl-terminated butadiene acrylonitrile (CTBN) rubber, an initiator was introduced into the mixture and heated to initiate the cross-linking reaction of CTBN. After the addition of curing agents, the CTBN/epoxy blends with a localized interpenetrating network structure were prepared. The mechanical properties and morphologies of pre-crosslinked and non-crosslinked CTBN/epoxy blends were investigated. The results show that the tensile strength, elongation at break and impact strength of pre-crosslinked CTBN/epoxy blends are significantly higher than those of non-crosslinked CTBN/epoxy blends, which is primarily due to the enhanced interfacial strength caused by the chemical bond between the two phases and the localized interpenetrating network structure. Both pre-crosslinked and non-crosslinked CTBN/epoxy blends show a bimodal distribution of micron- and nano-sized rubber particles. However, pre-crosslinked CTBN/epoxy blends have smaller micron-sized rubber particles and larger nano-sized rubber particles than non-crosslinked CTBN/epoxy blends. The dynamic mechanical analysis shows that the storage modulus of pre-crosslinked CTBN/epoxy blends is higher than that of non-crosslinked CTBN/epoxy blends. The glass transition temperature of the CTBN phase in pre-crosslinked CTBN/epoxy blends increases slightly compared with the CTBN/epoxy system. The pre-crosslinking of rubber is a promising method for compatibilization and controlling the morphology of rubber-modified epoxy materials.

Mechanical Properties and Morphologies of Carboxyl-Terminated Butadiene Acrylonitrile Liquid Rubber/Epoxy Blends Compatibilized by Pre-Crosslinking

PubMed Central

Xu, Shiai; Song, Xiaoxue; Cai, Yangben

2016-01-01

In order to enhance the compatibilization and interfacial adhesion between epoxy and liquid carboxyl-terminated butadiene acrylonitrile (CTBN) rubber, an initiator was introduced into the mixture and heated to initiate the cross-linking reaction of CTBN. After the addition of curing agents, the CTBN/epoxy blends with a localized interpenetrating network structure were prepared. The mechanical properties and morphologies of pre-crosslinked and non-crosslinked CTBN/epoxy blends were investigated. The results show that the tensile strength, elongation at break and impact strength of pre-crosslinked CTBN/epoxy blends are significantly higher than those of non-crosslinked CTBN/epoxy blends, which is primarily due to the enhanced interfacial strength caused by the chemical bond between the two phases and the localized interpenetrating network structure. Both pre-crosslinked and non-crosslinked CTBN/epoxy blends show a bimodal distribution of micron- and nano-sized rubber particles. However, pre-crosslinked CTBN/epoxy blends have smaller micron-sized rubber particles and larger nano-sized rubber particles than non-crosslinked CTBN/epoxy blends. The dynamic mechanical analysis shows that the storage modulus of pre-crosslinked CTBN/epoxy blends is higher than that of non-crosslinked CTBN/epoxy blends. The glass transition temperature of the CTBN phase in pre-crosslinked CTBN/epoxy blends increases slightly compared with the CTBN/epoxy system. The pre-crosslinking of rubber is a promising method for compatibilization and controlling the morphology of rubber-modified epoxy materials. PMID:28773762

Local Moment Instability of Os in Honeycomb Li 2.15Os 0.85O 3

DOE PAGES

Wallace, M. K.; LaBarre, P. G.; Li, Jun; ...

2018-04-26

Compounds with honeycomb structures occupied by strong spin orbit coupled (SOC) moments are considered to be candidate Kitaev quantum spin liquids. Here we present the first example of Os on a honeycomb structure, Li 2.15(3)Os 0.85(3)O3 (C2/c, a = 5.09 Å, b = 8.81 Å, c = 9.83 Å, β = 99.3°). Neutron diffraction shows large site disorder in the honeycomb layer and X-ray absorption spectroscopy indicates a valence state of Os (4.7 ± 0.2), consistent with the nominal concentration. We observe a transport band gap of Δ = 243 ± 23 meV, a large van Vleck susceptibility, and anmore » effective moment of 0.85 μ B, much lower than expected from 70% Os(+5). No evidence of long range order is found above 0.10 K but a spin glass-like peak in ac-susceptibility is observed at 0.5 K. The specific heat displays an impurity spin contribution in addition to a power law ∝T (0.63±0.06). Applied density functional theory (DFT) leads to a reduced moment, suggesting incipient itineracy of the valence electrons, and finding evidence that Li over stoichiometry leads to Os(4+)–Os(5+) mixed valence. Lastly, this local picture is discussed in light of the site disorder and a possible underlying quantum spin liquid state.« less

Local Moment Instability of Os in Honeycomb Li 2.15Os 0.85O 3

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

Wallace, M. K.; LaBarre, P. G.; Li, Jun

Compounds with honeycomb structures occupied by strong spin orbit coupled (SOC) moments are considered to be candidate Kitaev quantum spin liquids. Here we present the first example of Os on a honeycomb structure, Li 2.15(3)Os 0.85(3)O3 (C2/c, a = 5.09 Å, b = 8.81 Å, c = 9.83 Å, β = 99.3°). Neutron diffraction shows large site disorder in the honeycomb layer and X-ray absorption spectroscopy indicates a valence state of Os (4.7 ± 0.2), consistent with the nominal concentration. We observe a transport band gap of Δ = 243 ± 23 meV, a large van Vleck susceptibility, and anmore » effective moment of 0.85 μ B, much lower than expected from 70% Os(+5). No evidence of long range order is found above 0.10 K but a spin glass-like peak in ac-susceptibility is observed at 0.5 K. The specific heat displays an impurity spin contribution in addition to a power law ∝T (0.63±0.06). Applied density functional theory (DFT) leads to a reduced moment, suggesting incipient itineracy of the valence electrons, and finding evidence that Li over stoichiometry leads to Os(4+)–Os(5+) mixed valence. Lastly, this local picture is discussed in light of the site disorder and a possible underlying quantum spin liquid state.« less

Infrared nanoscopy down to liquid helium temperatures

NASA Astrophysics Data System (ADS)

Lang, Denny; Döring, Jonathan; Nörenberg, Tobias; Butykai, Ádám; Kézsmárki, István; Schneider, Harald; Winnerl, Stephan; Helm, Manfred; Kehr, Susanne C.; Eng, Lukas M.

2018-03-01

We introduce a scattering-type scanning near-field infrared microscope (s-SNIM) for the local scale near-field sample analysis and spectroscopy from room temperature down to liquid helium (LHe) temperature. The extension of s-SNIM down to T = 5 K is in particular crucial for low-temperature phase transitions, e.g., for the examination of superconductors, as well as low energy excitations. The low temperature (LT) s-SNIM performance is tested with CO2-IR excitation at T = 7 K using a bare Au reference and a structured Si/SiO2-sample. Furthermore, we quantify the impact of local laser heating under the s-SNIM tip apex by monitoring the light-induced ferroelectric-to-paraelectric phase transition of the skyrmion-hosting multiferroic material GaV4S8 at Tc = 42 K. We apply LT s-SNIM to study the spectral response of GaV4S8 and its lateral domain structure in the ferroelectric phase by the mid-IR to THz free-electron laser-light source FELBE at the Helmholtz-Zentrum Dresden-Rossendorf, Germany. Notably, our s-SNIM is based on a non-contact atomic force microscope (AFM) and thus can be complemented in situ by various other AFM techniques, such as topography profiling, piezo-response force microscopy (PFM), and/or Kelvin-probe force microscopy (KPFM). The combination of these methods supports the comprehensive study of the mutual interplay in the topographic, electronic, and optical properties of surfaces from room temperature down to 5 K.

Charge separation in photoredox reactions. Technical progress report, May 1, 1981-May 1, 1984. [N,N,N',N'-tetramethylbenzidine

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

Kevan, L.

1984-05-01

The structural aspects controlling charge separation in molecular photoionization reactions in organized molecular assemblies involving micelles and vesicles are being studied by optical and electron magnetic resonance techniques including the time domain technique of electron spin echo modulation (ESEM). Photoionization of N,N,N',N'-tetramethylbenzidine (TMB) to give the cation radical has been carried out in both liquid and frozen micellar and vesicular solutions. Cation-water interactions have been detected by ESEM analysis and indicate that the cation is localized asymmetrically within these organized molecular assemblies. x-Doxylstearic acid spin probes have been used to determine that the neutral TMB molecule before photoionization is alsomore » localized asymmetrically within such organized molecular assemblies. Electron spin echo detection of laser photogenerated TMB cation in liquid micellar solutions gives a direct measurement of the phase memory magnetic relaxation time which gives additional structural information. The photoionization efficiency has been related to cation-water interactions measured by ESEM. The photoionization efficiency is also dependent on surface charge and is about twofold greater in cationic micelles and vesicles compared to anionic micelles and vesicles. TMB is in a less polar environment in vesicles compared to micelles consistent with ESEM results. The preferential adsorption of metal species at micellar surfaces has been detected by ESEM. Modifications in the micelle surface have been effected by added salts and varying counterions which have been related to cation-water interactions and to the TMB photoionization efficiency. Corresponding changes in the surface and internal micellar structure have been investigated by x-doxylstearic acid spin probes and specifically deuterated surfactants. The decay kinetics of TMB cations in micelles have been interpreted in terms of a time dependent rate constant.« less

The NetLander mission: a geophysical network on the surface of Mars

NASA Astrophysics Data System (ADS)

Ferri, F.; Counil, J. L.; Marsal, O.; Rocard, F.; Bonneville, R.; NetLander Team

2001-12-01

The NetLander mission aims at deploying on the surface of Mars a network of four identical landers which will perform simultaneous measurements in order to study the internal structure of Mars, its subsurface, surface, atmosphere and ionosphere. Seismic measurements will evidence the main transitions (lithosphere-mantle-core) as well as mantle discontinuities and crustal structure. The geodetic measurements will allow to determine the state of the core, liquid or not, and to retrieve the density of the core and mantle. The magnetic experiment will retrieve the conductivity profile down to several hundred of kilometers depth, gathering information on temperature gradient and phase transitions. The search for ground water, liquid or solid, will be performed locally by three experiments: seismometers, magnetometers and a ground penetrating radar. Local geology and surface mineralogy will be investigated through a multispectral stereo panoramic camera. A dedicated package will study the thermal properties of the soil at the landing sites. The NetLander will investigate the atmospheric vertical structure at the entry sites, complementing the existing three profiles. The network's ability to measure spatial and seasonal variations of pressure and the near-surface relative humidity will provide an unprecedented opportunity to characterize the H2O cycle. The meteorological package will also provide data relevant to the initiation and evolution of dust processes. Ionospheric investigations, coming along mainly with radio science, radar and electromagnetic sounding, will allow studying ionization processes and monitoring both the large-scale and small-scale plasma variations. The NetLander is a CNES led European mission to be launched in 2007. The nine instruments forming the payload will be provided by space agencies and research laboratories from more than ten European countries and USA.

Multiorbital kinetic effects on charge ordering of frustrated electrons on the triangular lattice

NASA Astrophysics Data System (ADS)

Février, C.; Fratini, S.; Ralko, A.

2015-06-01

The role of the multiorbital effects on the emergence of frustrated electronic orders on the triangular lattice at half filling is investigated through an extended spinless fermion Hubbard model. By using two complementary approaches, unrestricted Hartree-Fock and exact diagonalizations, we unravel a very rich phase diagram controlled by the strength of both local and off-site Coulomb interactions and by the interorbital hopping anisotropy ratio t'/t . Three robust unconventional electronic phases, a pinball liquid, an inverse pinball liquid, and a large-unit-cell √{12 }×√{12 } droplet phase, are found to be generic in the triangular geometry, being controlled by the band structure parameters. The latter are also stabilized in the isotropic limit of our microscopic model, which recovers the standard SU(2) spinful extended single-band Hubbard model.

Fabrication and electrical characterization of silicon nanowires based resistors

NASA Astrophysics Data System (ADS)

Ni, L.; Demami, F.; Rogel, R.; Salaün, A. C.; Pichon, L.

2009-11-01

Silicon nanowires (SiNWs) are synthesized via the Vapor-Liquid-Solid (VLS) mechanism using gold (Au) as metal catalyst and silane (SiH4) as precursor gas. Au nanoparticles are employed as liquid droplets catalysis during the SiNWs growth performed in a hot wall LPCVD reactor at 480°C and 40 Pa. SiNWs local synthesis at micron scale is demonstrated using classical optical photolithography process. SiNWs grow with high density anchored at the dedicated catalyst islands. This resulting network is used to interconnect two heavily doped polysilicon interdigitated electrodes leading to the formation of electrical resistors in a coplanar structure. Current-voltage (I-V) characteristics highlight a symmetric shape. The temperature dependence of the electrical resistance is activated, with activation energy of 0.47 eV at temperatures greater than 300K.

Effect of water on structure and dynamics of [BMIM][PF6] ionic liquid: An all-atom molecular dynamics simulation investigation.

PubMed

Sharma, Anirban; Ghorai, Pradip Kr

2016-03-21

Composition dependent structural and dynamical properties of aqueous hydrophobic 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) ionic liquid (IL) have been investigated by using all-atom molecular dynamics simulation. We observe that addition of water does not increase significant number of dissociated ions in the solution over the pure state. As a consequence, self-diffusion coefficient of the cation and anion is comparable to each other at all water concentration similar to that is observed for the pure state. Voronoi polyhedra analysis exhibits strong dependence on the local environment of IL concentration. Void and neck distributions in Voronoi tessellation are approximately Gaussian for pure IL but upon subsequent addition of water, we observe deviation from the Gaussian behaviour with an asymmetric broadening with long tail of exponential decay at large void radius, particularly at higher water concentrations. The increase in void space and neck size at higher water concentration facilitates ionic motion, thus, decreasing dynamical heterogeneity and IL reorientation time and increases self-diffusion coefficient significantly.

Effect of water on structure and dynamics of [BMIM][PF{sub 6}] ionic liquid: An all-atom molecular dynamics simulation investigation

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

Sharma, Anirban; Ghorai, Pradip Kr., E-mail: pradip@iiserkol.ac.in

2016-03-21

Composition dependent structural and dynamical properties of aqueous hydrophobic 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF{sub 6}]) ionic liquid (IL) have been investigated by using all-atom molecular dynamics simulation. We observe that addition of water does not increase significant number of dissociated ions in the solution over the pure state. As a consequence, self-diffusion coefficient of the cation and anion is comparable to each other at all water concentration similar to that is observed for the pure state. Voronoi polyhedra analysis exhibits strong dependence on the local environment of IL concentration. Void and neck distributions in Voronoi tessellation are approximately Gaussian for pure ILmore » but upon subsequent addition of water, we observe deviation from the Gaussian behaviour with an asymmetric broadening with long tail of exponential decay at large void radius, particularly at higher water concentrations. The increase in void space and neck size at higher water concentration facilitates ionic motion, thus, decreasing dynamical heterogeneity and IL reorientation time and increases self-diffusion coefficient significantly.« less

Hierarchical lattice models of hydrogen-bond networks in water

NASA Astrophysics Data System (ADS)

Dandekar, Rahul; Hassanali, Ali A.

2018-06-01

We develop a graph-based model of the hydrogen-bond network in water, with a view toward quantitatively modeling the molecular-level correlational structure of the network. The networks formed are studied by the constructing the model on two infinite-dimensional lattices. Our models are built bottom up, based on microscopic information coming from atomistic simulations, and we show that the predictions of the model are consistent with known results from ab initio simulations of liquid water. We show that simple entropic models can predict the correlations and clustering of local-coordination defects around tetrahedral waters observed in the atomistic simulations. We also find that orientational correlations between bonds are longer ranged than density correlations, determine the directional correlations within closed loops, and show that the patterns of water wires within these structures are also consistent with previous atomistic simulations. Our models show the existence of density and compressibility anomalies, as seen in the real liquid, and the phase diagram of these models is consistent with the singularity-free scenario previously proposed by Sastry and coworkers [Phys. Rev. E 53, 6144 (1996), 10.1103/PhysRevE.53.6144].

Liquid crystalline ordering and charge transport in semiconducting materials.

PubMed

Pisula, Wojciech; Zorn, Matthias; Chang, Ji Young; Müllen, Klaus; Zentel, Rudolf

2009-07-16

Organic semiconducting materials offer the advantage of solution processability into flexible films. In most cases, their drawback is based on their low charge carrier mobility, which is directly related to the packing of the molecules both on local (amorphous versus crystalline) and on macroscopic (grain boundaries) length scales. Liquid crystalline ordering offers the possibility of circumventing this problem. An advanced concept comprises: i) the application of materials with different liquid crystalline phases, ii) the orientation of a low viscosity high temperature phase, and, iii) the transfer of the macroscopic orientation during cooling to a highly ordered (at best, crystalline-like) phase at room temperature. At the same time, the desired orientation for the application (OLED or field-effect transistor) can be obtained. This review presents the use of molecules with discotic, calamitic and sanidic phases and discusses the sensitivity of the phases with regard to defects depending on the dimensionality of the ordered structure (columns: 1D, smectic layers and sanidic phases: 2D). It presents ways to systematically improve charge carrier mobility by proper variation of the electronic and steric (packing) structure of the constituting molecules and to reach charge carrier mobilities that are close to and comparable to amorphous silicon, with values of 0.1 to 0.7 cm(2)  · V(-1)  · s(-1) . In this context, the significance of cross-linking to stabilize the orientation and liquid crystalline behavior of inorganic/organic hybrids is also discussed. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Continuous melting through a hexatic phase in confined bilayer water

NASA Astrophysics Data System (ADS)

Zubeltzu, Jon; Corsetti, Fabiano; Fernández-Serra, M. V.; Artacho, Emilio

2016-06-01

Liquid water is not only of obvious importance but also extremely intriguing, displaying many anomalies that still challenge our understanding of such an a priori simple system. The same is true when looking at nanoconfined water: The liquid between constituents in a cell is confined to such dimensions, and there is already evidence that such water can behave very differently from its bulk counterpart. A striking finding has been reported from computer simulations for two-dimensionally confined water: The liquid displays continuous or discontinuous melting depending on its density. In order to understand this behavior, we have analyzed the melting exhibited by a bilayer of nanoconfined water by means of molecular dynamics simulations. At high density we observe the continuous melting to be related to the phase change of the oxygens only, with the hydrogens remaining liquidlike throughout. Moreover, we find an intermediate hexatic phase for the oxygens between the liquid and a triangular solid ice phase, following the Kosterlitz-Thouless-Halperin-Nelson-Young theory for two-dimensional melting. The liquid itself tends to maintain the local structure of the triangular ice, with its two layers being strongly correlated yet with very slow exchange of matter. The decoupling in the behavior of the oxygens and hydrogens gives rise to a regime in which the complexity of water seems to disappear, resulting in what resembles a simple monoatomic liquid. This intrinsic tendency of our simulated water may be useful for understanding novel behaviors in other confined and interfacial water systems.

Surface modification of active material structures in battery electrodes

DOEpatents

Erickson, Michael; Tikhonov, Konstantin

2016-02-02

Provided herein are methods of processing electrode active material structures for use in electrochemical cells or, more specifically, methods of forming surface layers on these structures. The structures are combined with a liquid to form a mixture. The mixture includes a surface reagent that chemically reacts and forms a surface layer covalently bound to the structures. The surface reagent may be a part of the initial liquid or added to the mixture after the liquid is combined with the structures. In some embodiments, the mixture may be processed to form a powder containing the structures with the surface layer thereon. Alternatively, the mixture may be deposited onto a current collecting substrate and dried to form an electrode layer. Furthermore, the liquid may be an electrolyte containing the surface reagent and a salt. The liquid soaks the previously arranged electrodes in order to contact the structures with the surface reagent.

Complex dynamics induced by strong confinement - From tracer diffusion in strongly heterogeneous media to glassy relaxation of dense fluids in narrow slits

NASA Astrophysics Data System (ADS)

Mandal, Suvendu; Spanner-Denzer, Markus; Leitmann, Sebastian; Franosch, Thomas

2017-08-01

We provide an overview of recent advances of the complex dynamics of particles in strong confinements. The first paradigm is the Lorentz model where tracers explore a quenched disordered host structure. Such systems naturally occur as limiting cases of binary glass-forming systems if the dynamics of one component is much faster than the other. For a certain critical density of the host structure the tracers undergo a localization transition which constitutes a critical phenomenon. A series of predictions in the vicinity of the transition have been elaborated and tested versus computer simulations. Analytical progress is achieved for small obstacle densities. The second paradigm is a dense strongly interacting liquid confined to a narrow slab. Then the glass transition depends nonmonotonically on the separation of the plates due to an interplay of local packing and layering. Very small slab widths allow to address certain features of the statics and dynamics analytically.

Cooling rate dependence and local structure in aluminum monatomic metallic glass

NASA Astrophysics Data System (ADS)

Kbirou, M.; Trady, S.; Hasnaoui, A.; Mazroui, M.

2017-10-01

The local atomic structure in aluminium monatomic metallic glass is studied using molecular dynamics simulations combined with the embedded atom method (EAM). We have used a variety of analytical methods to characterise the atomic configurations of our system: the Pair Distribution Function (PDF), the Common Neighbour Analysis (CNA) and the Voronoi Tessellation Analysis. CNA was used to investigate the order change from liquid to amorphous phases, recognising that the amount of icosahedral clusters increases with the decrease of temperature. The Voronoi analysis revealed that the icosahedral-like polyhedral are the predominant ones. It has been observed that the PDF function shows a splitting in the second peak, which cannot be attributed to the only ideal icosahedral polyhedron 〈0, 0, 12, 0〉, but also to the formation of other Voronoi polyhedra 〈0, 1, 10, 2〉 . Further, the PDFs were then integrated giving the cumulative coordination number in order to compute the fractal dimension (df).

Microstructure and phase behavior in colloids and liquid crystals

NASA Astrophysics Data System (ADS)

Lohr, Matthew Alan

This thesis describes our investigation of microstructure and phase behavior in colloids and liquid crystals. The first set of experiments explores the phase behavior of helical packings of thermoresponsive microspheres inside glass capillaries as a function of volume fraction. Stable helical packings are observed with long-range orientational order. Some of these packings evolve abruptly to disordered states as the volume fraction is reduced. We quantify these transitions using correlation functions and susceptibilities of an orientational order parameter. The emergence of coexisting metastable packings, as well as coexisting ordered and disordered states, is also observed. These findings support the notion of phase-transition-like behavior in quasi-one-dimensional systems. The second set of experiments investigates cross-over behavior from glasses with attractive interactions to sparse gel-like states. In particular, the vibrational modes of quasi-two-dimensional disordered colloidal packings of hard colloidal spheres with short-range attractions are measured as a function of packing fraction. A crossover from glassy to sparse gel-like states is indicated by an excess of low-frequency phonon modes. This change in vibrational mode distribution appears to arise from highly localized vibrations that tend to involve individual and/or small clusters of particles with few local bonds. These mode behaviors and corresponding structural insights may serve as a useful signature for glass-gel transitions in wider classes of attractive packings. A third set of experiments explores the director structures of aqueous lyotropic chromonic liquid crystal (LCLC) films created on square lattice cylindrical-micropost substrates. The structures are manipulated by modulating of the concentration-dependent elastic properties of LCLC s via drying. Nematic LCLC films exhibit preferred bistable alignment along the diagonals of the micropost lattice. Columnar LCLC films form two distinct director and defect configurations: a diagonally aligned director pattern with local squares of defects, and an off-diagonal configuration with zig-zag defects. The formation of these patterns appears to be tied to the relative free energy costs of splay and bend deformations in the precursor nematic films. The observed nematic and columnar configurations are understood numerically using a Landau-de Gennes free energy model. This work provides first examples of quasi-2D micropatterning of LC films in the columnar phase and the first micropatterning of lyotropic LC films in general, as well as demonstrating alignment and configuration switching of typically difficult-to-align LCLC films via bulk elastic properties.

Electrocapillarity and zero-frequency differential capacitance at the interface between mercury and ionic liquids measured using the pendant drop method.

PubMed

Nishi, Naoya; Hashimoto, Atsunori; Minami, Eiji; Sakka, Tetsuo

2015-02-21

The structure of ionic liquids (ILs) at the electrochemical IL|Hg interface has been studied using the pendant drop method. From the electrocapillarity (potential dependence of interfacial tension) differential capacitance (Cd) at zero frequency (in other words, static differential capacitance or differential capacitance in equilibrium) has been evaluated. The potential dependence of zero-frequency Cd at the IL|Hg interface exhibits one or two local maxima near the potential of zero charge (Epzc), depending on the cation of the ILs. For 1-ethyl-3-methylimidazolium tetrafluoroborate, an IL with the cation having a short alkyl chain, the Cdvs. potential curve has one local maximum whereas another IL, 1-octyl-3-methylimidazolium tetrafluoroborate, with the cation having a long alkyl chain, shows two maxima. These behaviors of zero-frequency Cd agree with prediction by recent theoretical and simulation studies for the electrical double layer in ILs. At negative and positive potentials far from Epzc, the zero-frequency Cd increases for both the ILs studied. The increase in zero-frequency Cd is attributable to the densification of ionic layers in the electrical double layer.

Influence of elliptical structure on impinging-jet-array heat transfer performances

NASA Astrophysics Data System (ADS)

Arjocu, Simona C.; Liburdy, James A.

1997-11-01

A three-by-three square array of submerged, elliptic, impinging jets in water was used to study the heat transfer distribution in the cooling process of a constant heat flux surface. Tow jet aspect ratios were used, 2 and 3, both with the same hydraulic diameter. The array was tested at Reynolds numbers from 300 to 1500 and impinging distances of 1 to 5 hydraulic diameters. Thermochromic liquid crystals wee used to map the local heat transfer coefficient using a transient method, while the jet temperature was kept constant. The liquid crystal images were recorded through an optical fiber coupled with a CCD camera and a frame grabber and analyzed based on an RGB-temperature calibration technique. The results are reported relative to the unit cell that is used to delimitate the central jet. The heat transfer variation is shown to depend on the impingement distance and Reynolds number. The elliptic jets exhibit axis switching, jet column instability and jet swaying. All of these mechanisms affect the enhancement of the heat transfer rate and its distribution. The results are compared in terms of average and local heat transfer coefficients, for both major and minor planes for the two jet aspect ratios.

Microscopic structural change in a liquid Fe-C alloy of ~5 GPa

DOE PAGES

Shibazaki, Yuki; Kono, Yoshio; Fei, Yingwei

2015-07-04

The structure of a liquid Fe-3.5 wt% C alloy is examined for up to 7.2 GPa via multiangle energy-dispersive X-ray diffraction using a Paris-Edinburgh type large-volume press. X-ray diffraction data show clear changes in the pressure-dependent peak positions of structure factor and reduced pair distribution function at 5GPa. These results suggest that the liquid Fe-3.5wt%C alloys change structurally at approximately 5GPa. This finding serves as a microscopic explanation for the alloy’s previously observed density change at the same pressure. The pressure dependencies of the nearest and second neighbor distances of the liquid Fe-3.5 wt% C alloy are similar to thosemore » of liquid Fe which exhibits a structural change near the bcc-fcc-liquid triple point (5.2GPa and 1991 K). Here, similarities between Fe-3.5wt% C and Fe suggest that a density change also occurs in liquid Fe and that this structural change extends to other Fe-light element alloys.« less

A comparative study of Sm networks in Al-10 at.%Sm glass and associated crystalline phases

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

Lv, Xiaobao; Ye, Zhuo; Sun, Yang

Here, the Al–Sm system is selected as a model system to study the transition process from liquid and amorphous to crystalline states. In recent work, we have shown that, in addition to long-range translational periodicity, crystal structures display well-defined short-range local atomic packing motifs that transcends liquid, amorphous and crystalline states. In this paper, we investigate the longer range spatial packing of these short-range motifs by studying the interconnections of Sm–Sm networks in different amorphous and crystalline samples obtained from molecular dynamics simulations. In our analysis, we concentrate on Sm–Sm distances in the range ~5.0–7.2 Å, corresponding to Sm atomsmore » in the second and third shells of Sm-centred clusters. We discover a number of empirical rules characterising the evolution of Sm networks from the liquid and amorphous states to associated metastable crystalline phases experimentally observed in the initial stages of devitrification of different amorphous samples. As direct simulation of glass formation is difficult because of the vast difference between experimental quench rates and what is achievable on the computer, we hope these rules will be helpful in building a better picture of structural evolution during glass formation as well as a more detailed description of phase selection and growth during devitrification.« less

A comparative study of Sm networks in Al-10 at.%Sm glass and associated crystalline phases

DOE PAGES

Lv, Xiaobao; Ye, Zhuo; Sun, Yang; ...

2018-04-03

Here, the Al–Sm system is selected as a model system to study the transition process from liquid and amorphous to crystalline states. In recent work, we have shown that, in addition to long-range translational periodicity, crystal structures display well-defined short-range local atomic packing motifs that transcends liquid, amorphous and crystalline states. In this paper, we investigate the longer range spatial packing of these short-range motifs by studying the interconnections of Sm–Sm networks in different amorphous and crystalline samples obtained from molecular dynamics simulations. In our analysis, we concentrate on Sm–Sm distances in the range ~5.0–7.2 Å, corresponding to Sm atomsmore » in the second and third shells of Sm-centred clusters. We discover a number of empirical rules characterising the evolution of Sm networks from the liquid and amorphous states to associated metastable crystalline phases experimentally observed in the initial stages of devitrification of different amorphous samples. As direct simulation of glass formation is difficult because of the vast difference between experimental quench rates and what is achievable on the computer, we hope these rules will be helpful in building a better picture of structural evolution during glass formation as well as a more detailed description of phase selection and growth during devitrification.« less

Li-Doped Ionic Liquid Electrolytes: From Bulk Phase to Interfacial Behavior

NASA Technical Reports Server (NTRS)

Haskins, Justin B.; Lawson, John W.

2016-01-01

Ionic liquids have been proposed as candidate electrolytes for high-energy density, rechargeable batteries. We present an extensive computational analysis supported by experimental comparisons of the bulk and interfacial properties of a representative set of these electrolytes as a function of Li-salt doping. We begin by investigating the bulk electrolyte using quantum chemistry and ab initio molecular dynamics to elucidate the solvation structure of Li(+). MD simulations using the polarizable force field of Borodin and coworkers were then performed, from which we obtain an array of thermodynamic and transport properties. Excellent agreement is found with experiments for diffusion, ionic conductivity, and viscosity. Combining MD simulations with electronic structure computations, we computed the electrochemical window of the electrolytes across a range of Li(+)-doping levels and comment on the role of the liquid environment. Finally, we performed a suite of simulations of these Li-doped electrolytes at ideal electrified interfaces to evaluate the differential capacitance and the equilibrium Li(+) distribution in the double layer. The magnitude of differential capacitance is in good agreement with our experiments and exhibits the characteristic camel-shaped profile. In addition, the simulations reveal Li(+) to be highly localized to the second molecular layer of the double layer, which is supported by additional computations that find this layer to be a free energy minimum with respect to Li(+) translation.

Iridates and RuCl3 - from Heisenberg antiferromagnets to potential Kitaev spin-liquids

NASA Astrophysics Data System (ADS)

van den Brink, Jeroen

The observed richness of topological states on the single-electron level prompts the question what kind of topological phases can develop in more strongly correlated, many-body electron systems. Correlation effects, in particular intra- and inter-orbital electron-electron interactions, are very substantial in 3 d transition-metal compounds such as the copper oxides, but the spin-orbit coupling (SOC) is weak. In 5 d transition-metal compounds such as iridates, the interesting situation arises that the SOC and Coulomb interactions meet on the same energy scale. The electronic structure of iridates thus depends on a strong competition between the electronic hopping amplitudes, local energy-level splittings, electron-electron interaction strengths, and the SOC of the Ir 5d electrons. The interplay of these ingredients offers the potential to stabilise relatively well-understood states such as a 2D Heisenberg-like antiferromagnet in Sr2IrO4, but in principle also far more exotic ones, such a topological Kitaev quantum spin liquid, in (hyper)honeycomb iridates. I will discuss the microscopic electronic structures of these iridates, their proximity to idealized Heisenberg and Kitaev models and our contributions to establishing the physical factors that appear to have preempted the realization of quantum spin liquid phases so far and include a discussion on the 4d transition metal chloride RuCl3. Supported by SFB 1143 of the Deutsche Forschungsgemeinschaft.

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

PubMed

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

2005-01-22

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

Topological defects in a living nematic ensnare swimming bacteria [Linking bacterial motility and liquid crystallinity in a model of living nematic

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

Genkin, Mikhail Mikhailovich; Sokolov, Andrey; Lavrentovich, Oleg D.

Active matter exemplified by suspensions of motile bacteria or synthetic self-propelled particles exhibits a remarkable propensity to self-organization and collective motion. The local input of energy and simple particle interactions often lead to complex emergent behavior manifested by the formation of macroscopic vortices and coherent structures with long-range order. A realization of an active system has been conceived by combining swimming bacteria and a lyotropic liquid crystal. Here, by coupling the well-established and validated model of nematic liquid crystals with the bacterial dynamics, we develop a computational model describing intricate properties of such a living nematic. In faithful agreement withmore » the experiment, the model reproduces the onset of periodic undulation of the director and consequent proliferation of topological defects with the increase in bacterial concentration. It yields a testable prediction on the accumulation of bacteria in the cores of +1/2 topological defects and depletion of bacteria in the cores of -1/2 defects. Our dedicated experiment on motile bacteria suspended in a freestanding liquid crystalline film fully confirms this prediction. Lastly, our findings suggest novel approaches for trapping and transport of bacteria and synthetic swimmers in anisotropic liquids and extend a scope of tools to control and manipulate microscopic objects in active matter.« less

Topological defects in a living nematic ensnare swimming bacteria [Linking bacterial motility and liquid crystallinity in a model of living nematic

DOE PAGES

Genkin, Mikhail Mikhailovich; Sokolov, Andrey; Lavrentovich, Oleg D.; ...

2017-03-08

Active matter exemplified by suspensions of motile bacteria or synthetic self-propelled particles exhibits a remarkable propensity to self-organization and collective motion. The local input of energy and simple particle interactions often lead to complex emergent behavior manifested by the formation of macroscopic vortices and coherent structures with long-range order. A realization of an active system has been conceived by combining swimming bacteria and a lyotropic liquid crystal. Here, by coupling the well-established and validated model of nematic liquid crystals with the bacterial dynamics, we develop a computational model describing intricate properties of such a living nematic. In faithful agreement withmore » the experiment, the model reproduces the onset of periodic undulation of the director and consequent proliferation of topological defects with the increase in bacterial concentration. It yields a testable prediction on the accumulation of bacteria in the cores of +1/2 topological defects and depletion of bacteria in the cores of -1/2 defects. Our dedicated experiment on motile bacteria suspended in a freestanding liquid crystalline film fully confirms this prediction. Lastly, our findings suggest novel approaches for trapping and transport of bacteria and synthetic swimmers in anisotropic liquids and extend a scope of tools to control and manipulate microscopic objects in active matter.« less

Structure analysis of turbulent liquid phase by POD and LSE techniques

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

Munir, S., E-mail: shahzad-munir@comsats.edu.pk; Muthuvalu, M. S.; Siddiqui, M. I.

2014-10-24

In this paper, vortical structures and turbulence characteristics of liquid phase in both single liquid phase and two-phase slug flow in pipes were studied. Two dimensional velocity vector fields of liquid phase were obtained by Particle image velocimetry (PIV). Two cases were considered one single phase liquid flow at 80 l/m and second slug flow by introducing gas at 60 l/m while keeping liquid flow rate same. Proper orthogonal decomposition (POD) and Linear stochastic estimation techniques were used for the extraction of coherent structures and analysis of turbulence in liquid phase for both cases. POD has successfully revealed large energymore » containing structures. The time dependent POD spatial mode coefficients oscillate with high frequency for high mode numbers. The energy distribution of spatial modes was also achieved. LSE has pointed out the coherent structured for both cases and the reconstructed velocity fields are in well agreement with the instantaneous velocity fields.« less

Atomic and electronic structures of an extremely fragile liquid.

PubMed

Kohara, Shinji; Akola, Jaakko; Patrikeev, Leonid; Ropo, Matti; Ohara, Koji; Itou, Masayoshi; Fujiwara, Akihiko; Yahiro, Jumpei; Okada, Junpei T; Ishikawa, Takehiko; Mizuno, Akitoshi; Masuno, Atsunobu; Watanabe, Yasuhiro; Usuki, Takeshi

2014-12-18

The structure of high-temperature liquids is an important topic for understanding the fragility of liquids. Here we report the structure of a high-temperature non-glass-forming oxide liquid, ZrO2, at an atomistic and electronic level. The Bhatia-Thornton number-number structure factor of ZrO2 does not show a first sharp diffraction peak. The atomic structure comprises ZrO5, ZrO6 and ZrO7 polyhedra with a significant contribution of edge sharing of oxygen in addition to corner sharing. The variety of large oxygen coordination and polyhedral connections with short Zr-O bond lifetimes, induced by the relatively large ionic radius of zirconium, disturbs the evolution of intermediate-range ordering, which leads to a reduced electronic band gap and increased delocalization in the ionic Zr-O bonding. The details of the chemical bonding explain the extremely low viscosity of the liquid and the absence of a first sharp diffraction peak, and indicate that liquid ZrO2 is an extremely fragile liquid.

Atomic and electronic structures of an extremely fragile liquid

PubMed Central

Kohara, Shinji; Akola, Jaakko; Patrikeev, Leonid; Ropo, Matti; Ohara, Koji; Itou, Masayoshi; Fujiwara, Akihiko; Yahiro, Jumpei; Okada, Junpei T.; Ishikawa, Takehiko; Mizuno, Akitoshi; Masuno, Atsunobu; Watanabe, Yasuhiro; Usuki, Takeshi

2014-01-01

The structure of high-temperature liquids is an important topic for understanding the fragility of liquids. Here we report the structure of a high-temperature non-glass-forming oxide liquid, ZrO2, at an atomistic and electronic level. The Bhatia–Thornton number–number structure factor of ZrO2 does not show a first sharp diffraction peak. The atomic structure comprises ZrO5, ZrO6 and ZrO7 polyhedra with a significant contribution of edge sharing of oxygen in addition to corner sharing. The variety of large oxygen coordination and polyhedral connections with short Zr–O bond lifetimes, induced by the relatively large ionic radius of zirconium, disturbs the evolution of intermediate-range ordering, which leads to a reduced electronic band gap and increased delocalization in the ionic Zr–O bonding. The details of the chemical bonding explain the extremely low viscosity of the liquid and the absence of a first sharp diffraction peak, and indicate that liquid ZrO2 is an extremely fragile liquid. PMID:25520236

Experimental and computational study on the properties of pure and water mixed 1-ethyl-3-methylimidazolium L-(+)-lactate ionic liquid.

PubMed

Aparicio, Santiago; Alcalde, Rafael; Atilhan, Mert

2010-05-06

Ionic liquids have attracted great attention, from both industry and academe, as alternative fluids for a large collection of applications. Although the term green is used frequently to describe ionic liquids in general, it is obvious that it cannot be applied to the huge quantity of possible ionic liquids, and thus, those with adequate environmental and technological profiles must be selected for further and deeper studies, from both basic science and applied approaches. In this work, 1-ethyl-3-methylimidazolium L-(+)-lactate ionic liquid is studied, because of its remarkable properties, through a wide-ranging approach considering thermophysical, spectroscopic, and computational tools, to gain a deeper insight into its complex liquid structure, both pure and mixed with water, thus implying the main factors that would control the technological applications that could be designed using this fluid. The reported results shows a strongly structured pure ionic liquid, in which hydrogen bonding, because of the hydroxyl group of the lactate anion, develops a remarkable role, together with Coulombic forces to determine the fluid's behavior. Upon mixing with water, the ionic liquid retains its structure up to very high dilution levels, with the effect of the ionic liquid on the water structure being very large, even for very low ionic liquid mole fractions. Thus, in water solution, the studied ionic liquid evolves from noninteracting ions solvated by water molecules toward large interacting structures with increasing ionic liquid content.

Universality classes of order parameters composed of many-body bound states

DOE PAGES

Tsvelik, A. M.

2016-11-28

This theoretical paper discusses microscopic models giving rise to special types of order in which conduction electrons are bound together with localized spins to create composite order parameters. It is shown that composite order is related to the formation of a spin liquid with gapped excitations carrying quantum numbers which are a fraction of those of electron. These spin liquids are special in the sense that their formation necessarily involves spin degrees of freedom of both the conduction and the localized electrons and can be characterized by nonlocal order parameters. A detailed description of such spin liquid states is presentedmore » with a special care given to a demonstration of their robustness against local perturbations preserving the Lie group symmetry and the translational invariance.« less

Origins of phase contrast in the atomic force microscope in liquids

PubMed Central

Melcher, John; Carrasco, Carolina; Xu, Xin; Carrascosa, José L.; Gómez-Herrero, Julio; José de Pablo, Pedro; Raman, Arvind

2009-01-01

We study the physical origins of phase contrast in dynamic atomic force microscopy (dAFM) in liquids where low-stiffness microcantilever probes are often used for nanoscale imaging of soft biological samples with gentle forces. Under these conditions, we show that the phase contrast derives primarily from a unique energy flow channel that opens up in liquids due to the momentary excitation of higher eigenmodes. Contrary to the common assumption, phase-contrast images in liquids using soft microcantilevers are often maps of short-range conservative interactions, such as local elastic response, rather than tip-sample dissipation. The theory is used to demonstrate variations in local elasticity of purple membrane and bacteriophage ϕ29 virions in buffer solutions using the phase-contrast images. PMID:19666560

Origins of phase contrast in the atomic force microscope in liquids.

PubMed

Melcher, John; Carrasco, Carolina; Xu, Xin; Carrascosa, José L; Gómez-Herrero, Julio; José de Pablo, Pedro; Raman, Arvind

2009-08-18

We study the physical origins of phase contrast in dynamic atomic force microscopy (dAFM) in liquids where low-stiffness microcantilever probes are often used for nanoscale imaging of soft biological samples with gentle forces. Under these conditions, we show that the phase contrast derives primarily from a unique energy flow channel that opens up in liquids due to the momentary excitation of higher eigenmodes. Contrary to the common assumption, phase-contrast images in liquids using soft microcantilevers are often maps of short-range conservative interactions, such as local elastic response, rather than tip-sample dissipation. The theory is used to demonstrate variations in local elasticity of purple membrane and bacteriophage 29 virions in buffer solutions using the phase-contrast images.

Dewetting-mediated pattern formation in nanoparticle assemblies

NASA Astrophysics Data System (ADS)

Stannard, Andrew

2011-03-01

The deposition of nanoparticles from solution onto solid substrates is a diverse subfield of current nanoscience research. Complex physical and chemical processes underpin the self-assembly and self-organization of colloidal nanoparticles at two-phase (solid-liquid, liquid-air) interfaces and three-phase (solid-liquid-air) contact lines. This review discusses key recent advances made in the understanding of nonequilibrium dewetting processes of nanoparticle-containing solutions, detailing how such an apparently simple experimental system can give rise to such a strikingly varied palette of two-dimensional self-organized nanoparticle array morphologies. Patterns discussed include worm-like domains, cellular networks, microscale rings, and fractal-like fingering structures. There remain many unresolved issues regarding the role of the solvent dewetting dynamics in assembly processes of this type, with a significant focus on how dewetting can be coerced to produce nanoparticle arrays with desirable characteristics such as long-range order. In addition to these topics, methods developed to control nanofluid dewetting through routes such as confining the geometries of drying solutions, depositing onto pre-patterned heterogeneous substrates, and post-dewetting pattern evolution via local or global manipulation are covered.

Dewetting-mediated pattern formation in nanoparticle assemblies.

PubMed

Stannard, Andrew

2011-03-02

The deposition of nanoparticles from solution onto solid substrates is a diverse subfield of current nanoscience research. Complex physical and chemical processes underpin the self-assembly and self-organization of colloidal nanoparticles at two-phase (solid-liquid, liquid-air) interfaces and three-phase (solid-liquid-air) contact lines. This review discusses key recent advances made in the understanding of nonequilibrium dewetting processes of nanoparticle-containing solutions, detailing how such an apparently simple experimental system can give rise to such a strikingly varied palette of two-dimensional self-organized nanoparticle array morphologies. Patterns discussed include worm-like domains, cellular networks, microscale rings, and fractal-like fingering structures. There remain many unresolved issues regarding the role of the solvent dewetting dynamics in assembly processes of this type, with a significant focus on how dewetting can be coerced to produce nanoparticle arrays with desirable characteristics such as long-range order. In addition to these topics, methods developed to control nanofluid dewetting through routes such as confining the geometries of drying solutions, depositing onto pre-patterned heterogeneous substrates, and post-dewetting pattern evolution via local or global manipulation are covered.

Communication: Stiff and soft nano-environments and the "Octopus Effect" are the crux of ionic liquid structural and dynamical heterogeneity

NASA Astrophysics Data System (ADS)

Daly, Ryan P.; Araque, Juan C.; Margulis, Claudio J.

2017-08-01

In a recent set of articles [J. C. Araque et al., J. Phys. Chem. B 119(23), 7015-7029 (2015) and J. C. Araque et al., J. Chem. Phys. 144, 204504 (2016)], we proposed the idea that for small neutral and charged solutes dissolved in ionic liquids, deviation from simple hydrodynamic predictions in translational and rotational dynamics can be explained in terms of diffusion through nano-environments that are stiff (high electrostriction, charge density, and number density) and others that are soft (charge depleted). The current article takes a purely solvent-centric approach in trying to provide molecular detail and intuitive visual understanding of time-dependent local mobility focusing on the most common case of an ionic liquid with well defined polar and apolar nano-domains. We find that at intermediate time scales, apolar regions are fluid, whereas the charge network is much less mobile. Because apolar domains and cationic heads must diffuse as single species, at long time the difference in mobility also necessarily dissipates.

Vibration mitigation in partially liquid-filled vessel using passive energy absorbers

NASA Astrophysics Data System (ADS)

Farid, M.; Levy, N.; Gendelman, O. V.

2017-10-01

We consider possible solutions for vibration mitigation in reduced-order model (ROM) of partially filled liquid tank under impulsive forcing. Such excitations may lead to strong hydraulic impacts applied to the tank inner walls. Finite stiffness of the tank walls is taken into account. In order to mitigate the dangerous internal stresses in the tank walls, we explore both linear (Tuned Mass Damper) and nonlinear (Nonlinear Energy Sink) passive vibration absorbers; mitigation performance in both cases is examined numerically. The liquid sloshing mass is modeled by equivalent mass-spring-dashpot system, which can both perform small-amplitude linear oscillations and hit the vessel walls. We use parameters of the equivalent mass-spring-dashpot system for a well-explored case of cylindrical tanks. The hydraulic impacts are modeled by high-power potential and dissipation functions. Critical location in the tank structure is determined and expression of the corresponding local mechanical stress is derived. We use finite element approach to assess the natural frequencies for specific system parameters. Numerical evaluation criteria are suggested to determine the energy absorption performance.

Ps laser pulse induced stimulated Raman scattering of ammonium nitrate dissolved in water

NASA Astrophysics Data System (ADS)

Kumar, V. Rakesh; Kiran, P. Prem

2018-04-01

An intense picosecond laser pulse focused into a liquid medium generates a shock wave in the focal region. This shock wave while propagating into the medium varies the pressure and temperature of the liquid locally leading to the appearance of novel phases which are manifested by the appearance of Raman peaks. We present the phase changes of ammonium nitrate (AN) dissolved in water by studying the forward and backward stimulated Raman Scattering (FSRS and BSRS) signals due to propagation of 30 ps laser pulse induced shockwaves. The dominant peak corresponding to the NO3- symmetric stretching mode is observed with a Raman shift of 1045 cm-1 which represents phase IV of AN with an orthogonal crystalline structure. Apart from this peak, the dominant mode of liquid phase of water with a Raman shift of 3400 cm-1 and an ice VII peak at a Raman shift of 3050 cm-1 confirming the pressure of 10 GPa is observed. The effect of the concentration and input energy on the appearance of the phases will be presented.

40 CFR 98.400 - Definition of the source category.

Code of Federal Regulations, 2012 CFR

2012-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Natural Gas and Natural Gas Liquids § 98.400 Definition of the source category. This supplier category consists of natural gas liquids fractionators and local natural gas distribution companies. (a) Natural gas liquids fractionators are installations that...

40 CFR 98.400 - Definition of the source category.

Code of Federal Regulations, 2013 CFR

2013-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Natural Gas and Natural Gas Liquids § 98.400 Definition of the source category. This supplier category consists of natural gas liquids fractionators and local natural gas distribution companies. (a) Natural gas liquids fractionators are installations that...

40 CFR 98.400 - Definition of the source category.

Code of Federal Regulations, 2014 CFR

2014-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Natural Gas and Natural Gas Liquids § 98.400 Definition of the source category. This supplier category consists of natural gas liquids fractionators and local natural gas distribution companies. (a) Natural gas liquids fractionators are installations that...

40 CFR 98.400 - Definition of the source category.

Code of Federal Regulations, 2010 CFR

2010-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Natural Gas and Natural Gas Liquids § 98.400 Definition of the source category. This supplier category consists of natural gas liquids fractionators and local natural gas distribution companies. (a) Natural gas liquids fractionators are installations that...

40 CFR 98.400 - Definition of the source category.

Code of Federal Regulations, 2011 CFR

2011-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Natural Gas and Natural Gas Liquids § 98.400 Definition of the source category. This supplier category consists of natural gas liquids fractionators and local natural gas distribution companies. (a) Natural gas liquids fractionators are installations that...

Red and blue shift of liquid water's excited states: A many body perturbation study

NASA Astrophysics Data System (ADS)

Ziaei, Vafa; Bredow, Thomas

2016-08-01

In the present paper, accurate optical absorption spectrum of liquid H2O is calculated in the energy range of 5-20 eV to probe the nature of water's excited states by means of many body perturbation approach. Main features of recent inelastic X-ray measurements are well reproduced, such as a bound excitonic peak at 7.9 eV with a shoulder at 9.4 eV as well as the absorption maximum at 13.9 eV, followed by a broad shoulder at 18.4 eV. The spectrum is dominated by excitonic effects impacting the structures of the spectrum at low and higher energy regimes mixed by single particle effects at high energies. The exciton distribution of the low-energy states, in particular of S1, is highly anisotropic and localized mostly on one water molecule. The S1 state is essentially a HOCO-LUCO (highest occupied crystal orbital - lowest unoccupied crystal orbital) transition and of intra-molecular type, showing a localized valence character. Once the excitation energy is increased, a significant change in the character of the electronically excited states occurs, characterized through emergence of multiple quasi-particle peaks at 7.9 eV in the quasi-particle (QP) transition profile and in the occurring delocalized exciton density distribution, spread over many more water molecules. The exciton delocalization following a change of the character of excited states at around 7.9 eV causes the blue shift of the first absorption band with respect to water monomer S1. However, due to reduction of the electronic band gap from gas to liquid phase, following enhanced screening upon condensation, the localized S1 state of liquid water is red-shifted with respect to S1 state of water monomer. For higher excitations, near vertical ionization energy (11 eV), quasi-free electrons emerge, in agreement with the conduction band electron picture. Furthermore, the occurring red and blue shift of the excited states are independent of the coupling of resonant and anti-resonant contributions to the spectrum.

Red and blue shift of liquid water’s excited states: A many body perturbation study

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

Ziaei, Vafa, E-mail: ziaei@thch.uni-bonn.de; Bredow, Thomas, E-mail: bredow@thch.uni-bonn.de

In the present paper, accurate optical absorption spectrum of liquid H{sub 2}O is calculated in the energy range of 5–20 eV to probe the nature of water’s excited states by means of many body perturbation approach. Main features of recent inelastic X-ray measurements are well reproduced, such as a bound excitonic peak at 7.9 eV with a shoulder at 9.4 eV as well as the absorption maximum at 13.9 eV, followed by a broad shoulder at 18.4 eV. The spectrum is dominated by excitonic effects impacting the structures of the spectrum at low and higher energy regimes mixed by singlemore » particle effects at high energies. The exciton distribution of the low-energy states, in particular of S{sub 1}, is highly anisotropic and localized mostly on one water molecule. The S{sub 1} state is essentially a HOCO-LUCO (highest occupied crystal orbital - lowest unoccupied crystal orbital) transition and of intra-molecular type, showing a localized valence character. Once the excitation energy is increased, a significant change in the character of the electronically excited states occurs, characterized through emergence of multiple quasi-particle peaks at 7.9 eV in the quasi-particle (QP) transition profile and in the occurring delocalized exciton density distribution, spread over many more water molecules. The exciton delocalization following a change of the character of excited states at around 7.9 eV causes the blue shift of the first absorption band with respect to water monomer S{sub 1}. However, due to reduction of the electronic band gap from gas to liquid phase, following enhanced screening upon condensation, the localized S{sub 1} state of liquid water is red-shifted with respect to S{sub 1} state of water monomer. For higher excitations, near vertical ionization energy (11 eV), quasi-free electrons emerge, in agreement with the conduction band electron picture. Furthermore, the occurring red and blue shift of the excited states are independent of the coupling of resonant and anti-resonant contributions to the spectrum.« less

Nonlinear vibrational spectroscopy of surfactants at liquid interfaces

NASA Astrophysics Data System (ADS)

Miranda, Paulo Barbeitas

Surfactants are widely used to modify physical and chemical properties of interfaces. They play an important role in many technological problems. Surfactant monolayers are also of great scientific interest because they are two-dimensional systems that may exhibit a very rich phase transition behavior and can also be considered as a model system for biological interfaces. In this Thesis, we use a second-order nonlinear optical technique (Sum-Frequency Generation - SFG) to obtain vibrational spectra of surfactant monolayers at liquid/vapor and solid/liquid interfaces. The technique has several advantages: it is intrinsically surface-specific, can be applied to buried interfaces, has submonolayer sensitivity and is remarkably sensitive to the conformational order of surfactant monolayers. The first part of the Thesis is concerned with surfactant monolayers at the air/water interface (Langmuir films). Surface crystallization of an alcohol Langmuir film and of liquid alkanes are studied and their phase transition behaviors are found to be of different nature, although driven by similar intermolecular interactions. The effect of crystalline order of Langmuir monolayers on the interfacial water structure is also investigated. It is shown that water forms a well-ordered hydrogen-bonded network underneath an alcohol monolayer, in contrast to a fatty acid monolayer which induces a more disordered structure. In the latter case, ionization of the monolayer becomes more significant with increase of the water pH value, leading to an electric-field-induced ordering of interfacial water molecules. We also show that the orientation and conformation of fairly complicated molecules in a Langmuir monolayer can be completely mapped out using a combination of SFG and second harmonic generation (SHG). For a quantitative analysis of molecular orientation at an interface, local-field corrections must be included. The second part is a study of self-assembled surfactant monolayers at the solid/liquid interface. It is shown that the conformation of a monolayer adsorbed onto a solid substrate and immersed in a liquid is highly dependent on the monolayer surface density and on the nature of intermolecular interactions in the liquid. Fully packed monolayers are well ordered in any environment due to strong surfactant-surfactant interactions and limited liquid penetration into the monolayer. In contrast, loosely packed monolayers are very sensitive to the liquid environment. Non-polar liquids cause a mild increase in the surfactant conformational disorder. Polar liquids induce more disorder and hydrogen-bonding liquids produce highly disordered conformations due to the hydrophobic effect. When immersed in alkanes, under certain conditions the surfactant chains may become highly ordered due to their interaction with the liquid molecules (chain-chain interaction). In the case of long-chain alcohols, competition between the hydrophobic effect and chain-chain interaction is observed.

Apparatus and method for electrochemical modification of liquids

DOEpatents

James, Patrick I

2015-04-21

An apparatus for electrochemical modification of liquid streams employing an electrolytic cell which includes an anode compartment defined by an anode structure where oxidation is effected, containing a liquid electrolyte anolyte, and a cathode compartment defined by a cathode structure where reduction is effected containing a liquid electrolyte catholyte. In addition, the electrolytic cell includes at least one additional compartment arranged at least partially between the anode compartment and the cathode compartment and separated from the anode compartment and the cathode compartment by a separator structure arranged to supports ionic conduction of current between the anode structure and the cathode structure.

Flame structure and stabilization in miniature liquid film combustors

NASA Astrophysics Data System (ADS)

Pham, Trinh Kim

Liquid-fueled miniature combustion systems can be promising portable power devices when high specific power and long operation duration are required. A uniquely viable fueling option for small scale combustion is to introduce the liquid fuel as a film on the combustor walls. As one example of such systems, this dissertation characterizes 1-cm-diameter tubular combustors fed by liquid fuel films, and seeks to identify the mechanisms by which flames are stabilized within them. Early experimental work demonstrates that flame behavior is dependent upon steadiness in fuel and air injection and in geometric symmetry and uniformity. Significant discoveries in later work include the impact of direct strain on the flame by the airflow, the fact that no local recirculation zone appears to exist for stabilization as was previously believed, and that the film thickness, uniformity, and location directly affect the flame's characteristics and stability. A gradient in film thickness is required for stable operation, and this requirement may explain why the combustor maintains overall rich conditions. Initial numerical simulations of two-dimensional cold and reacting flows in a simplified model of the combustor yields flame shape and flow field results that do not match experiments in the burning case, therefore suggesting that local turbulence in the fuel injection region provides the necessary degree of mixing. A three-dimensional model of the combustor is needed if reacting flows are to be simulated accurately. It was also found that thermal conduction from the chamber exit to the chamber base plays an important role in fuel vaporization and the stability of the flame. Consequently, flames cannot be sustained in quartz and other transparent but thermally insulating materials for the selected geometry, so observation of the flame's entire structure cannot be accomplished without either the addition of other flameholding elements or the employment of a more thermally conductive chamber material. Such a material is sapphire, and successful operation of a chamber constructed from tubes of sapphire and other metals upon a steel base permitted the identification of stable operational envelopes for materials of various thermal conductivities. The sapphire chamber also allowed for chemiluminescence measurements, and a combination of flame observations, exit temperature measurements, and supporting evidence provided in literature demonstrate conclusively that the flame is stabilized at its ignition point by a triple flame structure created when the fuel rich zone near the wall film fades to a fuel lean region near the center of the chamber.

An unusual slowdown of fast diffusion in a room temperature

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

Chathoth,; Mamontov, Eugene; Fulvio, Pasquale F

2013-01-01

Using quasielastic neutron scattering in the temperature range from 290 to 350 K, we show that the diffusive motions in a room temperature ionic liquid [H2NC(dma)2][BETI] become faster for a fraction of cations when the liquid is confined in a mesoporous carbon. This applies to both the localized and long-range translational diffusive motions of the highly mobile cations, although the former exhibit an unusual trend of slowing-down as the temperature is increased, until the localized diffusivity is reduced to the bulk ionic liquid value at a temperature of 350 K.

Vitrification and gelation in sticky spheres

NASA Astrophysics Data System (ADS)

Royall, C. Patrick; Williams, Stephen R.; Tanaka, Hajime

2018-01-01

Glasses and gels are the two dynamically arrested, disordered states of matter. Despite their importance, their similarities and differences remain elusive, especially at high density, where until now it has been impossible to distinguish them. We identify dynamical and structural signatures which distinguish the gel and glass transitions in a colloidal model system of hard and "sticky" spheres. It has been suggested that "spinodal" gelation is initiated by gas-liquid viscoelastic phase separation to a bicontinuous network and the resulting densification leads to vitrification of the colloid-rich phase, but whether this phase has sufficient density for arrest is unclear [M. A. Miller and D. Frenkel, Phys. Rev. Lett. 90, 135702 (2003) and P. J. Lu et al., Nature 435, 499-504 (2008)]. Moreover alternative mechanisms for arrest involving percolation have been proposed [A. P. R. Eberle et al., Phys. Rev. Lett. 106, 105704 (2011)]. Here we resolve these outstanding questions, beginning by determining the phase diagram. This, along with demonstrating that percolation plays no role in controlling the dynamics of our system, enables us to confirm spinodal decomposition as the mechanism for gelation. We are then able to show that gels can be formed even at much higher densities than previously supposed, at least to a volume fraction of ϕ = 0.59. Far from being networks, these gels apparently resemble glasses but are still clearly distinguished by the "discontinuous" nature of the transition and the resulting rapid solidification, which leads to the formation of inhomogeneous (with small voids) and far-from-equilibrium local structures. This is markedly different from the glass transition, whose continuous nature leads to the formation of homogeneous and locally equilibrated structures. We further reveal that the onset of the attractive glass transition in the form of a supercooled liquid is in fact interrupted by gelation. Our findings provide a general thermodynamic, dynamic, and structural basis upon which we can distinguish gelation from vitrification.

Nonequilibrium stabilization of an RNA/protein droplet emulsion by nuclear actin

NASA Astrophysics Data System (ADS)

Brangwynne, Clifford

2013-03-01

Actin plays a structural role in the cytoplasm. However, actin takes on new functions and structures in the nucleus that are poorly understood. The nuclei of the large oocytes of the frog X. laevisspecifically accumulate actin to reach high concentrations; however, it remains unclear if this actin polymerizes into a network, and what, if any, structural role such an actin network might play. Here, we use microrheological and confocal imaging techniques to probe the local architecture and mechanics of the nucleus. Our data show that actin forms a weak network that spatially organizes the nucleus by kinetically stabilizing embedded liquid-like RNA/protein bodies which are important for cell growth. In actin-disrupted nuclei this RNA/protein droplet emulsion is destabilized leading to homotypic coalescence into single large droplets. Our data provide intriguing new insights into why large cell nuclei require an actin-based structural scaffold.

Multiscale polar theory of microtubule and motor-protein assemblies

DOE PAGES

Gao, Tong; Blackwell, Robert; Glaser, Matthew A.; ...

2015-01-27

Microtubules and motor proteins are building blocks of self-organized subcellular biological structures such as the mitotic spindle and the centrosomal microtubule array. These same ingredients can form new “bioactive” liquid-crystalline fluids that are intrinsically out of equilibrium and which display complex flows and defect dynamics. It is not yet well understood how microscopic activity, which involves polarity-dependent interactions between motor proteins and microtubules, yields such larger-scale dynamical structures. In our multiscale theory, Brownian dynamics simulations of polar microtubule ensembles driven by cross-linking motors allow us to study microscopic organization and stresses. Polarity sorting and cross-link relaxation emerge as two polar-specificmore » sources of active destabilizing stress. On larger length scales, our continuum Doi-Onsager theory captures the hydrodynamic flows generated by polarity-dependent active stresses. Finally, the results connect local polar structure to flow structures and defect dynamics.« less

Physical properties and electronic structure of a new barium titanate suboxide Ba 1+δTi 13-δO₁₂ (δ = 0.11)

DOE PAGES

Rotundu, Costel R.; Jiang, Shan; Deng, Xiaoyu; ...

2015-04-01

The structure, transport, thermodynamic properties, x-ray absorption spectra (XAS), and electronic structure of a new barium titanate suboxide, Ba 1+δTi 13-δO₁₂ (δ = 0.11), are reported. It is a paramagnetic poor metal with hole carriers dominating the transport. Fermi liquid behavior appears at low temperature. The oxidization state of Ti obtained by the XAS is consistent with the metallic Ti²⁺ state. Local density approximation band structure calculations reveal the material is near the Van Hove singularity. The pseudogap behavior in the Ti-d band and the strong hybridization between the Ti-d and O-p orbitals reflect the characteristics of the building blocksmore » of the Ti₁₃ semi-cluster and the TiO₄ quasi-squares, respectively.« less

Local Crystalline Structure in an Amorphous Protein Dense Phase

PubMed Central

Greene, Daniel G.; Modla, Shannon; Wagner, Norman J.; Sandler, Stanley I.; Lenhoff, Abraham M.

2015-01-01

Proteins exhibit a variety of dense phases ranging from gels, aggregates, and precipitates to crystalline phases and dense liquids. Although the structure of the crystalline phase is known in atomistic detail, little attention has been paid to noncrystalline protein dense phases, and in many cases the structures of these phases are assumed to be fully amorphous. In this work, we used small-angle neutron scattering, electron microscopy, and electron tomography to measure the structure of ovalbumin precipitate particles salted out with ammonium sulfate. We found that the ovalbumin phase-separates into core-shell particles with a core radius of ∼2 μm and shell thickness of ∼0.5 μm. Within this shell region, nanostructures comprised of crystallites of ovalbumin self-assemble into a well-defined bicontinuous network with branches ∼12 nm thick. These results demonstrate that the protein gel is comprised in part of nanocrystalline protein. PMID:26488663

Liquid structure and temperature invariance of sound velocity in supercooled Bi melt

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

Emuna, M.; Mayo, M.; Makov, G.

2014-03-07

Structural rearrangement of liquid Bi in the vicinity of the melting point has been proposed due to the unique temperature invariant sound velocity observed above the melting temperature, the low symmetry of Bi in the solid phase and the necessity of overheating to achieve supercooling. The existence of this structural rearrangement is examined by measurements on supercooled Bi. The sound velocity of liquid Bi was measured into the supercooled region to high accuracy and it was found to be invariant over a temperature range of ∼60°, from 35° above the melting point to ∼25° into the supercooled region. The structuralmore » origin of this phenomenon was explored by neutron diffraction structural measurements in the supercooled temperature range. These measurements indicate a continuous modification of the short range order in the melt. The structure of the liquid is analyzed within a quasi-crystalline model and is found to evolve continuously, similar to other known liquid pnictide systems. The results are discussed in the context of two competing hypotheses proposed to explain properties of liquid Bi near the melting: (i) liquid bismuth undergoes a structural rearrangement slightly above melting and (ii) liquid Bi exhibits a broad maximum in the sound velocity located incidentally at the melting temperature.« less

A molecular dynamics simulation study of dynamic process and mesoscopic structure in liquid mixture systems

NASA Astrophysics Data System (ADS)

Yang, Peng

The focus of this dissertation is the Molecular Dynamics (MD) simulation study of two different systems. In thefirst system, we study the dynamic process of graphene exfoliation, particularly graphene dispersion using ionic surfactants (Chapter 2). In the second system, we investigate the mesoscopic structure of binary solute/ionic liquid (IL) mixtures through the comparison between simulations and corresponding experiments (Chapter 3 and 4). In the graphene exfoliation study, we consider two separation mechanisms: changing the interlayer distance and sliding away the relative distance of two single-layer graphene sheets. By calculating the energy barrier as a function of separation (interlayer or sliding-away) distance and performing sodium dodecyl sulfate (SDS) structure analysis around graphene surface in SDS surfactant/water + bilayer graphene mixture systems, we find that the sliding-away mechanism is the dominant, feasible separation process. In this process, the SDS-graphene interaction gradually replaces the graphene-graphene Van der Waals (VdW) interaction, and decreases the energy barrier until almost zero at critical SDS concentration. In solute/IL study, we investigate nonpolar (CS2) and dipolar (CH 3CN) solute/IL mixture systems. MD simulation shows that at low concentrations, IL is nanosegregated into an ionic network and nonpolar domain. It is also found that CS2 molecules tend to be localized into the nonpolar domain, while CH3CN interacts with nonpolar domain as well as with the charged head groups in the ionic network because of its amphiphilicity. At high concentrations, CH3CN molecules eventually disrupt the nanostructural organization. This dissertation is organized in four chapters: (1) introduction to graphene, ionic liquids and the methodology of MD; (2) MD simulation of graphene exfoliation; (3) Nanostructural organization in acetonitrile/IL mixtures; (4) Nanostructural organization in carbon disulfide/IL mixtures; (5) Conclusions. Results of MD simulations of liquid mixture systems car-ried out in this research explain observed experiments and show the details of nanostructural organizations in small solute molecules/IL mixture. Additionally, the research successfully reveals the correct mechanism of graphene exfoliation process in liquid solution. (This will be summarized in Chapter 5.) The research presented in this dissertation enhances our understanding of the microscopic behaviors in complex liquid systems as well as the theoretical method to explore them.

Laminar flow in a microchannel with superhydrophobic walls exhibiting transverse ribs

NASA Astrophysics Data System (ADS)

Davies, J.; Maynes, D.; Webb, B. W.; Woolford, B.

2006-08-01

One approach recently proposed for reducing the frictional resistance to liquid flow in microchannels is the patterning of microribs and cavities on the channel walls. When treated with a hydrophobic coating, the liquid flowing in the microchannel wets only the surfaces of the ribs, and does not penetrate the cavities, provided the pressure is not too high. The net result is a reduction in the surface contact area between channel walls and the flowing liquid. For microribs and cavities that are aligned normal to the channel axis (principal flow direction), these micropatterns form a repeating, periodic structure. This paper presents results of a study exploring the momentum transport in a parallel-plate microchannel with such microengineered walls. The investigation explored the entire laminar flow Reynolds number range and characterized the influence of the vapor cavity depth on the overall flow field. The liquid-vapor interface (meniscus) in the cavity regions is treated as flat in the numerical analysis and two conditions are explored with regard to the cavity region: (1) The liquid flow at the liquid-vapor interface is treated as shear-free (vanishing viscosity in the vapor region), and (2) the liquid flow in the microchannel core and the vapor flow within the cavity are coupled by matching the velocity and shear stress at the interface. Regions of slip and no-slip behavior exist and the velocity field shows distinct variations from classical laminar flow in a parallel-plate channel. The local streamwise velocity profiles, interfacial velocity distributions, and maximum interfacial velocities are presented for a number of scenarios and provide a sound understanding of the local flow physics. The predictions and accompanying measurements reveal that significant reductions in the frictional pressure drop (enhancement in effective fluid slip at the channel walls) can be achieved relative to the classical smooth-channel Stokes flow. Reductions in the friction factor and enhancements in the fluid slip are greater as the cavity-to-rib length ratio is increased (increasing shear-free fraction) and as the channel hydraulic diameter is decreased. The results also show that the slip length and average friction factor-Reynolds number product exhibit a flow Reynolds dependence. Furthermore, the predictions reveal the global impact of the vapor cavity depth on the overall frictional resistance.

A spray flamelet/progress variable approach combined with a transported joint PDF model for turbulent spray flames

NASA Astrophysics Data System (ADS)

Hu, Yong; Olguin, Hernan; Gutheil, Eva

2017-05-01

A spray flamelet/progress variable approach is developed for use in spray combustion with partly pre-vaporised liquid fuel, where a laminar spray flamelet library accounts for evaporation within the laminar flame structures. For this purpose, the standard spray flamelet formulation for pure evaporating liquid fuel and oxidiser is extended by a chemical reaction progress variable in both the turbulent spray flame model and the laminar spray flame structures, in order to account for the effect of pre-vaporised liquid fuel for instance through use of a pilot flame. This new approach is combined with a transported joint probability density function (PDF) method for the simulation of a turbulent piloted ethanol/air spray flame, and the extension requires the formulation of a joint three-variate PDF depending on the gas phase mixture fraction, the chemical reaction progress variable, and gas enthalpy. The molecular mixing is modelled with the extended interaction-by-exchange-with-the-mean (IEM) model, where source terms account for spray evaporation and heat exchange due to evaporation as well as the chemical reaction rate for the chemical reaction progress variable. This is the first formulation using a spray flamelet model considering both evaporation and partly pre-vaporised liquid fuel within the laminar spray flamelets. Results with this new formulation show good agreement with the experimental data provided by A.R. Masri, Sydney, Australia. The analysis of the Lagrangian statistics of the gas temperature and the OH mass fraction indicates that partially premixed combustion prevails near the nozzle exit of the spray, whereas further downstream, the non-premixed flame is promoted towards the inner rich-side of the spray jet since the pilot flame heats up the premixed inner spray zone. In summary, the simulation with the new formulation considering the reaction progress variable shows good performance, greatly improving the standard formulation, and it provides new insight into the local structure of this complex spray flame.

Multiphase inclusions in plagioclase from anorthosites in the Stillwater Complex, Montana: implications for the origin of the anorthosites

USGS Publications Warehouse

Loferski, P.J.; Arculus, R.J.

1993-01-01

Multiphase inclusions, consisting of clinopyroxene+ilmenite+apatite, occur within cumulus plagioclase grains from anorthosites in the Stillwater Complex, Montana, and in other rocks from the Middle Banded series of the intrusion. The textures and constant modal mineralogy of the inclusions indicate that they were incorporated in the plagioclase as liquid droplets that later crystallized rather than as solid aggregates. Their unusual assemblage, including a distinctive manganiferous ilmenite and the presence of baddeleyite (ZrO2), indicates formation from an unusual liquid. A process involving silicater liquid immiscibility is proposed, whereby small globules of a liquid enriched in Mg, Fe, Ca, Ti, P, REE, Zr and Mn exsolved from the main liquid that gave rise to the anorthosites, became trapped in the plagioclase, and later crystallized to form the inclusions. The immiscibility could have occurred locally within compositional boundaries around crystallizing plagioclase grains or it could have occurred pervasively throughout the liquid. It is proposed that the two immiscible liquids were analogous, n terms of their melt structures, to immiscible liquid pairs reported in the literature both in experiments and in natural basalts. For the previously reported pairs, immiscibility is between a highly polymerized liquid, typically granitic in composition, and a depolymerized liquid, typically ferrobasaltic in composition. In the case of the anorthosites, the depolymerized liquid is represented by the inclusions, and the other liquid was a highly polymerized aluminosilicate melt with a high normative plagioclase content from which the bulk of the anorthosites crystallized. Crystallization of the anorthosites from this highly polymerized liquid accounts for various distinctive textural and chemical features of the anorthosites compared to other rocks in the Stillwater Complex. A lack of correlation between P contents and chondrite-normalized rare earth element (REE) ratios of plagioclase separates indicates that the amount of apatite in the inclusions is too low to affect the REE signature of the plagioclase separates. Nevertheless, workers should use caution when attempting REE modelling studies of cumulates having low REE contents, because apatite-bearing inclusions can potentially cause problems. ?? 1993 Springer-Verlag.

Comparison of the Supercooled Spin Liquid States in the Pyrochlore Magnets Dy2Ti2O7 and Ho2Ti2O7

NASA Astrophysics Data System (ADS)

Eyal, Anna; Eyvazov, Azar B.; Dusad, Ritika; Munsie, Timothy J. S.; Luke, Graeme M.; Davis, J. C. Séamus

Despite a well-ordered crystal structure and strong magnetic interactions between the Dy or Ho ions, no long-range magnetic order has been detected in the pyrochlore titanates Ho2Ti2O7 and Dy2Ti2O7. The low temperature state in these materials is governed by spin-ice rules. These constrain the Ising like spins in the materials, yet does not result in a global broken symmetry state. To explore the actual magnetic phases, we simultaneously measure the time- and frequency-dependent magnetization dynamics of Dy2Ti2O7 and Ho2Ti2O7 using toroidal, boundary-free magnetization transport techniques. We demonstrate a distinctive behavior of the magnetic susceptibility of both compounds, that is indistinguishable in form from the permittivity of supercooled dipolar liquids. Moreover, we show that the microscopic magnetic relaxation times for both materials increase along a super-Arrhenius trajectory also characteristic of supercooled glass-forming liquids. Both materials therefore exhibit characteristics of a supercooled spin liquid. Strongly-correlated dynamics of loops of spins is suggested as a possible mechanism which could account for these findings. Potential connections to many-body spin localization will also be discussed.

Topological Defects in a Living Nematic Ensnare Swimming Bacteria

NASA Astrophysics Data System (ADS)

Genkin, Mikhail M.; Sokolov, Andrey; Lavrentovich, Oleg D.; Aranson, Igor S.

2017-01-01

Active matter exemplified by suspensions of motile bacteria or synthetic self-propelled particles exhibits a remarkable propensity to self-organization and collective motion. The local input of energy and simple particle interactions often lead to complex emergent behavior manifested by the formation of macroscopic vortices and coherent structures with long-range order. A realization of an active system has been conceived by combining swimming bacteria and a lyotropic liquid crystal. Here, by coupling the well-established and validated model of nematic liquid crystals with the bacterial dynamics, we develop a computational model describing intricate properties of such a living nematic. In faithful agreement with the experiment, the model reproduces the onset of periodic undulation of the director and consequent proliferation of topological defects with the increase in bacterial concentration. It yields a testable prediction on the accumulation of bacteria in the cores of +1 /2 topological defects and depletion of bacteria in the cores of -1 /2 defects. Our dedicated experiment on motile bacteria suspended in a freestanding liquid crystalline film fully confirms this prediction. Our findings suggest novel approaches for trapping and transport of bacteria and synthetic swimmers in anisotropic liquids and extend a scope of tools to control and manipulate microscopic objects in active matter.

Toward comprehensive studies of liquids at high pressures and high temperatures: Combined structure, elastic wave velocity, and viscosity measurements in the Paris-Edinburgh cell

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

Kono, Yoshio; Park, Changyong; Kenney-Benson, Curtis

2014-08-19

Techniques for measuring liquid structure, elastic wave velocity, and viscosity under high pressure have been integrated using a Paris–Edinburgh cell at Beamline 16-BM-B, HPCAT of the Advanced Photon Source. The Paris–Edinburgh press allows for compressing large volume samples (up to 2 mm in both diameter and length) up to ~7 GPa and 2000 °C. Multi-angle energy dispersive X-ray diffraction provides structure factors of liquid to a large Q of ~19 Å. Ultrasonic techniques have been developed to investigate elastic wave velocity of liquids combined with the X-ray imaging. Falling sphere viscometry, using high-speed X-ray radiography (>1000 frames/s), enables us tomore » investigate a wide range of viscosity, from those of high viscosity silicates or oxides melts to low viscosity (<1 mPa s) liquids and fluids such as liquid metals or salts. The integration of these multiple techniques has promoted comprehensive studies of structure and physical properties of liquids as well as amorphous materials at high pressures and high temperatures, making it possible to investigate correlations between structure and physical properties of liquids in situ.« less

Functional Nanoclay Suspension for Printing-Then-Solidification of Liquid Materials.

PubMed

Jin, Yifei; Compaan, Ashley; Chai, Wenxuan; Huang, Yong

2017-06-14

Additive manufacturing (AM) enables the freeform fabrication of complex structures from various build materials. The objective of this study is to develop a novel Laponite nanoclay-enabled "printing-then-solidification" additive manufacturing approach to extrude complex three-dimensional (3D) structures made of various liquid build materials. Laponite, a member of the smectite mineral family, is investigated to serve as a yield-stress support bath material for the extrusion printing of liquid build materials. Using the printing-then-solidification approach, the printed structure remains liquid and retains its shape with the help of the Laponite support bath. Then the completed liquid structures are solidified in situ by applying suitable cross-linking mechanisms. Finally, the solidified structures are harvested from the Laponite nanoclay support bath for any further processing as needed. Due to its chemical and physical stability, liquid build materials with different solidification/curing/gelation mechanisms can be fabricated in the Laponite bath using the printing-then-solidification approach. The feasibility of the proposed Laponite-enabled printing-then-solidification approach is demonstrated by fabricating several complicated structures made of various liquid build materials, including alginate with ionic cross-linking, gelatin with thermal cross-linking, and SU-8 with photo-cross-linking. During gelatin structure printing, living cells are included and the postfabrication cell viability is above 90%.

Determining Quiescent Colloidal Suspension Viscosities Using the Green-Kubo Relation and Image-Based Stress Measurements

NASA Astrophysics Data System (ADS)

Lin, Neil Y. C.; Bierbaum, Matthew; Cohen, Itai

2017-09-01

By combining confocal microscopy and stress assessment from local structural anisotropy, we directly measure stresses in 3D quiescent colloidal liquids. Our noninvasive and nonperturbative method allows us to measure forces ≲50 fN with a small and tunable probing volume, enabling us to resolve the stress fluctuations arising from particle thermal motions. We use the Green-Kubo relation to relate these measured stress fluctuations to the bulk Brownian viscosity at different volume fractions, comparing against simulations and conventional rheometry measurements. We find that the Green-Kubo analysis gives excellent agreement with these prior results, suggesting that similar methods could be applied to investigations of local flow properties in many poorly understood far-from-equilibrium systems, including suspensions that are glassy, strongly sheared, or highly confined.

Segmented nanowires displaying locally controllable properties

DOEpatents

Sutter, Eli Anguelova; Sutter, Peter Werner

2013-03-05

Vapor-liquid-solid growth of nanowires is tailored to achieve complex one-dimensional material geometries using phase diagrams determined for nanoscale materials. Segmented one-dimensional nanowires having constant composition display locally variable electronic band structures that are determined by the diameter of the nanowires. The unique electrical and optical properties of the segmented nanowires are exploited to form electronic and optoelectronic devices. Using gold-germanium as a model system, in situ transmission electron microscopy establishes, for nanometer-sized Au--Ge alloy drops at the tips of Ge nanowires (NWs), the parts of the phase diagram that determine their temperature-dependent equilibrium composition. The nanoscale phase diagram is then used to determine the exchange of material between the NW and the drop. The phase diagram for the nanoscale drop deviates significantly from that of the bulk alloy.

Correlation of the fragility of metallic liquids with the high temperature structure, volume, and cohesive energy

NASA Astrophysics Data System (ADS)

Gangopadhyay, A. K.; Pueblo, C. E.; Dai, R.; Johnson, M. L.; Ashcraft, R.; Van Hoesen, D.; Sellers, M.; Kelton, K. F.

2017-04-01

The thermal expansion coefficients, structure factors, and viscosities of twenty-five equilibrium and supercooled metallic liquids have been measured using an electrostatic levitation (ESL) facility. The structure factor was measured at the Advanced Photon Source, Argonne, using the ESL. A clear connection between liquid fragility and structural and volumetric changes at high temperatures is established; the observed changes are larger for the more fragile liquids. It is also demonstrated that the fragility of metallic liquids is determined to a large extent by the cohesive energy and is, therefore, predictable. These results are expected to provide useful guidance in the future design of metallic glasses.

A possible structural signature of the onset of cooperativity in metallic liquids

NASA Astrophysics Data System (ADS)

Dai, R.; Ashcraft, R.; Kelton, K. F.

2018-05-01

It is widely, although not universally, believed that there must be a connection between liquid dynamics and the structure. Previous supporting studies, for example, have demonstrated a link between the structural evolution in the liquid and kinetic fragility. Here, new results are presented that strengthen the evidence for a connection. By combining the results from high-energy synchrotron X-ray scattering studies of containerlessly processed supercooled liquids with viscosity measurements, an accelerated rate of structural ordering beyond the nearest neighbors in the liquid is demonstrated to correlate with the temperature at which the viscosity transitions from Arrhenius to super-Arrhenius behavior. This is the first confirmation of predictions from several recent molecular dynamics studies.

Probing spatial locality in ionic liquids with the grand canonical adaptive resolution molecular dynamics technique

NASA Astrophysics Data System (ADS)

Shadrack Jabes, B.; Krekeler, C.; Klein, R.; Delle Site, L.

2018-05-01

We employ the Grand Canonical Adaptive Resolution Simulation (GC-AdResS) molecular dynamics technique to test the spatial locality of the 1-ethyl 3-methyl imidazolium chloride liquid. In GC-AdResS, atomistic details are kept only in an open sub-region of the system while the environment is treated at coarse-grained level; thus, if spatial quantities calculated in such a sub-region agree with the equivalent quantities calculated in a full atomistic simulation, then the atomistic degrees of freedom outside the sub-region play a negligible role. The size of the sub-region fixes the degree of spatial locality of a certain quantity. We show that even for sub-regions whose radius corresponds to the size of a few molecules, spatial properties are reasonably reproduced thus suggesting a higher degree of spatial locality, a hypothesis put forward also by other researchers and that seems to play an important role for the characterization of fundamental properties of a large class of ionic liquids.

Phenomenology and energetics of diffusion across cell phase states.

PubMed

Ashrafuzzaman, Md

2015-11-01

Cell based transport properties have been mathematically addressed. Cell contained cross boundary diffusion of materials has been explained using valid formalisms and related analytical expressions have been developed. Various distinguishable physical structures and their properties raise different general structure specific diffusion mechanisms and controlled transport related parameters. Some of these parameters play phenomenological roles and some cause regulatory effects. The cell based compartments may be divided into three major physical phase states namely liquid, plasma and solid phase states. Transport of ions, nutrients, small molecules like proteins, etc. across inter phase states and intraphase states follows general transport related formalisms. Creation of some localized permanent and/or temporary structures e.g., ion channels, clustering of constituents, etc. and the transitions between such structures appear as regulators of the transport mechanisms. In this article, I have developed mainly a theoretical analysis of the commonly observed cell transport phenomena. I have attempted to develop formalisms on general cell based diffusion followed by a few numerical computations to address the analytical expression phenomenologically. I have then extended the analysis to adopting with the local structure originated energetics. Independent or correlated molecular transport naturally relies on some general parameters that define the nature of local cell environment as well as on some occasionally raised or transiently active stochastic resonance due to localized interactions. Short and long range interaction energies play crucial roles in this regard. Physical classification of cellular compartments has led us developing analytical expressions on both biologically observed diffusion mechanisms and the diffusions's occasional stochasticity causing energetics. These analytical expressions help us address the diffusion phenomena generally considering the physical properties of the biostructures across the diffusion pathways. A specific example case of single molecule transport and localized interaction energetics in a specific cell phase has been utilized to address the diffusion quite clearly. This article helps to address the mechanisms of cell based diffusion and nutrient movements and thus helps develop strategic templates to manipulate the diffusion mechanisms. Application of the theoretical knowledge into designing or discovering drugs or small molecule inhibitors targeting cell based structures may open up new avenues in biomedical sciences.

Technogenic effect of liquidation of coal mines on earth’s entrails: hydrogeochemical aspect

NASA Astrophysics Data System (ADS)

Tarasenko, I. A.; Zinkov, A. V.; Chudaev, O. V.; Vetoshkina, A. V.; Holodilov, I. I.

2017-10-01

The authors of the paper have established the geochemical features of the composition of underground waters and regularities of their formation in the areas of the liquidated coal mines of Russia and Ukraine. It is shown that the mine flood resulted in the formation of technogenic waters which geochemical specificity originates in the feeding field and is transformed in the direction of the filtration flow. It depends on the geological structure of sedimentary basins and the presence in the coal and supra-coal beds of the marine, salt-bearing and freshwater groups of geological formations. The water types are distinguished characterizing the conditions and processes of their formation that may be the regional markers in the hydrochemical and geological constructions. The technogenic waters influenced the safety of the underground waters, sources of water supply of the regions, and surface water channels. The pollutions are of local character in space.

Dynamics and universal scaling law in geometrically-controlled sessile drop evaporation

PubMed Central

Sáenz, P. J.; Wray, A. W.; Che, Z.; Matar, O. K.; Valluri, P.; Kim, J.; Sefiane, K.

2017-01-01

The evaporation of a liquid drop on a solid substrate is a remarkably common phenomenon. Yet, the complexity of the underlying mechanisms has constrained previous studies to spherically symmetric configurations. Here we investigate well-defined, non-spherical evaporating drops of pure liquids and binary mixtures. We deduce a universal scaling law for the evaporation rate valid for any shape and demonstrate that more curved regions lead to preferential localized depositions in particle-laden drops. Furthermore, geometry induces well-defined flow structures within the drop that change according to the driving mechanism. In the case of binary mixtures, geometry dictates the spatial segregation of the more volatile component as it is depleted. Our results suggest that the drop geometry can be exploited to prescribe the particle deposition and evaporative dynamics of pure drops and the mixing characteristics of multicomponent drops, which may be of interest to a wide range of industrial and scientific applications. PMID:28294114

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

Garbuio, Viviana; Pulci, Olivia; Cascella, Michele

The proton disorder in ice has a key role in several properties such as the growth mode, thermodynamical properties, and ferroelectricity. While structural phase transitions from proton disordered to proton ordered ices have been extensively studied, much less is known about their electronic and optical properties. Here, we present ab initio many body perturbation theory-based calculations of the electronic and optical properties of cubic ice at different levels of proton disorder. We compare our results with those from liquid water, that acts as an example of a fully (proton- and oxygen-)disordered system. We find that by increasing the proton disorder,more » a shrinking of the electronic gap occurs in ice, and it is smallest in the liquid water. Simultaneously, the excitonic binding energy decreases, so that the final optical gaps result to be almost independent on the degree of proton disorder. We explain these findings as an interplay between the local dipolar disorder and the electronic correlation.« less